An Ylide-like Phosphasilene and Striking Formation of a 4π-Electron, Resonance-Stabilized 2,4-Disila-1,3-diphosphacyclobutadiene
An Ylide-like Phosphasilene and Striking Formation of a 4π-Electron, Resonance-Stabilized 2,4-Disila-1,3-diphosphacyclobutadiene
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DOI：
10.1021/ja200462y
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发表时间：
2011-03-09
影响因子：
15
通讯作者：
Driess, Matthias
中科院分区：
文献类型：
--
作者：
Inoue, Shigeyoshi;Wang, Wenyuan;Driess, Matthias
通过（Me3Si）(2) p取代的n杂环硅烯[LSi- p -(SiMe3)(2)]的1,2-硅基迁移，合成了首个n给体稳定的磷酸硅烯LSi(SiMe3)=PSiMe3 (L = PhC(NtBu)(2))，产率为87%。值得注意的是，后者与二氯三苯基磷烷Ph3PCl2反应，产生了前所未有的具有双配位磷原子的4个电子si2p2 -环异丁二烯[(LSi)(2)P-2]。两种产物的分子结构以及Si-29和P-31核磁共振谱特征表明存在两性离子Si=P键，这也与DFT计算结果一致。
The first N-donor-stabilized phosphasilene LSi(SiMe3)=PSiMe3 (L = PhC(NtBu)(2)) has been synthesized in 87% yield through 1,2-silyl migration of the (Me3Si)(2)P-substituted, N-heterocyclic silylene [LSi-P-(SiMe3)(2)]. Remarkably, the latter reacts with dichlorotri-phenylphosphorane Ph3PCl2 to give the unprecedented 4 pi-electron Si2P2-cycloheterobutadiene [(LSi)(2)P-2] with two-coordinate phosphorus atoms. The striking molecular structures as well as the Si-29 and P-31 NMR spectroscopic features of both products indicate the presence of zwitterionic Si=P bonds which is also in accordance with results by DFT calculations.