Hydroboration of Disilyne RSiSiR (R = Si^<i>i</i>Pr[CH(SiMe₃)₂]₂), Giving Boryl-Substituted Disilenes

The reaction of 1,1,4,4-tetrakis[bis(trimethylsilyl)methyl]-1,4-diisopropyltetrasila-2-yne (1) with hydroboranes afforded boryl-substituted disilenes R(R′2B)SiSiHR 3a and 3b (R = SiiPr[CH(SiMe3)2]2, R′2B = 9-borabicyclo[3.3.1]nonan-9-yl (3a), catecholboryl (3b)). Spectroscopic and X-ray crystallographic analyses of 3a and 3b showed that 3a has a nearly coplanar arrangement of the SiSi double bond and the boryl group, allowing π-conjugation between them, whereas 3b, with a markedly twisted arrangement, exhibits no such conjugation. Theoretical calculations suggest that π-conjugation between the π-orbital of the SiSi double bond and the vacant 2p-orbital on the boron atom is markedly influenced by the dihedral angle between the SiSi double-bond plane and boryl group plane.