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Reversible oxidative addition of a diaryl diselenide to a diorganopalladium(II) complex, carbon-selenium bond formation at palladium(IV), and structural studies of palladium(II) and platinum(IV) selenolates

Citation

Canty, AJ and Denney, MC and Patel, J and Sun, H and Skelton, BW and White, AH, Reversible oxidative addition of a diaryl diselenide to a diorganopalladium(II) complex, carbon-selenium bond formation at palladium(IV), and structural studies of palladium(II) and platinum(IV) selenolates, Journal of Organometallic Chemistry, 689, (3) pp. 672-677. ISSN 0022-328X (2004) [Refereed Article]

DOI: doi:10.1016/j.jorganchem.2003.12.010

Abstract

Methyl(4-methoxyphenyl)(2,2′-bipyridine)palladium(II) (1) reacts with bis(4-chlorophenyl) diselenide in dichloromethane to form an equilibrium with the Pd(IV) complex Pd(SeC6 H4Cl)2Me(C6H4OMe)(bpy) (2) for which the forward reaction exhibits "H=-130±12 kJ mol-1 and "S=-472±49 J K-1 mol-1, and with K=754±145 at -25 °C. The Pd(IV) complex is isolable at -40 °C, and when the equilibrium mixture is kept at -25 °C, a temperature at which the Pd(II) complex is stable, selective reductive elimination of Me-SeC6H4Cl occurs very slowly from the Pd(IV) complex to form Pd(SeC6H4Cl)(C6 H4OMe)(bpy) (3). In contrast, (ClC6 H4Se)2 reacts with PdMe2(dmpe) (4) [dmpe=1,2-bis(dimethylphosphino)ethane] to form Pd(SeC6H4Cl)Me(dmpe) (5) and Me-SeC6H4Cl. A second equivalent of (ClC6H4Se)2 reacts with 5 to cleave the second Pd-Me bond to give Pd(SeC6 H4Cl)2(dmpe) (6) and Me-SeC6H4Cl. Similarly, PdMeTol(dmpe) (7) (Tol=4-tolyl) forms predominantly Pd(SeC6 H4Cl)Tol(dmpe) (8) together with some Pd(SeC6H4Cl)Me(dmpe) (5), and 8 reacts with (ClC6H4Se)2 to form Pd(SeC6H4Cl)2(dmpe) (6) and Tol-SeC6H4Cl. Bis(4-chlorophenyl) diselenide reacts with PtTol2(bpy) (9) (Tol=4-tolyl) to form Pt(SeC6H4Cl)2Tol2(bpy) (10) which, together with 2, has a trans-configuration for the selenolate ligands. X-ray structural studies of octahedral 10 as the solvate 10 · 3CHCl3 and square planar 5 are reported. © 2003 Elsevier B.V. All rights reserved.

Item Details

Item Type:Refereed Article
Research Division:Chemical Sciences
Research Group:Other Chemical Sciences
Research Field:Organometallic Chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding Knowledge
Objective Field:Expanding Knowledge in the Chemical Sciences
Author:Canty, AJ (Professor Allan Canty)
Author:Denney, MC (Mrs Melanie Denney)
Author:Patel, J (Mr Jim Patel)
Author:Sun, H (Dr Haishun Sun)
ID Code:31950
Year Published:2004
Web of Science® Times Cited:28
Deposited By:Chemistry
Deposited On:2004-08-01
Last Modified:2009-12-10
Downloads:0

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