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Bond Angle Effects on the Migratory Insertion of Ethylene and Carbon Monoxide into Palladium(II)-Methyl Bonds in Complexes Bearing Bidentate Phosphine Ligands

Bond Angle Effects on the Migratory Insertion of Ethylene and Carbon Monoxide into Palladium(II)-Methyl Bonds in Complexes Bearing Bidentate Phosphine Ligands. Ledford, John; Shultz, C. Scott; Gates, Derek P.; White, Peter S.; DeSimone, Joseph M.; Brookhart, Maurice (Department of Chemistry, University of North Carolina, Chapel Hill, NC 27599-3290, USA). Organometallics, 20(25), 5266-5276 (English) 2001 American Chemical Society. CODEN: ORGND7. ISSN: 0276-7333. DOCUMENT TYPE: Journal CA Section: 29 (Organometallic and Organometalloidal Compounds) Section cross-reference(s): 22, 75 Labile (P-P)Pd(CH3)(OEt2)+BAr'4- complexes (2) have been prepd. via protonation of (P-P)PdMe2 (1), where P-P = cis-1,2-bis(diphenylphosphino)ethylene (a, dppee), 1,2-bis(diphenylphosphino)benzene (b, dpbz), 1,2-bis(diphenylphosphino)ethane (c, dppe), 1,2-bis(dimethylphosphino)ethane (d, dmpe), 1,3-bis(diphenylphosphino)propane (e, dppp), 1,3-bis(diisopropylphosphino)propane (f, dippp), 1,4-bis(diphenylphosphino)butane (g, dppb) and Ar' = 3,5-(CF3)2C6H3. Unstable complex 2d (P-P = dmpe) was generated in situ. X-ray structures are reported for 1e and 2e-g. Treatment of 2a-g with CO in CH2Cl2 at -90° yields the (P-P)Pd(CH3)(CO)+ complexes 3a-g. Barriers to migratory insertion in 3a-g were detd. with the ordering to be: 3f (dippp) u 3g (dppb) < 3e (dppp) ? 3a (dppee) u 3b (dpbz) u 3c (dppe) < 3d (dmpe). Exposure of 2a-g to ethylene at -80° yields the ethylene complexes (P-P)Pd(CH3)(C2H4)+ (5a-g). Barriers to migratory insertion in these complexes were detd. by NMR spectroscopy to be: 5b (dpbz) u 5e (dppp) u 5f (dippp) u 5g (dppb) < 5a (dppee) u 5c (dppe) < 5d (dmpe). Complexes (P-P)Pd(CH2CH3)(C2H4)+ (6a-e,g) produced from 5a-e,g under C2H4 are catalyst resting states for the dimerization of C2H4 to butenes. In the case of 5f (P-P = dippp), the catalyst resting state produced is the b-agostic Et complex (dippp)Pd(CH2CH2-m-H)+ (8f), which has been isolated. This complex exhibits two dynamic processes studied by VT-NMR:interchange of Ca and Cb (DGG = 10.3(2) kcal/mol) and rotation of the agostic Me group (DGG ca. 6.4 kcal/mol). The b-agostic Pr complex 7f has been generated and identified as the Pr isomer (dippp)Pd(CH2CH2-m-HCH3)+. Keywords bond angle effect migratory insertion ethylene carbon monoxide palladium methyl bidentate phosphine complex prepn migratory insertion crystal mol structure methyl palladium bidentate phosphine arylborate complex kinetics migratory insertion ethylene carbon monoxide palladium dimethyl complex Index Entries Bond agostic; bond angle effects on migratory insertion of ethylene and carbon monoxide into palladium-Me bonds in complexes bearing bidentate phosphine ligands Free energy of activation Insertion reaction kinetics Potential barrier bond angle effects on migratory insertion of ethylene and carbon monoxide into palladium-Me bonds in complexes bearing bidentate phosphine ligands Bond carbon-palladium; bond angle effects on migratory insertion of ethylene and carbon monoxide into palladium-Me bonds in complexes bearing bidentate phosphine ligands Bond angle effect; bond angle effects on migratory insertion of ethylene and carbon monoxide into palladium-Me bonds in complexes bearing bidentate phosphine ligands Insertion reaction intramol., migration; bond angle effects on migratory insertion of ethylene and carbon monoxide into palladium-Me bonds in complexes bearing bidentate phosphine ligands Crystal structure Molecular structure of methylpalladium complexes with bidentate phosphine ligands Dimerization catalysts prepn. of methylpalladium bidentate phosphine complexes as dimerization catalysts for alkenes 260994-21-6 389798-51-0 389798-53-2 389798-55-4 389798-57-6 389798-59-8 389798-61-2 74-85-1, reactions 51915-19-6 139362-04-2 15630-15-6 63455-39-0 210767-94-5 288155-73-7 389798-18-9 389798-19-0 389798-21-4 389798-23-6 389798-25-8 389798-27-0 389798-29-2 389798-31-6 389798-33-8 389798-35-0 389798-37-2 389798-39-4 bond angle effects on migratory insertion of ethylene and carbon monoxide into palladium-Me bonds in complexes bearing bidentate phosphine ligands 113530-46-4 113530-47-5 210767-70-7 260993-77-9 crystal structure; bond angle effects on migratory insertion of ethylene and carbon monoxide into palladium-Me bonds in complexes bearing bidentate phosphine ligands 288155-74-8 288155-77-1 389798-41-8 389798-43-0 389798-44-1 389798-45-2 389798-47-4 389798-49-6 389798-63-4 389798-65-6 389798-67-8 389798-69-0 389798-71-4 389798-73-6 389798-75-8 389798-77-0 prepn. of 113822-11-0 reaction with bidentate phosphines 983-80-2 1663-45-2 6737-42-4 7688-25-7 13991-08-7 23936-60-9 91159-11-4 reaction with dimethyl(tetramethylethylenediamine)palladium complex

