Metal coordination to a dimetallaoctatetrayne

Abstract

The reactions of the ditungstaoctatetrayne [(Tp*)(CO)₂W(CCCCCC)W(CO)₂(Tp*)] with several metal complexes have been investigated. Addition of [Co₂(CO)₈] occurs across the internal CC bonds, whereas [AuCl(SMe₂)] initially delivers ‘AuCl’ across the WC carbyne bonds before undergoing further reaction to oxidise the tungsten and replace the carbonyl ligands with chloride in [(Tp*)Cl₂W(CCCCCC)WCl₂(Tp*)] with retention of the ditungstaoctatetrayne bridge. Reaction with [AuCl(PR₃)] (R = Ph, Cy) in the presence of AgPF₆ prevents this oxidation and adds [AuPR₃]⁺ across the WC 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.