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

Naeem, S; Ogilvie, E; White, AJP; Hogarth, G; Wilton-Ely, JDET; (2010) The functionalisation of ruthenium(II) and osmium(II) alkenyl complexes with amine- and alkoxy-terminated dithiocarbamates. DALTON T , 39 (17) 4080 - 4089. 10.1039/b925536b.

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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=CHBut, CH=CHC6H4Me-4, CH=CHCPh2OH), [Ru(C(C=CBut)=CHBut) Cl(CO)(PPh3)(2)] and [Os(CH=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=CHBut, CH=CHC6H4Me-4, C(C=CBut)=CHBut) were also prepared. Treatment of [Ru(CH=CHBut){S2CN(CH2CH2CH2NMe2)(2)}(CO)(PPh3)(2)] and [Ru{S2CN(CH2CH2NEt2)(2)}( dppm)(2)]+ with tri. uoroacetic acid affords the ammonium complexes [Ru(CH=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(=CHCH=CPh2){S2CN(CH2CH2CH2NHMe2)(2)}(CO)(PPh3)(2)](3+) through loss of water from [Ru(CH=CHCPh2OH){S2CN(CH2CH2CH2NMe2)(2)}(CO)(PPh3)(2)]. The structures of [Ru{S2CN(CH2CH2OMe)(2)}(dppm)(2)]PF6 and [Ru(CH=CHC6H4Me-(4)){S2CN(CH2CH2OMe)(2)}(CO)(PPh3)(2)] were determined crystallographically.

Type:Article
Title:The functionalisation of ruthenium(II) and osmium(II) alkenyl complexes with amine- and alkoxy-terminated dithiocarbamates
DOI:10.1039/b925536b
Keywords:MIXED-DONOR LIGANDS, DIYNE COORDINATION CHEMISTRY, SIGMA-ORGANYL COMPLEXES, RAY CRYSTAL-STRUCTURE, MOLECULAR-STRUCTURES, TRANSFER HYDROGENATION, INSERTION REACTIONS, ALKYNYL COMPLEXES, BUILDING-BLOCKS, VINYL
UCL classification:UCL > School of BEAMS > Faculty of Maths and Physical Sciences > Chemistry

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