Issue 14, 2011
From the journal:

Dalton Transactions

Dithiocarboxylate complexes of ruthenium(ii) and osmium(ii)†

Saira Naeem,a   Amber L. Thompson,b   Andrew J. P. White,a   Lionel Delaudec  and  James D. E. T. Wilton-Ely*a  

* Corresponding authors

a Department of Chemistry, Imperial College London, South Kensington Campus, London, UK
E-mail: j.wilton-ely@imperial.ac.uk

b Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford, UK

c Laboratory of Macromolecular Chemistry and Organic Catalysis, Institut de Chimie (B6a), Université de Liège, Sart-Tilman par 4000 Liège, Belgium

Abstract

The ruthenium(II) complexes [Ru(R)(κ2-S2C·IPr)(CO)(PPh3)2]+ (R = CH[double bond, length as m-dash]CHBut, CH[double bond, length as m-dash]CHC6H4Me-4, C(C[triple bond, length as m-dash]CPh)[double bond, length as m-dash]CHPh) are formed on reaction of IPr·CS2 with [Ru(R)Cl(CO)(BTD)(PPh3)2] (BTD = 2,1,3-benzothiadiazole) or [Ru(C(C[triple bond, length as m-dash]CPh)[double bond, length as m-dash]CHPh)Cl(CO)(PPh3)2] in the presence of ammonium hexafluorophosphate. Similarly, the complexes [Ru(CH[double bond, length as m-dash]CHC6H4Me-4)(κ2-S2C·ICy)(CO)(PPh3)2]+ and [Ru(C(C[triple bond, length as m-dash]CPh)[double bond, length as m-dash]CHPh)(κ2-S2C·ICy)(CO)(PPh3)2]+ are formed in the same manner when ICy·CS2 is employed. The ligand IMes·CS2 reacts with [Ru(R)Cl(CO)(BTD)(PPh3)2] to form the compounds [Ru(R)(κ2-S2C·IMes)(CO)(PPh3)2]+ (R = CH[double bond, length as m-dash]CHBut, CH[double bond, length as m-dash]CHC6H4Me-4, C(C[triple bond, length as m-dash]CPh)[double bond, length as m-dash]CHPh). Two osmium analogues, [Os(CH[double bond, length as m-dash]CHC6H4Me-4)(κ2-S2C·IMes)(CO)(PPh3)2]+ and [Os(C(C[triple bond, length as m-dash]CPh)[double bond, length as m-dash]CHPh)(κ2-S2C·IMes)(CO)(PPh3)2]+ were also prepared. When the more bulky diisopropylphenyl derivative IDip·CS2 is used, an unusual product, [Ru(κ2-SC(H)S(CH[double bond, length as m-dash]CHC6H4Me-4)·IDip)Cl(CO)(PPh3)2]+, with a migrated vinyl group, is obtained. Over extended reaction times, [Ru(CH[double bond, length as m-dash]CHC6H4Me-4)Cl(BTD)(CO)(PPh3)2] also reacts with IMes·CS2 and NH4PF6 to yield the analogous product [Ru{κ2-SC(H)S(CH[double bond, length as m-dash]CHC6H4Me-4)·IMes}Cl(CO)(PPh3)2]+via the intermediate [Ru(CH[double bond, length as m-dash]CHC6H4Me-4)(κ2-S2C·IMes)(CO)(PPh3)2]+. Structural studies are reported for [Ru(CH[double bond, length as m-dash]CHC6H4Me-4)(κ2-S2C·IPr)(CO)(PPh3)2]PF6 and [Ru(C(C[triple bond, length as m-dash]CPh)[double bond, length as m-dash]CHPh)(κ2-S2C·ICy)(CO)(PPh3)2]PF6.

Graphical abstract: Dithiocarboxylate complexes of ruthenium(ii) and osmium(ii)

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Article information

DOI
https://doi.org/10.1039/C1DT10048C
Article type
Paper
Submitted
11 Jan 2011
Accepted
31 Jan 2011
First published
04 Mar 2011

Dalton Trans., 2011,40, 3737-3747

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Dithiocarboxylate complexes of ruthenium(II) and osmium(II)

S. Naeem, A. L. Thompson, A. J. P. White, L. Delaude and J. D. E. T. Wilton-Ely, Dalton Trans., 2011, 40, 3737 DOI: 10.1039/C1DT10048C

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