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Probing the non-innocent nature of an amino-functionalised β-diketiminate ligand in silylene/iminosilane systems.
Dalton Transactions ( IF 3.5 ) Pub Date : 2020-06-10 , DOI: 10.1039/d0dt01447h
Dinh Cao Huan Do 1 , Petra Vasko , M Ángeles Fuentes , Jamie Hicks , Simon Aldridge
Affiliation  

Electron-rich β-diketiminate ligands, featuring amino groups at the backbone β positions (“N-nacnac” ligands) have been employed in the synthesis of a range of silylene (SiII) complexes of the type (N-nacnac)SiX (where X = H, Cl, N(SiMe3)2, P(SiMe3)2 and Si(SiMe3)3). A combination of experimental and quantum chemical approaches reveals (i) that in all cases rearrangement to give an aza-butadienyl SiIV imide featuring a contracted five-membered heterocycle is thermodynamically favourable (and experimentally viable); (ii) that the kinetic lability of systems of the type (N-nacnac)SiX varies markedly as a function of X, such that compounds of this type can be isolated under ambient conditions for X = Cl and P(SiMe3)2, but not for X = H, N(SiMe3)2 and Si(SiMe3)3; and (iii) that the ring contraction process is most facile for systems bearing strongly electron-donating and sterically less encumbered X groups, since these allow most ready access to a transition state accessed via intramolecular nucleophilic attack by the SiII centre at the β-carbon position of the N-nacnac ligand backbone.

中文翻译:

探索甲硅烷基/亚氨基硅烷体系中氨基官能化的β-二酮基配体的非清白性质。

富含电子的β-二酮配体(在主链β位置具有氨基基团)(“ N-nacnac”配体)已用于合成一系列(N-nacnac)SiX类型的甲硅烷基(Si II)配合物(其中X = H,Cl,N(SiMe 32,P(SiMe 32和Si(SiMe 33)。实验方法和量子化学方法的结合揭示了(i)在所有情况下都进行重排以形成氮杂-丁二烯基Si IV具有收缩的五元杂环的酰亚胺在热力学上是有利的(并且在实验上可行);(ii)(N-nacnac)SiX型系统的动力学不稳定性随X的变化而显着变化,因此可以在环境条件下分离出X = Cl和P(SiMe 32的这类化合物,但不是X = H,N(SiMe 32和Si(SiMe 33;(iii)对于带有强电子给体和空间上较少受累的X基团的系统,环收缩过程最容易,因为这些基团最容易进入通过Si II分子内亲核攻击获得的过渡态 中心位于N-nacnac配体骨架的β-碳位置。
更新日期:2020-06-29
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