Issue 17, 2010
From the journal:

Dalton Transactions

The functionalisation of ruthenium(ii) and osmium(ii) alkenyl complexes with amine- and alkoxy-terminated dithiocarbamates†

Saira Naeem,a   Eleanor Ogilvie,a   Andrew J. P. White,a   Graeme Hogarthb  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 Department of Chemistry, University College London, 20 Gordon Street, London, UK

Abstract

The complex cis-[RuCl2(dppm)2] reacts with the amine-terminated dithiocarbamates KS2CN(CH2CH2NEt2)2 and KS2CN(CH2CH2CH2NMe2)2 to form the compounds [Ru{S2CN(CH2CH2NEt2)2}(dppm)2]+ and [Ru{S2CN(CH2CH2CH2NMe2)2}(dppm)2]+, respectively. The methoxy-terminated dithiocarbamate compound [Ru{S2CN(CH2CH2OMe)2}(dppm)2]+ was also prepared from the same precursor using KS2CN(CH2CH2OMe)2. The alkenyl complexes [RuRCl(CO)(BTD)(PPh3)2] (R = CH[double bond, length as m-dash]CHBut, CH[double bond, length as m-dash]CHC6H4Me-4, CH[double bond, length as m-dash]CHCPh2OH), [Ru(C(C[triple bond, length as m-dash]CBut)[double bond, length as m-dash]CHBut)Cl(CO)(PPh3)2] and [Os(CH[double bond, length as m-dash]CHC6H4Me-4)Cl(CO)(BTD)(PPh3)2] also react cleanly with KS2CN(CH2CH2CH2NMe2)2 and KS2CN(CH2CH2NEt2)2 to yield [MR{S2CN(CH2CH2CH2NMe2)2}(CO)(PPh3)2] and [MR{S2CN(CH2CH2NEt2)2}(CO)(PPh3)2], respectively. In a similar fashion, the compounds [RuR{S2CN(CH2CH2OMe2)2}(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]CBut)[double bond, length as m-dash]CHBut) were also prepared. Treatment of [Ru(CH[double bond, length as m-dash]CHBut){S2CN(CH2CH2CH2NMe2)2}(CO)(PPh3)2] and [Ru{S2CN(CH2CH2NEt2)2}(dppm)2]+ with trifluoroacetic acid affords the ammonium complexes [Ru(CH[double bond, length as m-dash]CHBut){S2CN(CH2CH2CH2NHMe2)2}(CO)(PPh3)2]2+ and [Ru{S2CN(CH2CH2NHEt2)2}(dppm)2]2+, while the same reagent generates the tricationic vinylcarbene complex [Ru([double bond, length as m-dash]CHCH[double bond, length as m-dash]CPh2){S2CN(CH2CH2CH2NHMe2)2}(CO)(PPh3)2]3+ through loss of water from [Ru(CH[double bond, length as m-dash]CHCPh2OH){S2CN(CH2CH2CH2NMe2)2}(CO)(PPh3)2]. The structures of [Ru{S2CN(CH2CH2OMe)2}(dppm)2]PF6 and [Ru(CH[double bond, length as m-dash]CHC6H4Me-4){S2CN(CH2CH2OMe)2}(CO)(PPh3)2] were determined crystallographically.

Graphical abstract: The functionalisation of ruthenium(ii) and osmium(ii) alkenyl complexes with amine- and alkoxy-terminated dithiocarbamates

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Article information

DOI
https://doi.org/10.1039/B925536B
Article type
Paper
Submitted
03 Dec 2009
Accepted
22 Jan 2010
First published
11 Mar 2010

Dalton Trans., 2010,39, 4080-4089

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The functionalisation of ruthenium(II) and osmium(II) alkenyl complexes with amine- and alkoxy-terminated dithiocarbamates

S. Naeem, E. Ogilvie, A. J. P. White, G. Hogarth and J. D. E. T. Wilton-Ely, Dalton Trans., 2010, 39, 4080 DOI: 10.1039/B925536B

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