Rearrangement of bis(alkylidynyl)phosphines to phospha-acyls
Rearrangement of bis(alkylidynyl)phosphines to phospha-acyls
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DOI：
10.1039/c6cc09764b
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发表时间：
2017-02-07
影响因子：
4.9
通讯作者：
Ward, Jas S.
中科院分区：
文献类型：
--
作者：
Colebatch, Annie L.;Han, Yong-Shen;Ward, Jas S.
通过[M(相当于ClI)(CO)(2)(Tp*)]与Cl2PR反应或通过钯(0)介导的[W(相当于CBr)(CO)(2)(Tp*)]与RP2(R=Py，Cy)的反应，得到了一系列双(烷基)基膦Rp{C相当于M(CO)(Tp*)}(2)(M=Mo，W；R=Cl，Ph，Cy；Tp*=氢化三(二甲基吡唑基)硼酸盐)。配合物Rp{C相当于W(CO)(2)(Tp*)}(2)缓慢重排(R=Cl)或加热(R=Ph)得到同分异构体[W-2(Mu：ETA(1)-C；ETA(2)-C，P-CCPR)(CO)(4)(Tp*)(2)]。
A range of bis(alkylidynyl)phosphines RP{C equivalent to M(CO)(2)(Tp*)}(2) (M = Mo, W; R = Cl, Ph, Cy; Tp* = hydrotris(dimethylpyrazolyl)borate) are obtained from the reactions of [M(equivalent to CLi)(CO)(2)(Tp*)] with Cl2PR or alternatively via the palladium(0)-mediated reactions of [W(equivalent to CBr)(CO)(2)(Tp*)] with RPH2 (R = Py, Cy). The complexes RP{C equivalent to W(CO)(2)(Tp*)}(2) rearrange slowly (R = Cl) or on heating (R = Ph) to afford the isomeric phosphaacyls [W-2(mu:eta(1)-C; eta(2)-C,P-CCPR)(CO)(4)(Tp*)(2)].