一条通往炔丙二炔配合物的[C + C]路线。

A [C + C] route to propargylidyne complexes.

作者信息

Hill Anthony F, Manzano Richard A

机构信息

Research School of Chemistry, The Australian National University, Canberra, ACT 2601, Australia.

出版信息

Dalton Trans. 2019 May 15;48(19):6596-6610. doi: 10.1039/c9dt00876d.

DOI:10.1039/c9dt00876d

PMID:31017161

Abstract

The reactions of [W([triple bond, length as m-dash]CBr)(CO)2(Tp*)] (Tp* = hydrotris(dimethylpyrazolyl)borate) with a range of terminal alkynes (RC[triple bond, length as m-dash]CH), mediated by [Pd(PPh3)4] and CuI, afford new proparylidynes [W([triple bond, length as m-dash]C-C[triple bond, length as m-dash]CR)(CO)2(Tp*)] [R = tBu, C6H4X (X = H, NH2, NO2), ferrocenyl, APh3 (A = C, Si, Ge), B(O2CCH2)2NMe]. Similar treatment of [W([triple bond, length as m-dash]CBr)(CO)2(Tp*)] with Ph2Si(C[triple bond, length as m-dash]CH)2 affords the ditungstaoctatetrayne [W2(μ-C6)(CO)4(Tp*)2] while the bimetallic complex [W2{μ-([triple bond, length as m-dash]CC[triple bond, length as m-dash]C)2SiPh2}(CO)4(Tp*)2], which is obtained from [W([triple bond, length as m-dash]CBr)(CO)2(Tp*)] and Ph2Si(C[triple bond, length as m-dash]CSnPh3)2, reacts with [AuCl(THT)] (THT = tetrahydrothiophene) to provide the tetrametallic complex [W2Au2{μ-([triple bond, length as m-dash]CC[triple bond, length as m-dash]C)2SiPh2}Cl2(CO)4(Tp*)2].

摘要

在[Pd(PPh₃)₄]和CuI的介导下，[W(≡CBr)(CO)₂(Tp*)]（Tp* = 氢三(二甲基吡唑基)硼酸酯）与一系列末端炔烃（RC≡CH）反应，得到新的丙炔基化合物[W(≡C-C≡CR)(CO)₂(Tp*)] [R = tBu、C₆H₄X（X = H、NH₂、NO₂）、二茂铁基、APh₃（A = C、Si、Ge）、B(O₂CCH₂)₂NMe]。用Ph₂Si(C≡CH)₂对[W(≡CBr)(CO)₂(Tp*)]进行类似处理，得到二钨辛四炔[W₂(μ-C₆)(CO)₄(Tp*)₂]，而由[W(≡CBr)(CO)₂(Tp*)]和Ph₂Si(C≡CSnPh₃)₂制得的双金属配合物[W₂{μ-(≡CC≡C)₂SiPh₂}(CO)₄(Tp*)₂]与[AuCl(THT)]（THT = 四氢噻吩）反应，生成四金属配合物[W₂Au₂{μ-(≡CC≡C)₂SiPh₂}Cl₂(CO)₄(Tp*)₂]。