Stepwise Formation of -Alkynyl, Vinylidene, and Vinylphosphonium Complexes of Manganese(I)
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- 作者：Javier Ruiz ; Roberto Quesada ; Marilí ; n Vivanco ; Eduardo E. Castellano ; and Oscar E. Piro
- 刊名：Organometallics
- 出版年：2005
- 出版时间：May 9, 2005
- 年：2005
- 卷：24
- 期：10
- 页码：2542 - 2545
- 全文大小：98K
- 年卷期：v.24,no.10(May 9, 2005)
- ISSN：1520-6041
文摘
Reaction of methyl propiolate with the diphosphinomethanide complex [Mn(CO)4{(PPh2)2CH}] (1) produces simultaneously the insertion of the alkyne into theC-H bond, giving [Mn(CO)4{(PPh2)2C-C(H)=C(CO2Me)H}] (2), and the deprotonation of the alkyne mediatedby the diphosphinomethanide ligand, affording the
fchars/sigma.gif" BORDER=0 >-alkynyl derivative fac-[Mn(C
f">C-CO2Me)(CO)3(dppm)](3). Protonation of 3 with HBF4 at 200 K affords thecorresponding vinylidene compound fac-[Mn(C=C(H)CO2Me)(CO)3(dppm)]BF4 (5), which, on raising the temperature to 243 K, undergoes the spontaneous insertionof the vinylidene ligand into a Mn-P bond.
fchars/sigma.gif" BORDER=0 >-alkynyl derivative fac-[Mn(Cf">C-CO2Me)(CO)3(dppm)](3). Protonation of 3 with HBF4 at 200 K affords thecorresponding vinylidene compound fac-[Mn(C=C(H)CO2Me)(CO)3(dppm)]BF4 (5), which, on raising the temperature to 243 K, undergoes the spontaneous insertionof the vinylidene ligand into a Mn-P bond.