Metal Catalyzed Redox Reactions
|
|
- Logan Butler
- 7 years ago
- Views:
Transcription
1 tal Catalyzed edox eactions athan Jui MacMillan Group eting January 27, 2010
2 tal Catalyzed edox eactions! Many metal-catalyzed reactions involve redox processes Cross-Coupling Chemistry eduction Chemistry M catalyst catalyst H 2 Heck-Type Chemistry xidation Chemstry Ar catalyst Ar DG catalyst [] DG! These reactions and their mechanisms will not be addressed
3 tal Catalyzed edox eactions! Many metal-catalyzed reactions involve redox processes Constraints Applied 1. Catalytic in metal S M n S 2. Single electron transfer processes 3. et redox neutral (no terminal oxidant) 4. o light (purely chemical activation) S M n+1 ATA Cycle M n+1 S 5. Selective generation of organic radicals If electron transfer is accompanied occurs via inner-sphere mechanism Atom Transfer adical Chemistry
4 adical Addition chanism as First Defined! The The 'Peroxide 'Peroxide Effect' Effect' as as observed observed by by Kharasch Kharasch and and co-workers co-workers (1933) (1933) HBr HBr H 3 C 3 room temp room temp Br Br sole product sole product HBr, HBr, room temp room temp H 3 C 3 Br Br minor minor Br Br major major "The "The presence presence of of benzoyl benzoyl peroxide peroxide or or ascaridole ascaridole modified modified profoundly profoundly the the course course of of the the addition addition and and the the product product of of the the reaction reaction was was largely, largely, if if not not all, all, normal normal propyl propyl bromide" bromide" -Morris Kharasch -Morris Kharasch Kharasch, M. S. J. Am. Chem. Soc. 1933, 55, Kharasch, M. S. J. Am. Chem. Soc. 1933, 55, 2531.
5 adical Addition chanism as First Defined adical Addition chanism as First Defined! The 'Peroxide Effect' independantly defined by Kharash et al. as well as Hey and Waters (1937)! The 'Peroxide Effect' independantly defined by Kharash et al. as well as Hey and Waters (1937) HBr, HBr, HBr, room temp room room temp temp H 3 C H 3 C Br Br Br minor minor minor Br Br Br major major major "...it may be suggested that the addition process is one Kharasch, requiring M. S. the J. rg. transient Chem. 1937, 2, 288. "...it may be suggested that the addition process is one requiring the transient production of neutal atoms of hydrogen and broming from hydrogen bromide"! Kharasch production later reported of neutal the radical atoms addition of hydrogen of halomethanes and broming from to olefins hydrogen (1945) bromide" -Hey and Waters -Hey and Waters (Bz) 2, heat Bz H Br C 4 Br Bz H Br Br > 60% yield 3 CBr H Br Br H Br Kharasch, M. S. J. rg. Chem. 1937, 2, 288. Hey, Kharasch, D.; Waters, M. M. S. W. S. et Chem. J. al. rg. Science, ev. Chem. 1937, , 21, 122, 2, Hey, D.; Waters, W. Chem. ev. 1937, 21, 1969.
6 adical Addition chanism as First Defined! The 'Peroxide Effect' independantly defined by Kharash et al. as well as Hey and Waters (1937) HBr, room temp H 3 C Br minor Br major Kharasch, M. S. J. rg. Chem. 1937, 2, 288.! Kharasch later reported the radical addition of halomethanes to olefins (1945) C 4 (Bz) 2, heat > 60% yield 3 C Kharasch, M. S. et al. Science, , 108.
7 The Kharasch Addition eaction of Halomethanes to lefins! Kharasch reported the radical addition of carbon-based radicals to olefins (1945) C 4 Ac! Ac 3 C Ac Ac 2 H 3 C 2 C 2 Initiation H 3 C C 4 CH 3 3 C 3 C 3 C 3 C C 3 C 4 3 C Propagation 3 C 3 C Polymerization = Ar Kharasch, M. S. Science 1945, 122, 108.
8 The Kharasch Addition eaction of Halomethanes to lefins! Kharasch reported the use of several radical electrophiles in his new radical reaction hex hex Br CBr 3 hex Br C 3 hex Br Et (Ac) 2, 40% yield h!, 88% yield (Ac) 2, 78% yield (Ac) 2, 54% yield JACS, 1945, 1626 JACS, 1946, 154 JACS, 1947, 1105 JACS, 1948, 1055 Halogen was used in excess (3- or 4-fold) for optimum yields Higher order products made up mass balances Highly activated bromomethanes were the best substrates Br CBr 3 CBr 4, light C 4, (Ac) 2 C 3 96% quant n
9 The Failed Polymerizations of Minisci! Surprisingly, substantial monoadduct formation was observed with carbon tetrachloride C C 4, autoclave, 160 C C C 3 n C C 3 'significant amount' C CH 3, autoclave, 160 C H C C 3 n C CH 2 new regioisomer! Standard peroxide initiated radical mechanisms occur via hydrogen abstraction C H C 3 3 C C C 3 C C 3 H H C 3 3 C Complete selectivity for opposite regioisomer suggested a new mechanism Minisci, F. Chem. Ind. (Milan), 1956, 122, 371.
10 adical Chain Termination by tal Halide Salts (Jay Kochi)! Also in 1956, Kochi was studying the oxidation of alkyl radicals by metal salts 2 Cu or Fe 2 acetone good yields 0% polymer Cu erwein Arylation!Cu Cu 2 Cu 1. The rate of benzylic radical oxidation by Cu 2 (or Fe 3 ) is much faster than styrene addition 2. xidation occurs through a 'ligand transfer' mechanism (inner-sphere electron transfer) Minisci's reaction could have contained metal halides Kochi, J. J. Am. Chem. Soc. 1956, 78, 4815.
11 Accidental Discovery of Catalytic Atom Transfer adical Chemstry! Minisci's steel autoclave was corroded and had likely leached iron into the reaction and could have been oxidized to Fe 3 by chlorine radicals 2 C 4 Fe (s) 2 3 C Fe 2 C 4 Fe 2 3 C Fe 3! Minisci's group and Vofsi and Asscher first describe catalytic atom transfer radical addition 1 equiv 2 equiv 1 mol% Cu (or Fe 2 ) 2 equiv solvent, 80!120 C 3 C 46-89% yield C C 2 Et C 6 H 13 Minisci, F. et al. Gazzeta 1961, 91, Asscher, M. et al. J. Chem. Soc. 1963, 1887.
12 Proposed chanism of Atom Transfer adical Addition (ATA)! tal catalyst participates in both initiation and termination steps, relative rates dictate selectivity Catalytic edox chanism:! ed. halogen abstraction Cu I ' monoadduct generates radical! xid. halogen abstraction terminates radical k a1 k d1 k a2 k d2 ' ' ' Selective ATA equires: Cu II 2 k add ' k t ' telomer 1. Low radical concentration k t ' k t k p k d1 and k d2 >> k a1 and k a2 n ' 2. Slow product activation (vs sm) k a1 >> k a2 ' ' polymer 3. xidation must be fast vs prop. k d2 >> k p Figure adapted from: Matyjaszewski, K. et al. Chem. Soc. ev. 2008, 1087.
