Structural Distortions in M[E(SiMe3)2]3 Complexes (M = Group 15, f-Element; E = N, CH): Is Three a Crowd?

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• 作者：Nicholas C. Boyde ; Stephen C. Chmely ; Timothy P. Hanusa ; Arnold L. Rheingold ; William W. Brennessel
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：September 15, 2014
• 年：2014
• 卷：53
• 期：18
• 页码：9703-9714
• 全文大小：503K
• ISSN：1520-510X

文摘

The tris(bistrimethylsilylamido) species P[N(SiMe₃)₂]₃ (1) and As[N(SiMe₃)₂]₃ (2) have been prepared through halide metathesis in high yield. Their single crystal X-ray structures, along with that of Sb[N(SiMe₃)₂]₃ (3), complete the series of structurally authenticated group 15 M[N(SiMe₃)₂]₃ complexes (the bismuth analogue (4) has been previously reported). All four complexes possess the expected pyramidal geometries, with progressively longer M鈥揘 bond distances from P to Bi but closely similar N鈥揗鈥揘 angles (107鈥?04掳). The structures of 1鈥?b>4 also display distortions that are similar to those in f-element M[N(SiMe₃)₂]₃ and M[CH(SiMe₃)₂]₃ complexes, in which M路路路(尾-Si鈥揅) interactions have been identified. Such structural features include distorted M鈥?N,CH)鈥揝i and (N,CH)鈥揝i鈥揅 angles and close M路路路C and M路路路Si contacts. DFT calculations confirm that there are no M路路路(尾-Si鈥揅) interactions in 1鈥?b>4; the bond distortions appear to result from the particular steric crowding that arises in pyramidal M[(N,CH)(SiMe₃)₂]₃ complexes. This is likely the source of the most of the distortions in the structures of the f-element analogues as well, even though the latter possess attractive M路路路Si鈥揅 interactions.