eCite Digital Repository

Oxidation of complexes by (O2CPh)(2) and (ER)(2) (E = S, Se), including structures of Pd(CH2CH2CH2CH2)(SePh)(2)(bpy) (bpy = 2,2 '-bipyridine) and MMe2(SePh)(2)(L-2) (M = Pd, Pt; L-2 = bpy, 1,10-phenanthroline) and C···O and C···E bond formation at palladium(IV)

Citation

Canty, AJ and Jin, H and Skelton, BW and White, AH, Oxidation of complexes by (O2CPh)(2) and (ER)(2) (E = S, Se), including structures of Pd(CH2CH2CH2CH2)(SePh)(2)(bpy) (bpy = 2,2 '-bipyridine) and MMe2(SePh)(2)(L-2) (M = Pd, Pt; L-2 = bpy, 1,10-phenanthroline) and C···O and C···E bond formation at palladium(IV), Inorganic Chemistry, 37, (16) pp. 3975-3981. ISSN 0020-1669 (1998) [Refereed Article]

DOI: doi:10.1021/ic9715005

Abstract

Oxidation of PdMe 2(L 2) [L 2 = 2,2′-bipyridine (bpy), 1,10-phenanthroline (phen)] by diphenyl diselenide provides the first examples of stable dimethylpalladium(IV) complexes PdMe 2(SePh) 2(L 2), and pallada(IV)cyclic Pd(CH 2- CH 2CH 2CH 2)(SePh) 2(bpy) may be similarly isolated. X-ray structural studies of the octahedral dimethylpalladium-(IV) complexes and their isomorphous platinum(IV) analogues have been completed [L 2 = bpy, orthorhombic Pnma; L 2 = phen, triclinic P1̄; an additional phase for PtMe 2(SePh) 2(phen), tetragonal, I4 1/a]. The complexes PdMe 2(SePh) 2(L 2) decompose at moderate temperatures in CDCl 3 following first-order behavior [L 2 = bpy, E a ̃ 46 kJ mol -1, "S‡(20°C) ∼ -170 J K -1 mol -1; L 2 = phen, E a ∼36 kJ mol -1, "S‡(20°C) ∼ -204 J K -1 mol -1] to give ethane and Se(Ph)Me, together with small quantities of SePh 2. Similar C⋯C, C⋯O, C⋯S, and C⋯Se bond formation processes occur on decomposition of palladium(IV) species that are too unstable to be isolated on the oxidation of PdMe 2(bpy) or Pd(CH 2CH 2CH 2CH 2)(bpy) by (O 2CPh) 2 or (SPh) 2.

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:Jin, H (Dr Hong Jin)
ID Code:14065
Year Published:1998
Web of Science® Times Cited:64
Deposited By:Chemistry
Deposited On:1998-08-01
Last Modified:2011-08-09
Downloads:0

Repository Staff Only: item control page