13 So Many Different Catalysts... Y Y Y ML n n (cat.) Y Y Y! The many metals that catalyze CH 3, CHBr 3, C 4, and/or CBr 4 radical addition! The most commonly used catalysts for ATA reactions are Cu I and u II 2 derivatives! Exact nature of free radical intermediates is not known
14 Evaluation of the Proposed adical chanism! Kharasch systems likely proceed via radical intermediates (u, Cu, Fe, Mo, Cr) C 4 hex u 2 (P 3 ) 3 galvinoxyl 3 C hex 0% yield (76%, no spintrap) 80 C, 4 h Matsumoto, H. et al. Tetrahedron Lett. 1973, 14, 5147.! tal catalyst impacts diastereoselectivity of C 4 addition to cyclohexene u 2 (P 3 ) 3 C 4 80 C, 4 h C 3 77% yield 96:4 (trans:cis) C 4 (Bz) 2 80 C, 4 h C 3 low yield 53:47 (trans:cis) Matsumoto, H. et al. Tetrahedron Lett. 1975, 15, 899. Effect not seen with Cu: Asscher, M. et al. J. Chem. Soc. Perkin Trans , Intermediate radical species likely exist as coordinated radical pairs (u system)
15 Attempts at Enantioselective Kharasch Addition! Chiral ligands could potentially induce enantioselectivity 73% yield C 3 u 2 4 (diop) 3 C 4 13% ee 100 C, 6 h! Coordinated metal-radical pair should participate in enantiodetermining chlorination 3 C ul* n 2 C 4 L* = (!)-diop 3 CCH 2 CH u III 3 ATA Cycle 3 C u III 3 H H CH 2 P 2 CH 2 P 2 Kamigata,. et al. Bull. Chem. Soc. Jpn. 1987, 60, Similar result with h-diop system: Murai, S. et al. Angew. Chem. Int. Ed. Eng. 1981, 20, 475.
16 Selected Examples of Atom Transfer adical Addition Chemistry! Area 1. Intramolecular Atom Transfer eactions (ATC) ML 2 n FG FG (cat.)! Area 2. Intermolecular Kharasch Type Haloalkylation eactions FG ML 2 n (cat.) FG
17 Selected Intramolecular ATA: 5-Exo Trig Cyclizations! A variety of cyclization substrates and catalytic systems have been developed over 35+ years u 2 (P 3 ) 3 catalysts: 1973 (agai) Cu catalysts: 1963 (Asscher & Vofsi) 1-10% typical loadings, > 80 C temperatures ~30% typical loading, > 100 C temperatures u 2 (P 3 ) 3 H, 155 C 79% yield Cu C, 110 C 95% yield 2 C u 2 (P 3 ) 3 H, 165 C 77%, 1:1 dr 2 C H H Cu C, 140 C 57% yield H 2 C u 2 (P 3 ) 3 H, 165 C 71%, 2:1 dr 2 C H F F Br H CuBr C, 80 C F F 84% yield H Br Weinreb, S. et al. J. rg. Chem. 1990, 55, ark, A. Chem. Soc. ev. 2002, 31, 1.
18 Intramolecular Atom Transfer adical Cyclization Ligand Effects! 5-Exo trig cyclization of unsaturated!-haloamide substrates yields lactam scaffolds 30 mol% catalyst solvent, temp Ts Ts Catalyst Solvent Temp. Time Yield Cu C 80 C 24 h 97% Cu-bipy (5%) CH C 0.2 h 91% Cu-bipy H CH C 24 h 0% Cu-PMI H CH C 72 h 15% Cu-tren- 6 H CH C 2 h 90% 2 bipy PMI 2 2 tren- 6 ark, A. Tetrahdron Lett. 1999, 40, 4885.
19 adical-polar Crossover chanism: Addition to Enamides! Electrophilic radicals add to acyl enamines, terminate via radical-polar crossover mechanism Br Bn 30 mol% CuBr L CH 2 2, rt, 20 min 82%, 1:1 ratio Bn 2 = L 2 2 CuLBr CuLBr 2!H +!CuLBr 2!CuLBr Bn Bn Bn! While this triethylenetetramine ligand is highly active, the perfect Cu system remains unknown 30 mol% CuBr L 0% yield CH 2 2, rt complex mixture Bn Bn ark, A. Tetrahdron Lett. 1999, 40, 4885.
20 Cascade Cyclization Using Copper edox Catalyst! adical mono- and bicyclization utilizing copper-bipy as catalyst (Dan Yang) Et Cu bipy DCE, 80 C 21 h C 2 Et 79% yield 3:1 dr! Bicyclization under the conditions outlined above give modest yields and diastereocontrol Et 61% C 2 Et Et 33% C 2 Et 2:1 dr 3:2 dr Yang, D. et al. rg. Lett. 2006, 8, 5757.
21 Intramolecular Atom Transfer adical Cyclization! dium ring heterocycle formation via redox reaction affords 8 and 9 membered lactones n 3 30 mol% Cu-bipy 0.1 M DCE 80 C, 18 h n n = 1: 60% yield n = 2: 59% yield Pirrung, F. et al. Synlett. 1993, 50, 739.! Macrocyclization reactions were also accomplished using a tridentate ligand 10 mol% Cu-ligand C M DCE, 80 C 70% yield ark, A. et al. J. Chem. Soc. Perkin Trans. 1, 2000, 671.
22 Selected Examples of Atom Transfer adical Addition Chemistry! Area 1. Intramolecular Atom Transfer adical Addition eactions (ATC) ML 2 n FG FG (cat.) n n= 0-13 n! Successful radical precursors in ATC reactions so far are highly activated 2 2 F I F 2 2 H 2 2
23 Selected Examples of Atom Transfer adical Addition Chemistry! Area 1. Intramolecular Atom Transfer adical Addition eactions (ATC) ML 2 n FG FG (cat.) n n= 0-13 n! Successful Area 2. Intermolecular radical precursors Kharasch in ATC Addition reactions eactions so far of are Polyhaloalkanes highly activated Y 2 Y ' 2 ML 2 n F (cat.) I F ' Y 2 Y 2 H 2 2
24 Perfluoroalkylation of lefins Using ATA! Kamigata's group describe a ruthenium catalyzed radical trifluromethylation protocol F 3 C S 1 equiv 2 equiv 1 mol% u 2 (P 3 ) 2 benzene, 120 C! The reaction works well with highly activated olefins but is sensitive to sterics (1,2-substitution) F 3 C ul* n 2 F 3 CS % yield ATA 87% yield Cycle S 2 46% yield Et u III 3 u III 3 41% yield 66% yield 23% yield Kamigata. J. Chem. Soc. Perkin Trans , 627.
25 Perfluoroalkylation of lefins Using ATA! Kamigata's group describe a ruthenium catalyzed radical trifluromethylation protocol F 3 C S 1 equiv 2 equiv 1 mol% u 2 (P 3 ) 2 benzene, 120 C! The reaction works well with highly activated olefins but is sensitive to sterics (1,2-substitution) 2 79% yield 87% yield 46% yield Et 41% yield 66% yield 23% yield Kamigata. J. Chem. Soc. Perkin Trans , 627.
26 Arene Perfluoroalkylation Using Sulfonyl Chloride eagents! Kamigata's group describe a ruthenium catalyzed radical trifluromethylation protocol F 3 C S 1 equiv 2-5 equiv 1 mol% u 2 (P 3 ) 2 benzene, 120 C! Benzene substrates react but are completely regio-permiscuous 53% yield 2:1:1 (o:m:p) 36% yield 1:1:1 (o:m:p) 41% yield Br 39% yield 1:1:1 (o:m:p) trace C 63% yield Kamigata.. J. Chem. Soc. Perkin Trans , 1339.
27 Arene Perfluoroalkylation Using Sulfonyl Chloride eagents! Kamigata's group describe a ruthenium catalyzed radical trifluromethylation protocol F 3 C S F 3 C S 1 1 equiv equiv 1 1 mol% mol% u u 2 (P 3 ) 2 2 (P 3 ) 2 benzene, benzene, C C CF 3! Five-membered Benzene substrates heterocyclic react but compounds are completely work regio-permiscuous with increased regiocontrol 53% yield 36% yield S S HC S CF 2:1:1 (o:m:p) 1:1:1 (o:m:p) 3 30% 77% 73% 26% 41% yield CF 3 39% yield H Bn Br 1:1:1 (o:m:p) CF 3 C trace 0% 53% 61% 92% Ac C 63% yield Kamigata.. J. Chem. Soc. Perkin Trans , 1339.
