Sterically encumbered metalla-diphosphines: unlocking alkyne rotation by PtII coordination

We present the synthesis and coordination chemistry of a series of WII alkyne complexes with symmetric and asymmetric acetylene diphosphines. Chelate-like P,P′-coordination of PtCl2 cause a drastic potential change of the W centered oxidation proving intermetallic cooperativity. The choice of peripheric P-substituents has a measurable influence on the potential itself as well on the respective potential change upon coordination. The enlarged deviation of the diphosphino alkyne from linearity in the dinuclear complexes unlock alkyne rotation making different isomers accessible.