Transition metal complexes with wide-angle dithio-, diseleno- and ditelluroethers: properties and structural systematics

Levason, William, Nirwan, Manisha, Ratnani, Raju, Reid, Gillian, Tsoureas, Nikolaos and Webster, Michael (2007) Transition metal complexes with wide-angle dithio-, diseleno- and ditelluroethers: properties and structural systematics. Dalton Transactions, (4), 439-448. (doi:10.1039/b613501c).

Abstract

The ligands o-C6H4(CH2EMe)(2) (E = S or Se) have been prepared and characterised spectroscopically. A systematic study of the coordination chemistry of these, together with the telluroether analogue, o-C6H4(CH2TeMe)(2), with late transition metal centers has been undertaken. The planar complexes [MCl2{o-C6H4(CH2SMe)(2)}] and [M{o-C6H4(CH2EMe)(2)}(2)](PF6)(2) (M = Pd or Pt; E = S or Se), the distorted octahedral [RhCl2{o-C6H4(CH2EMe)(2)}(2)]Y (E = S or Se: Y = PF6; E = Te: Y = Cl) and [RuCl2{o-C6H4(CH2EMe)(2)}(2)] (E = S, Se or Te), the dithioether-bridged binuclear [{RuCl2(p-cymene)}(2){mu-o-C6H4(CH2SMe)(2)}] and the tetrahedral [M'{o-C6H4(CH2EMe)(2)}(2)]BF4 (M' = Cu or Ag; E = S, Se or Te) have been obtained and characterised by IR and multinuclear NMR spectroscopy (H-1, Cu-63, Se-77{H-1}, Te-125{H-1} and Pt-195), electrospray MS and microanalyses. Crystal structures of the parent o-C6H4(CH2SMe)(2) and seven complexes are described, which show three different stereoisomeric forms for the chelated ligands, as well as the first example of a bridging coordination mode in [{RuCl2(p-cymene)}(2){mu-o-C6H4(CH2SMe)(2)}]. These studies reveal the consequences of the sterically demanding o-xylyl backbone, which typically leads to unusually obtuse E-M-E chelate angles of similar to 100 degrees.

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Contributors

Author: William Levason

Author: Gillian Reid

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