28 Trifluoromethylation of Electron-Poor Enolsilane Substrates! uthenium catalyzed sulfonyl chloride decomposition also works on silyl enol ethers TMS F 3 C S ' 1 equiv 2 equiv 1 mol% u 2 (P 3 ) 2 benzene, 120 C ' CF3 CF3 2 55% yield 51% yield 58% yield 0% yield H Bn CF3 t Bu CF3 28% yield 35% yield 43% yield 0% yield Kamigata.. osporus, Sulphur, and Silicon 1997, 155.
29 Atom Transfer adical Addition eactions With Titanium Enolates! Zakarian group published the first highly diastereoselective intermolecular Kharasch addition Ti 4, i-pr 2 Et, CH 2 2 ' BrC 3 (3 equiv) ' 7 mol% u 2 (P 3 ) 3 45 C, 12 h C 3 4 Ti 4 Ti ' ' C 3 BrC 3 u III + Br u II 4 Ti ' 4 Ti ' 4 Ti ' C 3 C 3 C 3 Zakarian, A. et al. J. Am. Chem. Soc. 2010, ASAP.
30 Atom Transfer adical Addition eactions With Titanium Enolates! Zakarian group published the first highly diastereoselective intermolecular Kharasch addition Ti 4, i-pr 2 Et, CH 2 2 ' BrC 3 (3 equiv) ' 7 mol% u 2 (P 3 ) 3 45 C, 12 h C 3 4 Ti Bn 89%, >98:2 dr 4 Ti ' ' C 3 Bn 4 Ti 4 Ti C 4 H 9 ' C 3 C 3 Bn Bn 99%, >98:2 dr 63%, >98:2 dr 87%, >98:2 dr C 3 6 BrC 3 C 3 u III + Br u II ' Bn 4 C C 3 C 3 3 Bn 61%, >98:2 dr Zakarian, A. et al. J. Am. Chem. Soc. 2010, ASAP. Bn 4 Ti C 3 91%, >98:2 dr Ts ' C 3
31 Atom Transfer adical Addition eactions With Titanium Enolates! Zakarian group published the first highly diastereoselective intermolecular Kharasch addition Ti 4, i-pr 2 Et, CH 2 2 ' BrC 3 (3 equiv) ' 7 mol% u 2 (P 3 ) 3 45 C, 12 h C 3 4 Ti Bn Bn ' 64%, >98:2 dr 4 Ti 71%, 1.6:1 dr ' C 3 4 Ti ' Bn 4 Ti Bn C 3 83%, >98:2 dr ' 76%, >98:2 dr Et u III + Br C 3 C 2 Bn u II BrC 3 75%, 1.3:1 dr Zakarian, A. et al. J. Am. Chem. Soc. 2010, ASAP. Bn 4 Ti Bn 71%, >98:2 dr C 3 '
32 Atom Transfer adical Polymerization (ATP) Atom Transfer adical Polymerization (ATP)! In In 1995, Krzysztof Matyjaszewski and Mitsuo Sawamoto picked up up where Minisci left off off (1956)! In They 1995, independantly Krzysztof Matyjaszewski reported a a new and method Mitsuo (ATP Sawamoto or or living picked radical up where polymerization) Minisci left off (1956)! They independantly reported a new method (ATP or living radical polymerization) Sawamoto Kyoto University Sawamoto Kyoto University Matyjaszewski Carnegie Matyjaszewski llon Carnegie llon 'Living adical Polymerization' 'Atom Transfer adical Polymerization' submitted September 6, 6, 1994 'Living adical Polymerization' submitted February 16, 1995 'Atom Transfer adical Polymerization' Macromolecules, 1995, 28, submitted September 6, 1994 J. J. Am. Chem. Soc., 1995, 117, submitted February 16, 1995 cited 1,571 times Macromolecules, 1995, 28, cited 2,374 times J. Am. Chem. Soc., 1995, 117, cited 1,571 times cited 2,374 times
33 Atom Transfer adical Polymerization (ATP)! In 1995, Krzysztof Matyjaszewski and Mitsuo Sawamoto picked up where Minisci left off (1956) Selective ATA equires: Cu I ' monoadduct 1. Low radical concentration ' k d1 and k d2 >> k a1 and k a2 k d1 k a2 2. Slow product activation (vs sm) k a1 k d2 ' ' k a1 >> k a2 3. xidation must be fast vs prop. Cu II 2 ' k t ' teleomer k d2 >> k p k add k t ' k t k p Polymerization Can ccur If: 1. Above requirements are met ' ' n polymer ' 2. Starting Halogen is consumed Figure adapted from: Matyjaszewski, K. et al. Chem. Soc. ev. 2008, 1087.
34 Atom Transfer adical Polymerization (ATP)! In 1995, Krzysztof Matyjaszewski and Mitsuo Sawamoto picked up where Minisci left off (1956) Selective ATA equires: Cu I ' monoadduct 1. Low radical concentration ' k d1 and k d2 >> k a1 and k a2 k d1 k a2 2. Slow product activation (vs sm) k a1 k d2 ' ' k a1 >> k a2 3. xidation must be fast vs prop. Cu II 2 ' k t ' teleomer k d2 >> k p k add k t ' k t k p Polymerization Can ccur If: 1. Above requirements are met ' ' n polymer ' 2. Starting Halogen is consumed Figure adapted from: Matyjaszewski, K. et al. Chem. Soc. ev. 2008, 1087.
35 Atom Transfer adical Polymerization (ATP)! In 1995, Krzysztof Matyjaszewski and Mitsuo Sawamoto picked up where Minisci left off (1956) Selective ATA equires: Cu I ' monoadduct 1. Low radical concentration k d1 and k d2 >> k a1 and k a2 k d1 k a2 2. Slow product activation (vs sm) k a1 k d2 k a1 >> k a2 3. xidation must be fast vs prop. Cu II 2 ' ' k d2 >> k p k add ' kp Polymerization Can ccur If: ' n ' 1. Above requirements are met P M n n P M n n polymer +m 2. Starting Halogen is consumed Figure adapted from: Matyjaszewski, K. et al. Chem. Soc. ev. 2008, 1087.
36 Atom Transfer adical Polymerization (ATP)! Matyjaszewski polymerized styrene using a copper chloride bipy system Atom Transfer adical Polymerization (ATP)! Matyjaszewski polymerized styrene using a copper chloride bipy system 1 mol% Cu 95% consumption! Matyjaszewski polymerized styrene using a copper chloride bipy system 3 mol% bipy n PDI = 1.3! equiv 0.01 equiv 1130 mol% C, Cu 3 h 95% consumption 1 mol% Cu 95% consumption 3 mol% bipy n PDI = 1.3!1.45 Atom Transfer adical 3 mol% bipy Polymerization (ATP) PDI = 1.3!1.45 n 1 equiv 0.01 equiv 130 C, 3 h 1 equiv 0.01 equiv! PDI = polydispersity index, 130 a measure C, 3 h of how consistent chain growth is! Matyjaszewski! PDI equal polymerized to one: all of styrene the chains using in a a copper given chloride sample are bipy of system the same length! Sawamoto PDI = polydispersity system utilized index, some a well-developed measure of how ruthenium consistent phosphine chain growth conditions is! Good PDI values are typically > 1.5! PDI equal to one: all of the 1 mol% chains Cu in a given sample are of the same length M n = number average molecular 95% weight consumption 0.5! Good PDI values are typically 3 mol% u > bipy (P 3 ) 3 n C 2 PDI 90% = consumption 1.3!1.45 C 2 C 4 total weight / number of molecules C 1 equiv 0.01 equiv PDI = M n / mol% M C, w 3 Al(Ar) h 2 PDI = 1.3!1.4 n M n = number average molecular weight 1 equiv 0.01 equiv toluene, 60 C, 4 M h w = weight average molecular weight total weight / number of molecules PDI = M n / M w average weight of average molecule! Upon! PDI complete = polydispersity conversion, index, more a measure monomer of was how added consistent and completely chain growth incorporated is M w = weight average molecular weight! adical! PDI scavengers equal to one: completely all of the chains inhibited a / stopped given average sample reactions weight are of of average the same molecule length Matyjaszewski, K. et al. J. Am. Chem. Soc. 1995, 117, 5614.! Addition! Good of PDI different values monomers are typically allowed > 1.5 for 'Block polymers' (""""####) PDI = M n / M w Matyjaszewski, M n = number K. average et al. J. Am. molecular Chem. weight Soc. 1995, 117, Sawamoto, M. et al. Macromolecules 1995, 28, total weight / number of molecules Matyjaszewski, K. et al. J. Am. Chem. Soc. 1995, 117, M w = weight average molecular weight
37 Atom Transfer adical Polymerization (ATP)! Matyjaszewski polymerized styrene using a copper chloride bipy system 1 mol% Cu 95% consumption 1 equiv 0.01 equiv 3 mol% bipy 130 C, 3 h n PDI = 1.3!1.45! Sawamoto system utilized some well-developed ruthenium phosphine conditions C 2 C 4 1 equiv 0.01 equiv 0.5 mol% u 2 (P 3 ) mol% Al(Ar) 2 toluene, 60 C, 4 h C 2 C 3 n 90% consumption PDI = 1.3!1.4! Upon complete conversion, more monomer was added and completely incorporated! adical scavengers completely inhibited / stopped reactions! Addition of different monomers allowed for 'Block polymers' (""""####) Sawamoto, M. et al. Macromolecules 1995, 28, Matyjaszewski, K. et al. J. Am. Chem. Soc. 1995, 117, 5614.
