Carbene- and Carbyne-like Behavior of the Mo-P Multiple Bond in a Dimolybdenum Complex Inducing Trigonal-Pyramidal Coordination of a Phosphinidene Ligand
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- 作者：M. Angeles Alvarez ; Inmaculada Amor ; M. Esther Garcí ; a ; Daniel Garcí ; a-Vivó ; Miguel A. Ruiz
- 刊名：Inorganic Chemistry
- 出版年：2007
- 出版时间：August 6, 2007
- 年：2007
- 卷：46
- 期：16
- 页码：6230 - 6232
- 全文大小：111K
- 年卷期：v.46,no.16(August 6, 2007)
- ISSN：1520-510X
文摘
The phosphinidene complex [Mo2Cp(
-
1:1,
5-PC5H4)(CO)2(6-R*H)] (2; Cp = 5-C5H5; R* = 2,4,6-C6H2tBu3) has substantiallydifferent Mo-P bonds and displays a high reactivity located at theshort Mo-P bond. Sideways cycloaddition or addition processesare observed toward RC
CR, HCl, and [Fe2(CO)9], to giverespectively metallacyclobutene and arylphosphide-bridged andheterometallic phosphinidene-bridged derivatives, a behaviorreminiscent of the nucleophilic mononuclear phosphinidene complexes (carbene-like behavior), which is in good agreement withthe ground-state electronic structure of 2 derived from densityfunctional theory calculations. However, the reaction of 2 with [Co2(CO)8] implies the addition of two cobalt fragments to its shortMo-P bond and thus reveals a carbyne-like behavior of compound2. In most of the new products, the P atom displays anunprecedented trigonal-pyramidal-like environment, instead of theexpected tetrahedral distribution of bonds.
-1:1,5-PC5H4)(CO)2(6-R*H)] (2; Cp = 5-C5H5; R* = 2,4,6-C6H2tBu3) has substantiallydifferent Mo-P bonds and displays a high reactivity located at theshort Mo-P bond. Sideways cycloaddition or addition processesare observed toward RCCR, HCl, and [Fe2(CO)9], to giverespectively metallacyclobutene and arylphosphide-bridged andheterometallic phosphinidene-bridged derivatives, a behaviorreminiscent of the nucleophilic mononuclear phosphinidene complexes (carbene-like behavior), which is in good agreement withthe ground-state electronic structure of 2 derived from densityfunctional theory calculations. However, the reaction of 2 with [Co2(CO)8] implies the addition of two cobalt fragments to its shortMo-P bond and thus reveals a carbyne-like behavior of compound2. In most of the new products, the P atom displays anunprecedented trigonal-pyramidal-like environment, instead of theexpected tetrahedral distribution of bonds.