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

A pyridine-stabilized silanonetungsten complex Cp*(OC)₂W{O[double bond, length as m-dash]SiMes₂(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([double bond, length as m-dash]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{O[double bond, length as m-dash]SiMes₂(DMAP)}(SiMe₃) (1a, DMAP = 4-NMe₂C₆H₄N). The Si[double bond, length as m-dash]O 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([double bond, length as m-dash]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)([triple bond, length as m-dash]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){[double bond, length as m-dash]C(SiMe₃)C([double bond, length as m-dash]O)OSiMes₂S} (6), indicating that complex 1b and the theoretically proposed silanethione complex are transformed via a similar reaction pathway.