38 Atom Transfer adical Polymerization (ATP) I M n / Ligand I M n+1 2 / Ligand k act P M n / Ligand P M n+1 2 / Ligand k deact +m m k t k p termination! Different ATP systems possess discrete rate properties based on the following I Initiator (Alkyl Halide) redox potential M n / Ligand Catalyst solubilities, redox potentials m monomer unique ATP k eq Matyjaszewski, K. et al. Chem. ev. 2001, 101, 2921.
39 Atom Transfer adical Polymerization (ATP) I M n / Ligand I M n+1 2 / Ligand k act P M n / Ligand P M n+1 2 / Ligand k deact +m m k t k p termination! Different ATP systems possess discrete rate properties based on the following! Each monomer has a specific k eq (k act /k deact ) and requires specific conditions for ATP! nly copper catalysts have been successful in polymerizing all of the above classes Matyjaszewski, K. et al. Chem. ev. 2001, 101, 2921.
40 Atom Transfer adical Polymerization (ATP) I M n / Ligand I M n+1 2 / Ligand k act P M n / Ligand P M n+1 2 / Ligand k deact +m m k t k p termination! Different ATP systems possess discrete rate properties based on the following! Each monomer has a specific k eq (k act /k deact ) and requires specific conditions for ATP P! nly copper catalysts have been successful in polymerizing all of the above classes Matyjaszewski, K. et al. Chem. ev. 2001, 101, 2921.
41 Atom Transfer adical Polymerization (ATP) I M n / Ligand I M n+1 2 / Ligand k act P M n / Ligand P M n+1 2 / Ligand k deact +m m k t k p termination! Different ATP systems possess discrete rate properties based on the following! Each monomer has a specific k eq (k act /k deact ) and requires specific conditions for ATP P M! nly copper catalysts have been successful in polymerizing all of the above classes Matyjaszewski, K. et al. Chem. ev. 2001, 101, 2921.
42 Atom Transfer adical Polymerization (ATP) I M n / Ligand I M n+1 2 / Ligand k act P M n / Ligand P M n+1 2 / Ligand k deact +m m k t k p termination! Different ATP systems possess discrete rate properties based on the following! Each monomer has a specific k eq (k act /k deact ) and requires specific conditions for ATP P! nly copper catalysts have been successful in polymerizing all of the above classes Matyjaszewski, K. et al. Chem. ev. 2001, 101, 2921.
43 Atom Transfer adical Polymerization (ATP) I M n / Ligand I M n+1 2 / Ligand k act P M n / Ligand P M n+1 2 / Ligand k deact +m m k t k p termination! Different ATP systems possess discrete rate properties based on the following! Each monomer has a specific k eq (k act /k deact ) and requires specific conditions for ATP P! Initiators tend to look like the desired monomer units (similar redox, kinetic properties) Matyjaszewski, K. et al. Chem. ev. 2001, 101, 2921.
44 Atom Transfer adical Polymerization (ATP) I M n / Ligand I M n+1 2 / Ligand k act P M n / Ligand P M n+1 2 / Ligand k deact +m m k t k p termination! Different ATP systems possess discrete rate properties based on the following! Each monomer has a specific k eq (k act /k deact ) and requires specific conditions for ATP P Cu Cu, u 2, i 2 i 2, u 2 Fe 2, Cu Cu! tals typically used to initiate each indicated monomer class (ligands play huge role)
45 Atom Transfer adical Polymerization (ATP) I M n / Ligand I M n+1 2 / Ligand m k act P M n / Ligand P M n+1 2 / Ligand k deact +m k t k p termination! Different ATP systems possess discrete rate properties based on the following! Each monomer has a specific k eq (k act /k deact ) and requires specific conditions for ATP more stable cations P ubrcp*p 3 2 faster ATP catalysts ucp*p 3 Cu(TPA) Fe III (phen) 3 u 2 (P 3 ) 3 Cu(bipy) 2 Cu( 6 -tren) Cu Cu, u 2, i 2 i 2, u 2 Fe 2, Cu Cu +1 V ! Initiators tend to look like the desired monomer units (similar redox, kinetic properties) -1 V (vs SCE)! tals typically used to initiate each indicated Matyjaszewski, monomer class K. et (ligands al. Chem. play ev. huge 2001, role) 101,
46 Atom Transfer adical Polymerization (ATP) I M n / Ligand I M n+1 2 / Ligand m k act P M n / Ligand P M n+1 2 / Ligand k deact +m k t k p termination! Different ATP systems possess discrete rate properties based on the following! Each monomer has a specific k eq (k act /k deact ) and requires specific conditions for ATP more stable cations P ubrcp*p 3 2 faster ATP catalysts ucp*p 3 Cu(TPA) Fe III (phen) 3 u 2 (P 3 ) 3 Cu(bipy) 2 Cu( 6 -tren) Cu Cu, u 2, i 2 i 2, u 2 Fe 2, Cu Cu +1 V ! Initiators tend to look like the desired monomer units (similar redox, kinetic properties) -1 V (vs SCE)! tals typically used to initiate each indicated Matyjaszewski, monomer class K. et (ligands al. Chem. play ev. huge 2001, role) 101,
47 Atom Transfer adical Polymerization (ATP) I M n / Ligand I M n+1 2 / Ligand m k act P M n / Ligand P M n+1 2 / Ligand k deact +m k t k p termination! Different ATP systems possess discrete rate properties based on the following! Each monomer has a specific k eq (k act /k deact ) and requires specific conditions for ATP more stable cations P ubrcp*p 3 2 faster ATP catalysts ucp*p 3 Cu(TPA) Fe III (phen) 3 u 2 (P 3 ) 3 Cu(bipy) 2 Cu( 6 -tren) Cu Cu, u 2, i 2 i 2, u 2 Fe 2, Cu Cu +1 V ! Initiators tend to look like the desired monomer units (similar redox, kinetic properties) -1 V (vs SCE)! tals typically used to initiate each indicated Matyjaszewski, monomer class K. et (ligands al. Chem. play ev. huge 2001, role) 101,
48 Atom Transfer adical Polymerization (ATP) I M n / Ligand I M n+1 2 / Ligand m k act P M n / Ligand P M n+1 2 / Ligand k deact +m k t k p termination! Different ATP systems possess discrete rate properties based on the following! Each monomer has a specific k eq (k act /k deact ) and requires specific conditions for ATP more stable cations P ubrcp*p 3 2 faster ATP catalysts ucp*p 3 Cu(TPA) Fe III (phen) 3 u 2 (P 3 ) 3 Cu(bipy) 2 Cu( 6 -tren) Cu Cu, u 2, i 2 i 2, u 2 Fe 2, Cu Cu +1 V ! Initiators tend to look like the desired monomer units (similar redox, kinetic properties) -1 V (vs SCE)! tals typically used to initiate each indicated Matyjaszewski, monomer class K. et (ligands al. Chem. play ev. huge 2001, role) 101,
49 ew Catalyst Systems Allow for ATA eactions Under Mild Conditions! ewer highly active ruthenium catalysts initiate rapidly at room temperature Et u 3 P 0.1 mol% catalyst Mg powder Et H 2 equiv 1 equiv toluene, rt 24 h, 97% yield 5% u 2 (P 3 ) 3 : 155 C, 16 h: 71% yield Severin, K. Chem. Eur. J. 2007, 6899.
