期刊
CHEMICAL SCIENCE
卷 4, 期 11, 页码 4212-4222出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c3sc51797g
关键词
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资金
- EPSRC
- University of Bath
- EPSRC [EP/I014519/1] Funding Source: UKRI
- Engineering and Physical Sciences Research Council [EP/I014519/1] Funding Source: researchfish
The homoleptic alkaline earth hexamethyldisilazides, [M{N(SiMe3)(2)}(2)](2) (1:M = Mg; 2: M = Ca; 3: M = Sr), have been demonstrated as active pre-catalysts for the cross-dehydrocoupling of Si-H and N-H bonds under mild (25-60 degrees C) conditions. The reactions are applicable to the coupling of a wide variety of amine and silane substrates and are proposed to occur via a sequence of discrete Si-H/M-N and N-H/M-H metathesis steps. Whereas reactions of dialkyl group 2 species with 2,6-di-iso-propylaniline and phenylsilane delivered a series of well-defined compounds consistent with this rationale, kinetic analysis of the cross-coupling of diethylamine with diphenylsilane provided evidence for a more complex and subtly variable mechanistic landscape. Although reactions performed with all three pre-catalysts presented a number of common features, in every case the calcium species, 2, was found to provide notably superior catalytic activity, an order of magnitude higher than both 1 and 3 and in excess of many previously described benchmark transition metal- or f-element-mediated processes. Variations in overall reaction order, mode of pre-catalyst activation and the nature of the rate determining process are postulated to arise as a consequence of the marked change in M2+ radius and resultant charge density as group 2 is descended.
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