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Syntheses, structures, and reductive elimination studies of six-membered diaryl platinacycle complexes

Citation

Robinson, R and Sharp, PR, Syntheses, structures, and reductive elimination studies of six-membered diaryl platinacycle complexes, Organometallics, 29, (6) pp. 1388-1395. ISSN 0276-7333 (2010) [Refereed Article]

Copyright Statement

Copyright 2010 American Chemical Society

DOI: doi:10.1021/om901033z

Abstract

The six-membered platinacycles PtL2(C6H4XC6H4) (X=CH2, O, NMe; L = PEt3, L2 = 1,3- bis(diphenylphosphino)propane (dppp), 4,40-bis-tert-butyl-2,20-bipyridine (tBu2bpy)), have been prepared from cis-PtL2Cl2 and the appropriate dilithio reagents. Reductive elimination studies on the platinacycles with L = PEt3 show that the bridging group (X) dramatically influences the reductive elimination rate. Thermodynamic activation parameters were determined for the platinacycles and showed a Hq trend X = NMe , O < CH2 with an essentially zero value for Sq. Rate constants at 95 C show over a million-fold increase on going from X = CH2 to X = NMe. DFT calculations support direct elimination without phosphine ligand loss and indicate a progressively earlier transition state in the seriesX=CH2, O,NMe. The earlier transition state and the accelerated rate are associated with the beginning of aromatization in the eliminating organic unit. Computed thermodynamic activation parameters are in good agreement with the experimental results.

Item Details

Item Type:Refereed Article
Research Division:Chemical Sciences
Research Group:Inorganic Chemistry
Research Field:Transition Metal Chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding Knowledge
Objective Field:Expanding Knowledge in the Chemical Sciences
Author:Robinson, R (Dr Robert Robinson)
ID Code:81055
Year Published:2010
Web of Science® Times Cited:7
Deposited By:Chemistry
Deposited On:2012-11-22
Last Modified:2013-05-08
Downloads:0

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