Spectroscopic and Structural Study of Some Oligosilanylalkyne Complexes of Cobalt, Molybdenum and Nickel

Metal induced stabilization of α-carbocations is well known for cobalt- and molybdenum complexed propargyl cations. The same principle also allows access to reactivity enhancement of metal coordinated halo- and hydrosilylalkynes. In a previous study, we have shown that coordination of oligosilanylalkynes to the dicobalthexacarbonyl fragment induces striking reactivity to the oligosilanyl part. The current paper extends this set of oligosilanylalkyne complexes to a number of new dicobalthexacarbonyl complexes but also to 1,2-bis(cyclopentadienyl)tetracarbonyldimolybdenum and (dippe)Ni complexes. NMR-Spectroscopic and crystallographic analysis of the obtained complexes clearly show that the dimetallic cobalt and molybdenum complexes cause rehybridization of the alkyne carbon atoms to sp³, while in the nickel complexes one π-bond of the alkyne is retained. For the dicobalt and dimolybdenum complexes, strongly deshielded ²⁹Si NMR resonances of the attached silicon atoms indicate enhanced reactivity, whereas the ²⁹Si NMR shifts of the respective nickel complexes are similar to that of respective vinylsilanes.