Were Reactions of Triplet Silylenes Observed?

The observation that (iPr(3)Si)(tBu(3)Si)Si: (1) yields an intramolecular C-H bond insertion product at room temperature, together with earlier computational predictions that triplet 1 is slightly more stable (or isoenergetic) than singlet 1 and additional considerations, led previous investigators to conclude that 1 is the first silylene to exhibit triplet electronic state reactivity. In this paper we test, using DFT and ab initio methods, whether the occurrence of intramolecular C-H bond insertion indeed indicates the presence of a triplet-state silylene. DFT calculations at the B3LYP/6-31+G(d,p)//B3LYP/6-31+G(d,p) level show that singlet (iPr(3)Si)(tBuMe(2)Si)Si: (9), a close model of singlet 1, inserts intramolecularly into a C-H bond of the tBu group with a barrier of 22.7 kcal/mol (22.2 kcal/mol at SCS-MP2/cc-PVTZ). However, for triplet 9 the barrier of this insertion reaction is significantly higher, 34.6 kcal/mol (41.9 kcal/mol at SCS-MP2/cc-PVTZ). This implies that at room temperature the intramolecular insertion reaction of the singlet is 10(9)-10(12) faster than that of the triplet. We conclude, in contrast to previous conclusions, that the observed intramolecular C-H bond insertion reactions of 1 as well as of (tBu(3)Si)(2)Si: (2) occur from the singlet state. Furthermore, the occurrence of an intramolecular C-H bond insertion cannot serve as evidence for the presence of a triplet silylene, either in cases where the singlet and triplet states are nearly isoenergetic (e.g., 1 and 9) or even for silylenes where the triplet state is the ground state (e.g., 2), because the corresponding singlet silylenes insert intramolecularly much faster. The search for a genuine reaction of a triplet silylene has to continue.