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The absolute rate constants for quenching of the transient absorption assigned to dimesitylgermylene with oxygen, triethylsilane, ethanol, and 1-bromohexane have been determined by nanosecond laser flash photolysis to be (7.3 ± 0.8) × 106, (1.1 ± 0.1) × 105, <103, and (5.4 ± 0.5) × 105 M-1 s-1, respectively. The rate constants are compared to those obtained for the quenching of dimethyl- and diphenylgermylene and dimesitylsilylene.

The preparation and photolysis (350 nm) of Si, Si'-di-terf-butyltetramesitylsiladigermirane, 1, has been investigated. The structure of the siladigermirane 1 has been determined by x-ray crystallography: crystals are monoclinic, space group C2/c with Ζ = 4 in a unit cell of dimensions a = 11.5830(9) A, b = 21.268(3) A, c = 17.534(2) A and β = 108.60(1)°. The structure was solved by direct methods and refined by full-matrix least squares on F 2 on the basis of 2361 observed reflections (Ι>2σ(Ι)) to R, and wR 2 values of 0.0495 and 0.0939, respectively. Photolysis of 1 in the presence of methanol gave two major products: MeSjGehKOMe) and i-Bu 2 Si(OMe)GeHMes 2 , 2 in a 1:1 ratio.Similarly, photolysis of 1 in the presence of water led to the isolation of f-Bi^SKOhOGeHMeSz, 3. The formation of compounds 2 and 3 is best explained by the regioselective photochemical cleavage of the siladigermirane to give MeSzGe: and /-Bu 2 Si=GeMes2, 4, followed by trapping of the germasilene, regioseledively, by water and methanol. Attempts to prepare a solution of germasilene 4 by photolysis of siladigermirane 1 in triethylsilane, a selective trapping reagent for MeSjGe:, were unsuccessful. The germasilene 4 undergoes photodissociation to yield another equivalent of Mes^e: and f-Bu 2 Si:, which were subsequently trapped by the silane.Brought to you by | Purdue University Libraries Authenticated Download Date | 5/27/15 7:32 PM

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