50 ML 2 n FG n (cat.) n= 0-13 Potential Future Atom Transfer adical Chemistry n Potential Future Atom Transfer adical Chemistry! Successful radical precursors in ATC reactions so far are highly activated 2 2 F I F 2 2 H 2 2 Br Br ' Br ' Br ' Br ' Br Br ' Br ' Br ' Br '
Cleavage of Cyclobutanols and Cyclobutanones
Literature Report VII Transition Metal-Catalyzed Enantioselective C-C C Bond Cleavage of Cyclobutanols and Cyclobutanones Huang, W.-X. checker: Yu, C.-B. 2014-04-2904 29 1 Contents 1. Background Information
More informationUnit 2: Quantities in Chemistry
Mass, Moles, & Molar Mass Relative quantities of isotopes in a natural occurring element (%) E.g. Carbon has 2 isotopes C-12 and C-13. Of Carbon s two isotopes, there is 98.9% C-12 and 11.1% C-13. Find
More informationammonium salt (acidic)
Chem 360 Jasperse Ch. 19 otes. Amines 1 eactions of Amines 1. eaction as a proton base (Section 19-5 and 19-6) amine base -X (proton acid) a X ammonium salt (acidic) Mechanism: equired (protonation) everse
More informationAllyl Metals. oxidative addition. transmet. + M(n) η 1 -allyl. n = 0, 1. base. X η 3 -allyl. Nuc. insertion. insertion. M(n+2)X MgX + MX2 MX 2
Allyl tals Virtually all transition metals can form η 3 -allyl complexes, but few are synthetically useful. Pd is most widely studied and has broad utility. Allyl complexes of h, Ir, u and Mo are becoming
More information17.2 REACTIONS INVOLVING ALLYLIC AND BENZYLIC RADICALS
17. REACTINS INVLVING ALLYLIC AND BENZYLIC RADICALS 793 As Eq. 17. shows, the products derived from the reaction of water at the ring carbons are not formed. The reason is that these products are not aromatic
More informationChapter 6 An Overview of Organic Reactions
John E. McMurry www.cengage.com/chemistry/mcmurry Chapter 6 An Overview of Organic Reactions Why this chapter? To understand organic and/or biochemistry, it is necessary to know: -What occurs -Why and
More informationQuantifying Nucleophilicity and Electrophilicity: The Mayr Scales. log k = s(n + E)
Quantifying ucleophilicity and Electrophilicity: The Mayr Scales E k E R R log k = s( + E) Valerie Shurtleff MacMillan Group Meeting July 10, 2013 A Brief History of Polar Reactivity Scales 1920s: G..
More informationWittig Reaction - Phosphorous Ylides
Wittig eaction - osphorous Ylides 3 P CC 3 3 C ylide tereoselectivity increases as the size of increases cis-olefin is derived from non-stabilized ylides Mechanism: Irreversible [22] cycloaddition P 3
More informationElectrophilic Addition Reactions
Electrophilic Addition Reactions Electrophilic addition reactions are an important class of reactions that allow the interconversion of C=C and C C into a range of important functional groups. Conceptually,
More informationStille, Suzuki, and Sonogashira Couplings Cross-Coupling reactions: catalyst R-X + R'-M
Stille, Suzuki, and Sonogashira Couplings Cross-Coupling reactions: catalyst -X '-M -' M-X, ' are usually sp 2 hybridized X= (best), Tf, r, Cl M=Sn,, Zn, Zr, n Catalyst= Pd, sometimes Ni Example: Pd(0)
More informationElectrophilic Aromatic Substitution
Electrophilic Aromatic Substitution Electrophilic substitution is the typical reaction type for aromatic rings. Generalized electrophilic aromatic substitution: E E Electrophile Lewis acid: may be or neutral.
More informationQ.1 Draw out some suitable structures which fit the molecular formula C 6 H 6
Aromatic compounds GE 1 BENZENE Structure Primary analysis revealed benzene had an... empirical formula of and a molecular formula of 6 6 Q.1 Draw out some suitable structures which fit the molecular formula
More informationChapter 5 Classification of Organic Compounds by Solubility
Chapter 5 Classification of Organic Compounds by Solubility Deductions based upon interpretation of simple solubility tests can be extremely useful in organic structure determination. Both solubility and
More informationFormulae, stoichiometry and the mole concept
3 Formulae, stoichiometry and the mole concept Content 3.1 Symbols, Formulae and Chemical equations 3.2 Concept of Relative Mass 3.3 Mole Concept and Stoichiometry Learning Outcomes Candidates should be
More information17.5 ALLYLIC AND BENZYLIC OXIDATION
17.5 ALLYLI AND BENZYLI XIDATIN 803 Nuc d d Nuc d 2 3 2 overlap of 2p orbitals X d no p-orbital overlap X d (a) (b) Figure 17.2 Transition states for N 2 reactions at (a) an allylic carbon and (b) a nonallylic
More informationKurs: Metallorganische Reagenzien. Cericammoniumnitrate (CAN)
Kurs: Metallorganische eagenzien Cericammoniumnitrate (CAN) by Laura Munoz Senovilla and Arthur Fedoseev. CAN as one-electronelectron oxidant CAN as one-electron electron oxidant Based on: Salt of high-valent
More informationChapter 11. Free Radical Reactions
hapter 11 Free Radical Reactions A free radical is a species containing one or more unpaired electrons Free radicals are electron-deficient species, but they are usually uncharged, so their chemistry is
More informationChapter 15 Radical Reactions. Radicals are reactive species with a single unpaired electron, formed by
Chapter 15 Radical Reactions Radicals are reactive species with a single unpaired electron, formed by homolysis of a covalent bond; a radical contains an atom that does not have an octet of electrons,
More informationCHEM 211 CHAPTER 16 - Homework
CHEM 211 CHAPTER 16 - Homework SHORT ANSWER Consider the Friedel-Crafts alkylation reaction below to answer the following question(s): 1. Refer to the reaction above. Draw the structure of the electrophilic
More informationCarboxylic Acid Structure and Chemistry: Part 2
Principles of Drug Action 1, pring 2005, Carboxylic Acids Part 2 Carboxylic Acid tructure and Chemistry: Part 2 Jack Deuiter IV. eactions of the Carboxylic Acid eactions Depending on their overall structure,
More informationREACTIONS OF AROMATIC COMPOUNDS
A STUDENT SHOULD BE ABLE TO: REACTIONS OF AROMATIC COMPOUNDS 1. Predict the product(s) of Electrophilic Aromatic Substitution (EAS), Nucleophilic Aromatic Substitution (S N Ar) and Elimination-Addition
More informationChemistry B11 Chapter 4 Chemical reactions
Chemistry B11 Chapter 4 Chemical reactions Chemical reactions are classified into five groups: A + B AB Synthesis reactions (Combination) H + O H O AB A + B Decomposition reactions (Analysis) NaCl Na +Cl
More informationAldehydes can react with alcohols to form hemiacetals. 340 14. Nucleophilic substitution at C=O with loss of carbonyl oxygen
340 14. Nucleophilic substitution at C= with loss of carbonyl oxygen Ph In Chapter 13 we saw this way of making a reaction go faster by raising the energy of the starting material. We also saw that the
More informationBonding in Elements and Compounds. Covalent
Bonding in Elements and Compounds Structure of solids, liquids and gases Types of bonding between atoms and molecules Ionic Covalent Metallic Many compounds between metals & nonmetals (salts), e.g. Na,
More informationEXPERIMENT 12: Empirical Formula of a Compound
EXPERIMENT 12: Empirical Formula of a Compound INTRODUCTION Chemical formulas indicate the composition of compounds. A formula that gives only the simplest ratio of the relative number of atoms in a compound
More informationDavid W. C. MacMillan Career-in-Review. Sujun Wei BreslowGroup Columbia University September 28, 2007
David W. C. MacMillan Career-in-Review Sujun Wei BreslowGroup Columbia University September 28, 2007 Biography 1968: Born in Bellshill, Scotland 1987-1991: B.S. at the University of Glasgow, Scotland 1991-1996:.D.
