Metal coordination to a dimetallaoctatetrayne

The reactions of the ditungstaoctatetrayne [(Tp*)(CO) 2 W(&z.tbd;CC&z.tbd;CC&z.tbd;CC&z.tbd;)W(CO) 2 (Tp*)] with several metal complexes have been investigated. Addition of [Co 2 (CO) 8 ] occurs across the internal C&z.tbd;C bonds, whereas [AuCl(SMe 2 )] initially delivers 'AuCl' across the W&z.tbd;C carbyne bonds before undergoing further reaction to oxidise the tungsten and replace the carbonyl ligands with chloride in [(Tp*)Cl 2 W(&z.tbd;CC&z.tbd;CC&z.tbd;CC&z.tbd;)WCl 2 (Tp*)] with retention of the ditungstaoctatetrayne bridge. Reaction with [AuCl(PR 3 )] (R = Ph, Cy) in the presence of AgPF 6 prevents this oxidation and adds [AuPR 3 ] + across the W&z.tbd;C bonds to give dicationic derivatives. Finally, the reaction with [Pt(nbe) 3 ] (nbe = norbornene, bicyclo[2.2.1]hept-2-ene) and 1,5-cyclooctadiene (COD) adds a 'Pt(COD)' unit to one or both tungsten-carbon bonds, allowing both the mono- and diplatinum complexes to be isolated. The ditungstaoctatetrayne [(Tp*)(CO) 2 W&z.tbd;CC&z.tbd;CC&z.tbd;CC&z.tbd;W(CO) 2 (Tp*)] (Tp* = hydrotris(dimethylpyrazolyl)borate) regioselectively adds extraneous metal-ligand fragments to the internal C&z.tbd;C or terminal W&z.tbd;C triple bonds leading to new tri-, tetra- or hexametallic assemblies.