Synthesis, structure, and reactivity of a pyridine-stabilized silanonetungsten complex

Abstract

A pyridine-stabilized silanonetungsten complex Cp*(OC)₂W{OSiMes₂(py)}(SiMe₃) (1b, Cp* = η⁵-C₅Me₅, Mes = 2,4,6-Me₃C₆H₂, py = C₅H₅N) was obtained by the reaction of a silyl(silylene) complex Cp*(OC)₂W(SiMes₂)(SiMe₃) (3) with pyridine-N-oxide in pyridine. X-ray crystal structure determination revealed that complex 1b shows a similar geometry to that observed for a previously synthesized DMAP-stabilized analogue, Cp*(OC)₂W{OSiMes₂(DMAP)}(SiMe₃) (1a, DMAP = 4-NMe₂C₆H₄N). The SiO and W–O bond distances in 1b are comparable to those observed in 1a, but the nitrogen to silicon coordination bond of 1b is slightly longer (ca. 0.05 Å) than that of 1a, indicating the weaker coordination of pyridine than that of DMAP. The reaction of 1b with excess PMe₃ in C₆D₆ at r. t. proceeded via elimination of pyridine to afford a five-membered metallacyclic carbene complex, Cp*(OC)W(C(SiMe₃)OSiMes₂O)(PMe₃) (5), but that of 1a with PMe₃ did not proceed at all. Complex 5 was further transformed in C₇D₈ at 100 °C for 4 h to give a four-membered W–O–Si–O metallacyclic complex with carbyne and PMe₃ ligands, Cp*W(OSiMes₂O)(CSiMe₃)(PMe₃) (7). The structural features of complexes 1b, 5, and 7 are comparable to those suggested theoretically as intermediates in the reaction of 3 with a sulfuration reagent to afford a six-membered metallacyclic carbene complex, Cp*W(S){C(SiMe₃)C(O)OSiMes₂S} (6), indicating that complex 1b and the theoretically proposed silanethione complex are transformed via a similar reaction pathway.