More information1. How many hydrogen atoms are in 1.00 g of hydrogen?
MOLES AND CALCULATIONS USING THE MOLE CONCEPT INTRODUCTORY TERMS A. What is an amu? 1.66 x 10-24 g B. We need a conversion to the macroscopic world. 1. How many hydrogen atoms are in 1.00 g of hydrogen?
More informationSaturated NaCl solution rubber tubing (2) Glass adaptor (2) thermometer adaptor heating mantle
EXPERIMENT 5 (Organic Chemistry II) Pahlavan/Cherif Dehydration of Alcohols - Dehydration of Cyclohexanol Purpose - The purpose of this lab is to produce cyclohexene through the acid catalyzed elimination
More informationConjugation is broken completely by the introduction of saturated (sp3) carbon:
Chapter 16 Conjugation, resonance, and dienes Conjugation relies on the partial overlap of p-orbitals on adjacent double or triple bonds. A common conjugated system involves 1,3-dienes, such as 1,3-butadiene.
More informationChapter 11 Homework and practice questions Reactions of Alkyl Halides: Nucleophilic Substitutions and Eliminations
Chapter 11 Homework and practice questions Reactions of Alkyl Halides: Nucleophilic Substitutions and Eliminations SHORT ANSWER Exhibit 11-1 Circle your response in each set below. 1. Circle the least
More informationFIVE-MEMBERED RING FORMATION 138. 5 Membered Rings. Intramolecular S N 2 Reaction
5 mbered ings FIVE-MEMBEED IG FMATI 138 C 2 C 2 PGF 2α PGE 2 irsutene Modhephane Isocumene 1. Intramolecular S 2 eactions 2. Intramolecular Aldol Condensation and Michael Addition 3. Intramolecular Wittig
More informationName Lab #3: Solubility of Organic Compounds Objectives: Introduction: soluble insoluble partially soluble miscible immiscible
Lab #3: Solubility of rganic Compounds bjectives: - Understanding the relative solubility of organic compounds in various solvents. - Exploration of the effect of polar groups on a nonpolar hydrocarbon
More informationIdentification of Unknown Organic Compounds
Identification of Unknown Organic Compounds Introduction The identification and characterization of the structures of unknown substances are an important part of organic chemistry. Although it is often
More informationReminder: These notes are meant to supplement, not replace, the textbook and lab manual. Electrophilic Aromatic Substitution notes
Reminder: These notes are meant to supplement, not replace, the textbook and lab manual. Electrophilic Aromatic Substitution notes History and Application: The rate of a reaction directly impacts the commercial
More informationSCH 4C1 Unit 2 Problem Set Questions taken from Frank Mustoe et all, "Chemistry 11", McGraw-Hill Ryerson, 2001
SCH 4C1 Unit 2 Problem Set Questions taken from Frank Mustoe et all, "Chemistry 11", McGraw-Hill Ryerson, 2001 1. A small pin contains 0.0178 mol of iron. How many atoms of iron are in the pin? 2. A sample
More informationstoichiometry = the numerical relationships between chemical amounts in a reaction.
1 REACTIONS AND YIELD ANSWERS stoichiometry = the numerical relationships between chemical amounts in a reaction. 2C 8 H 18 (l) + 25O 2 16CO 2 (g) + 18H 2 O(g) From the equation, 16 moles of CO 2 (a greenhouse
More informationBenzene Benzene is best represented as a resonance hybrid:
Electrophilic Aromatic Substitution (EAS) is a substitution reaction usually involving the benzene ring; more specifically it is a reaction in which the hydrogen atom of an aromatic ring is replaced as
More informationChapter 1 The Atomic Nature of Matter
Chapter 1 The Atomic Nature of Matter 6. Substances that cannot be decomposed into two or more simpler substances by chemical means are called a. pure substances. b. compounds. c. molecules. d. elements.
More informationAromaticity and Reactions of Benzene
Aromaticity and eactions of Benzene ark College Benzene is a unique molecule it is highly unsaturated with 6 carbons and 6 hydrogens, it is planar, and has a high degree of symmetry. These features explain
More informationPage 1. 6. Which hydrocarbon is a member of the alkane series? (1) 1. Which is the structural formula of methane? (1) (2) (2) (3) (3) (4) (4)
1. Which is the structural formula of methane? 6. Which hydrocarbon is a member of the alkane series? 7. How many carbon atoms are contained in an ethyl group? 1 3 2 4 2. In the alkane series, each molecule
More informationCambridge International Examinations Cambridge International General Certificate of Secondary Education
Cambridge International Examinations Cambridge International General Certificate of Secondary Education *0123456789* CHEMISTRY 0620/03 Paper 3 Theory (Core) For Examination from 2016 SPECIMEN PAPER 1 hour
More information4/18/2011. 9.8 Substituent Effects in Electrophilic Substitutions. Substituent Effects in Electrophilic Substitutions
9.8 Substituent effects in the electrophilic substitution of an aromatic ring Substituents affect the reactivity of the aromatic ring Some substituents activate the ring, making it more reactive than benzene
More informationChemical Calculations: Formula Masses, Moles, and Chemical Equations
Chemical Calculations: Formula Masses, Moles, and Chemical Equations Atomic Mass & Formula Mass Recall from Chapter Three that the average mass of an atom of a given element can be found on the periodic
More informationAROMATIC COMPOUNDS A STUDENT SHOULD BE ABLE TO:
A STUDENT SHULD BE ABLE T: ARMATIC CMPUNDS 1. Name benzene derivatives given the structures, and draw the structures given the names. This includes: Monosubstituted benzenes named as derivatives of benzene:
More informationIB Chemistry. DP Chemistry Review
DP Chemistry Review Topic 1: Quantitative chemistry 1.1 The mole concept and Avogadro s constant Assessment statement Apply the mole concept to substances. Determine the number of particles and the amount
More informationORGANIC CHEM I Practice Questions for Ch. 4
ORGANIC CHEM I Practice Questions for Ch. 4 1) Write an equation to describe the initiation step in the chlorination of methane. 2) Reaction intermediates that have unpaired electrons are called. 3) When
More informationChapter 12: Oxidation and Reduction.
207 Oxidation- reduction (redox) reactions Chapter 12: Oxidation and Reduction. At different times, oxidation and reduction (redox) have had different, but complimentary, definitions. Compare the following
More informationCode number given on the right hand side of the question paper should be written on the title page of the answerbook by the candidate.
