Peter Blenkiron

From butadiynyl (–CC–CCR) ligands to alkylidyne–carbides: synthesis and characterisation of the unusual hexanuclear ruthenium carbido clusters [Ru6(CO)13(µ-CO)2(µ-PPh2)(µ5-C)(µ3-C–CCR)](R = But, Ph)

The preparation from [Ru3(CO)11(PPh2CC-CC–R)](R = But, Ph) of the hexanuclear complexes [Ru6(CO)13(µ-CO)2(µ-PPh2)(µ5-C)(µ3-C–CCR)](R = But1, Ph 2) containing a novel alkylidyne–carbide ligand is described; the structure of 1 is determined by a single-crystal X-ray diffraction study.

Chemistry of µ-η1: η2α,β-butadiynyls: chain extension on C4 polycarbon ligands

The binuclear butadiynyl compounds Ru2(CO)6(µ-η1, η2α, β-CC-CCR)(µ-PPh2)(R = But1a or Ph 1b), with one π-coordinated and one free triple bond, synthesised via thermolysis of Ru3(CO)11(PPh2CC-CCR), react with NEt2H to generate the novel diethylaminobutatriene complexes Ru2(CO)6[µ-η1, η1-Et2NCCCC(H)R](µ-PPh2)(R = But2a or Ph 2b) in high yields: the molecular structures of 1a and 2a are determined.

Polycarbon ligand chemistry. Novel behaviour ofµ-η1,η2α,β-butadiynyls towards metal fragment additions

Reaction of [Ru 2 (CO) 6 (µ-PPh 2 )(µ-η 1 ,η 2 α,β -CC–C CR)] (R = Bu t 1a, Ph 1b) with the labile complexes [Pt(PPh 3 ) 2 (η-C 2 H 4 ], [Pt(dppb)(η-C 2 H 4 )] and [Ni(cod) 2 ] or [Ni(CO) 4 ] leads to the heteronuclear derivatives [Ru 2 Pt(CO) 7 (PPh 3 )(µ 3 -η 1 ,η 1 ,η 1 -CC–C CR)(µ-PPh 2 )] 2a,b, [Ru 2 Pt(CO) 6 (dppb)(µ 3 -η 1 ,η 1 ,η 1 -CC–CCBu t )(µ-PPh 2 )] 2c and [Ru 4 Ni(CO) 12 (µ-PPh 2 ) 2 (µ 4 -η 1 ,η 1 ,η 2 ,η 4 -Bu t CCC 4 CC-Bu t )] 3 resulting from addition of a PtL 2 fragment and Ni-assisted stoichiometric coupling of two molecules of 1a respectively; the X-ray crystal structures of 2a and 3 are described.