Toward the Design of Double Metal Cyanides for the Copolymerization of CO2 and Epoxides

Toward the Design of Double Metal Cyanides for the Copolymerization of CO2 and Epoxides. Darensbourg, Donald J.; Adams, M. Jason; Yarbrough, Jason C. ( Department of Chemistry, Texas A&M University, College Station, TX 77843, USA). Inorganic Chemistry, 40(26), 6543-6544 (English) 2001 American Chemical Society. CODEN: INOCAJ. ISSN: 0020-1669. DOCUMENT TYPE: Journal CA Section: 29 (Organometallic and Organometalloidal Compounds) Section cross-reference(s): 35, 75 The syntheses and structures of heterometallic derivs. of zinc and iron contg. bridging cyano groups are reported. Thus, [K][CpFe(CN)2CO] with ZnCl2 gave [Zn][CpFe(CN)2CO]2. To synthesized a more tractable deriv., ZnI2 was reacted with [K][CpFe(CN)2PPh3] which afforded [CpFe(PPh3)(m-CN)2ZnI(CH3CN)]2. Finally, reaction of ZnI2 with [KCpFe(CN)2PPh2(CH2)1.5]2, obtained photochem. from [K][CpFe(CN)2CO] and 0.5 equiv. of dppp, gave {[CpFe(m-CN)2ZnI(THF)]2-m-dppp}, (I). Complex I was characterized by x-ray crystallog. Using complex I as a catalyst for the copolymn. of CO2 and cyclohexene oxide resulted in the prodn. of the cis cyclic carbonate, cis-7-9-dioxabicyclo[4.3.0]nonan-8-one. Keywords polymn catalyst iron zinc cyanide complex epoxide carbon dioxide crystal structure iron zinc cyanide complex prepn mol structure iron zinc cyanide complex Index Entries Crystal structure Molecular structure of iron zinc cyanide complex Polyethers, preparation polycarbonate-; prepn. of iron zinc cyanide complex as catalyst for copolymn. of carbon dioxide and epoxides Polycarbonates, preparation polyether-; prepn. of iron zinc cyanide complex as catalyst for copolymn. of carbon dioxide and epoxides Polymerization catalysts prepn. and crystal structure of iron zinc cyanide complex as catalyst for copolymn. of carbon dioxide and epoxides 19456-20-3 31631-20-6 390368-91-9 390368-92-0 prepn. of 124-38-9, reactions 286-20-4 6737-42-4 7646-85-7, reactions 10139-47-6 34802-15-8 53897-03-3 390368-93-1 prepn. of iron zinc cyanide complex as catalyst for copolymn. of carbon dioxide and epoxides 390368-94-2 prepn., crystal structure, and use as catalyst for copolymn. of carbon dioxide and epoxides