Series ONS SET-3 Roll No. Candiates must write code on the title page of the answer book Please check that this question paper contains 15 printed pages. Code number given on the right hand side of the
More informationOxidation / Reduction Handout Chem 2 WS11
Oxidation / Reduction Handout Chem 2 WS11 The original concept of oxidation applied to reactions where there was a union with oxygen. The oxygen was either furnished by elemental oxygen or by compounds
More informationPART I: MULTIPLE CHOICE (30 multiple choice questions. Each multiple choice question is worth 2 points)
CHEMISTRY 123-07 Midterm #1 Answer key October 14, 2010 Statistics: Average: 74 p (74%); Highest: 97 p (95%); Lowest: 33 p (33%) Number of students performing at or above average: 67 (57%) Number of students
More informationBut in organic terms: Oxidation: loss of H 2 ; addition of O or O 2 ; addition of X 2 (halogens).
Reactions of Alcohols Alcohols are versatile organic compounds since they undergo a wide variety of transformations the majority of which are either oxidation or reduction type reactions. Normally: Oxidation
More informationChemical Calculations: The Mole Concept and Chemical Formulas. AW Atomic weight (mass of the atom of an element) was determined by relative weights.
1 Introduction to Chemistry Atomic Weights (Definitions) Chemical Calculations: The Mole Concept and Chemical Formulas AW Atomic weight (mass of the atom of an element) was determined by relative weights.
More informationAlkanes. Chapter 1.1
Alkanes Chapter 1.1 Organic Chemistry The study of carbon-containing compounds and their properties What s so special about carbon? Carbon has 4 bonding electrons. Thus, it can form 4 strong covalent bonds
More informationUnit 9 Compounds Molecules
Unit 9 Compounds Molecules INTRODUCTION Compounds are the results of combinations of elements. These new substances have unique properties compared to the elements that make them up. Compounds are by far
More informationChemical Reactions in Water Ron Robertson
Chemical Reactions in Water Ron Robertson r2 f:\files\courses\1110-20\2010 possible slides for web\waterchemtrans.doc Properties of Compounds in Water Electrolytes and nonelectrolytes Water soluble compounds
More informationINTERMOLECULAR FORCES
INTERMOLECULAR FORCES Intermolecular forces- forces of attraction and repulsion between molecules that hold molecules, ions, and atoms together. Intramolecular - forces of chemical bonds within a molecule
More informationChemistry 1050 Chapter 13 LIQUIDS AND SOLIDS 1. Exercises: 25, 27, 33, 39, 41, 43, 51, 53, 57, 61, 63, 67, 69, 71(a), 73, 75, 79
Chemistry 1050 Chapter 13 LIQUIDS AND SOLIDS 1 Text: Petrucci, Harwood, Herring 8 th Edition Suggest text problems Review questions: 1, 5!11, 13!17, 19!23 Exercises: 25, 27, 33, 39, 41, 43, 51, 53, 57,
More information19.2 Chemical Formulas
In the previous section, you learned how and why atoms form chemical bonds with one another. You also know that atoms combine in certain ratios with other atoms. These ratios determine the chemical formula
More informationFormulas, Equations and Moles
Chapter 3 Formulas, Equations and Moles Interpreting Chemical Equations You can interpret a balanced chemical equation in many ways. On a microscopic level, two molecules of H 2 react with one molecule
More informationStoichiometry. Lecture Examples Answer Key
Stoichiometry Lecture Examples Answer Key Ex. 1 Balance the following chemical equations: 3 NaBr + 1 H 3 PO 4 3 HBr + 1 Na 3 PO 4 2 C 3 H 5 N 3 O 9 6 CO 2 + 3 N 2 + 5 H 2 O + 9 O 2 2 Ca(OH) 2 + 2 SO 2
More informationNucleophilic Substitution and Elimination
Nucleophilic Substitution and Elimination What does the term "nucleophilic substitution" imply? A nucleophile is an the electron rich species that will react with an electron poor species A substitution
More informationIB Chemistry 1 Mole. One atom of C-12 has a mass of 12 amu. One mole of C-12 has a mass of 12 g. Grams we can use more easily.
The Mole Atomic mass units and atoms are not convenient units to work with. The concept of the mole was invented. This was the number of atoms of carbon-12 that were needed to make 12 g of carbon. 1 mole
More informationmethyl RX example primary RX example secondary RX example secondary RX example tertiary RX example
ucleophilic Substitution & Elimination hemistry 1 eginning patterns to knowfor S and E eactions - horizontal and vertical templates for practice Example 1 - two possible perspectives (deuterium and tritium
More informationWhich substance contains positive ions immersed in a sea of mobile electrons? A) O2(s) B) Cu(s) C) CuO(s) D) SiO2(s)
BONDING MIDTERM REVIEW 7546-1 - Page 1 1) Which substance contains positive ions immersed in a sea of mobile electrons? A) O2(s) B) Cu(s) C) CuO(s) D) SiO2(s) 2) The bond between hydrogen and oxygen in
More informationOrganometallics Study Seminar Chapter 13: Metal-Ligand Multiple Bonds
Organometallics Study Seminar Chapter 13: Metal-Ligand Multiple Bonds Contents 1. Carbene Complexes 2. Silylene Complexes 3. Metal-Heteroatom Multiple Bonds 1. Carbene Complexes 1.1 Classes of Carbene
More informationCandidate Style Answer
Candidate Style Answer Chemistry A Unit F321 Atoms, Bonds and Groups High banded response This Support Material booklet is designed to accompany the OCR GCE Chemistry A Specimen Paper F321 for teaching
More informationneutrons are present?
AP Chem Summer Assignment Worksheet #1 Atomic Structure 1. a) For the ion 39 K +, state how many electrons, how many protons, and how many 19 neutrons are present? b) Which of these particles has the smallest
More informationElement of same atomic number, but different atomic mass o Example: Hydrogen
Atomic mass: p + = protons; e - = electrons; n 0 = neutrons p + + n 0 = atomic mass o For carbon-12, 6p + + 6n 0 = atomic mass of 12.0 o For chlorine-35, 17p + + 18n 0 = atomic mass of 35.0 atomic mass
More informationCHE 232 - Organic Chemistry Exam 1, February 10, 2004
CE 232 - rganic Chemistry Exam 1, February 10, 2004 ame Student ID o. Before you begin this exam: First: You are allowed to have a simple model set at your seat. Please put away all other materials. Second:
More informationEXPERIMENT 3 (Organic Chemistry II) Nitration of Aromatic Compounds: Preparation of methyl-m-nitrobenzoate
EXPERIMENT 3 (Organic Chemistry II) Nitration of Aromatic Compounds: Preparation of methyl-m-nitrobenzoate Pahlavan/Cherif Purpose a) Study electrophilic aromatic substitution reaction (EAS) b) Study regioselectivity
More informationChem 115 POGIL Worksheet - Week 4 Moles & Stoichiometry Answers
Key Questions & Exercises Chem 115 POGIL Worksheet - Week 4 Moles & Stoichiometry Answers 1. The atomic weight of carbon is 12.0107 u, so a mole of carbon has a mass of 12.0107 g. Why doesn t a mole of
More informationAP CHEMISTRY 2006 SCORING GUIDELINES
AP CHEMISTRY 2006 SCORING GUIDELINES Question 6 6. Answer each of the following in terms of principles of molecular behavior and chemical concepts. (a) The structures for glucose, C 6 H 12 O 6, and cyclohexane,
More informationORGANIC CHEMISTRY I PRACTICE EXERCISE Sn1 and Sn2 Reactions
ORGANIC CEMISTRY I PRACTICE EXERCISE Sn1 and Sn2 Reactions 1) Which of the following best represents the carbon-chlorine bond of methyl chloride? d d - d - d d d d - d - I II III IV V 2) Provide a detailed,
More informationStudying an Organic Reaction. How do we know if a reaction can occur? And if a reaction can occur what do we know about the reaction?
