Zahl A, van Eldik R, Liehr G (2005)
Publication Type: Journal article, Original article
Publication year: 2005
Original Authors: Procelewska J., Zahl A., Liehr G., Van Eldik R., Smythe N., Williams B., Goldberg K.
Publisher: American Chemical Society
Book Volume: 44
Pages Range: 7732-7742
Journal Issue: 22
DOI: 10.1021/ic050478+
Cationic complexes of the type fac-[(L)PtMe (pyr-X)][OTf] (pyr-X = 4-substituted pyridines; L = diphosphine, viz., dppe = bis(diphenylphosphino)ethane and dppbz = o-bis(diphenylphosphino)benzene; OTf = trifluoromethane-sulfonate) undergo C-C reductive elimination reactions to form [LPtMe(pyr-X)] [OTf] and ethane. Detailed studies indicate that these reactions proceed by a two-step pathway, viz., initial reversible dissociation of the pyridine ligand from the cationic complex to generate a five-coordinate Pt intermediate, followed by irreversible concerted C-C bond formation. The reaction is inhibited by pyridine. The highly positive values for ΔS = +180 ± 30 J K mol , ΔH = 160 ± 10 kJ mol, and ΔV = +16 ± 1 cm mol can be accounted for in terms of significant bond cleavage and/or partial reduction from Pt to Pt in going from the ground to the transition state. These cationic complexes have provided the first opportunity to carry out detailed studies of C-C reductive elimination from cationic Pt complexes in a variety of solvents. The absence of a significant solvent effect for this reaction provides strong evidence that the C-C reductive coupling occurs from an unsaturated five-coordinate Pt intermediate rather than from a six-coordinate Pt solvento species. © 2005 American Chemical Society.
APA:
Zahl, A., van Eldik, R., & Liehr, G. (2005). Mechanistic information on the reductive elimination from cationic trimethylplatinum(IV) complexes to form carbon-carbon bonds. Inorganic Chemistry, 44(22), 7732-7742. https://doi.org/10.1021/ic050478+
MLA:
Zahl, Achim, Rudi van Eldik, and Günter Liehr. "Mechanistic information on the reductive elimination from cationic trimethylplatinum(IV) complexes to form carbon-carbon bonds." Inorganic Chemistry 44.22 (2005): 7732-7742.
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