Studying an Organic Reaction How do we know if a reaction can occur? And if a reaction can occur what do we know about the reaction? Information we want to know: How much heat is generated? How fast is
More informationChapter 8: Energy and Metabolism
Chapter 8: Energy and Metabolism 1. Discuss energy conversions and the 1 st and 2 nd law of thermodynamics. Be sure to use the terms work, potential energy, kinetic energy, and entropy. 2. What are Joules
More informationChemical Kinetics. 2. Using the kinetics of a given reaction a possible reaction mechanism
1. Kinetics is the study of the rates of reaction. Chemical Kinetics 2. Using the kinetics of a given reaction a possible reaction mechanism 3. What is a reaction mechanism? Why is it important? A reaction
More informationElectrophilic Aromatic Substitution Reactions
Electrophilic Aromatic Substitution Reactions, Course Notes Archive, 1 Electrophilic Aromatic Substitution Reactions An organic reaction in which an electrophile substitutes a hydrogen atom in an aromatic
More informationChemistry Diagnostic Questions
Chemistry Diagnostic Questions Answer these 40 multiple choice questions and then check your answers, located at the end of this document. If you correctly answered less than 25 questions, you need to
More informationChapter 22 Carbonyl Alpha-Substitution Reactions
John E. McMurry www.cengage.com/chemistry/mcmurry Chapter 22 Carbonyl Alpha-Substitution Reactions The α Position The carbon next to the carbonyl group is designated as being in the α position Electrophilic
More informationUnit 6 The Mole Concept
Chemistry Form 3 Page 62 Ms. R. Buttigieg Unit 6 The Mole Concept See Chemistry for You Chapter 28 pg. 352-363 See GCSE Chemistry Chapter 5 pg. 70-79 6.1 Relative atomic mass. The relative atomic mass
More informationAvg. 16.4 / 25 Stnd. Dev. 8.2
QUIZ TREE Avg. 16.4 / 25 Stnd. Dev. 8.2 xidation of Alcohols with Chromium (VI): Jones xidation 2 Alcohols are oxidized by a solution of chromium trioxide in aqueous acetone (2), in the presence of an
More informationCHEMISTRY II FINAL EXAM REVIEW
Name Period CHEMISTRY II FINAL EXAM REVIEW Final Exam: approximately 75 multiple choice questions Ch 12: Stoichiometry Ch 5 & 6: Electron Configurations & Periodic Properties Ch 7 & 8: Bonding Ch 14: Gas
More informationChem101: General Chemistry Lecture 9 Acids and Bases
: General Chemistry Lecture 9 Acids and Bases I. Introduction A. In chemistry, and particularly biochemistry, water is the most common solvent 1. In studying acids and bases we are going to see that water
More informationActivation of Carbon-Hydrogen Bonds at Transition Metal Centers!
Activation of arbon-ydrogen Bonds at Transition Metal enters! Thanks to John Bercaw for many nice figures for this lecture! oxidative addition/reductive elimination [L n M q ] L n M q2 L n M q σ complex
More informationLecture 35: Atmosphere in Furnaces
Lecture 35: Atmosphere in Furnaces Contents: Selection of atmosphere: Gases and their behavior: Prepared atmospheres Protective atmospheres applications Atmosphere volume requirements Atmosphere sensors
More informationConcept 1. The meaning and usefulness of the mole. The mole (or mol) represents a certain number of objects.
Chapter 3. Stoichiometry: Mole-Mass Relationships in Chemical Reactions Concept 1. The meaning and usefulness of the mole The mole (or mol) represents a certain number of objects. SI def.: the amount of
More informationChapter 4. Chemical Composition. Chapter 4 Topics H 2 S. 4.1 Mole Quantities. The Mole Scale. Molar Mass The Mass of 1 Mole
Chapter 4 Chemical Composition Chapter 4 Topics 1. Mole Quantities 2. Moles, Masses, and Particles 3. Determining Empirical Formulas 4. Chemical Composition of Solutions Copyright The McGraw-Hill Companies,
More informationChapter 4 Chemical Reactions
Chapter 4 Chemical Reactions I) Ions in Aqueous Solution many reactions take place in water form ions in solution aq solution = solute + solvent solute: substance being dissolved and present in lesser
More informationAPPENDIX B: EXERCISES
BUILDING CHEMISTRY LABORATORY SESSIONS APPENDIX B: EXERCISES Molecular mass, the mole, and mass percent Relative atomic and molecular mass Relative atomic mass (A r ) is a constant that expresses the ratio
More informationAmount of Substance. http://www.avogadro.co.uk/definitions/elemcompmix.htm
Page 1 of 14 Amount of Substance Key terms in this chapter are: Element Compound Mixture Atom Molecule Ion Relative Atomic Mass Avogadro constant Mole Isotope Relative Isotopic Mass Relative Molecular
More informationThe Periodic Table: Periodic trends
Unit 1 The Periodic Table: Periodic trends There are over one hundred different chemical elements. Some of these elements are familiar to you such as hydrogen, oxygen, nitrogen and carbon. Each one has
More information10. Calculate the mass percent nitrogen in (NH 4 ) 2 CO 3 (molar mass = 96.09 g/mol). a. 29.1 % c. 17.9 % e. 14.6 % b. 35.9 % d. 0.292 % f. 96.
Chem 171-2-3: Final Exam Review Multiple Choice Problems 1. What is the molar mass of barium perchlorate, Ba(ClO 4 ) 2? a. 189.90 g/mol c. 272.24 g/mol e. 336.20 g/mol b. 240.24 g/mol d. 304.24 g/mol f.
More information1. Oxidation number is 0 for atoms in an element. 3. In compounds, alkalis have oxidation number +1; alkaline earths have oxidation number +2.
à xidation numbers In the Lewis model of bonding, when nonidentical atoms are bonded together, an important consideration is how the bonding electrons are apportioned between the atoms. There are two different
More informationA. Essentially the order of Pt II affinity for these ligands (their Lewis basicity or nucleophilicity)
(c) Entering Ligand Effects 284 The second order rate constant k 2 in square planar complexes in the rate law below that we just discussed is strongly dependent on the nature of Y, the entering ligand
More informationMolarity of Ions in Solution
APPENDIX A Molarity of Ions in Solution ften it is necessary to calculate not only the concentration (in molarity) of a compound in aqueous solution but also the concentration of each ion in aqueous solution.
More informationAtomic Structure. Name Mass Charge Location Protons 1 +1 Nucleus Neutrons 1 0 Nucleus Electrons 1/1837-1 Orbit nucleus in outer shells
Atomic Structure called nucleons Name Mass Charge Location Protons 1 +1 Nucleus Neutrons 1 0 Nucleus Electrons 1/1837-1 Orbit nucleus in outer shells The number of protons equals the atomic number This
More informationA Perspective on Professor Scott Eric Denmark: The Man, The Myth, The Chemist O
A Perspective on Professor Scott Eric Denmark: The Man, The Myth, The Chemist Si 3 2 C 2 S P (C 2 ) 5 2 n-c 5 9 ussell C. Smith Stoltz/eisman Group eting January 24, 2011 Si M From umble Beginnings Born
More informationChapter 2 Polar Covalent Bonds: Acids and Bases
John E. McMurry www.cengage.com/chemistry/mcmurry Chapter 2 Polar Covalent Bonds: Acids and Bases Modified by Dr. Daniela R. Radu Why This Chapter? Description of basic ways chemists account for chemical
More informationATOMS. Multiple Choice Questions
Chapter 3 ATOMS AND MOLECULES Multiple Choice Questions 1. Which of the following correctly represents 360 g of water? (i) 2 moles of H 2 0 (ii) 20 moles of water (iii) 6.022 10 23 molecules of water (iv)
More informationEDEXCEL INTERNATIONAL GCSE CHEMISTRY EDEXCEL CERTIFICATE IN CHEMISTRY ANSWERS SECTION E
EDEXCEL INTERNATIONAL GCSE CHEMISTRY EDEXCEL CERTIFICATE IN CHEMISTRY ANSWERS SECTION E (To save endless repetition, wherever they are included, comments are intended for homeschooling parents who may
More information