Efficient Synthesis and Multisite Reactivity of a Phosphinidene-Bridged Mo–Re Complex. A Platform Combining Nucleophilic and Electrophilic Features
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https://figshare.com/articles/dataset/Efficient_Synthesis_and_Multisite_Reactivity_of_a_Phosphinidene-Bridged_Mo_Re_Complex_A_Platform_Combining_Nucleophilic_and_Electrophilic_Features/12616603
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资源简介：
The heterometallic
complex [MoReCp(μ-PR*)(CO)6] (3) was
prepared in 60% overall yield from syn-[MoCp(PHR*)(CO)2] via a three-step procedure
involving complexes syn-[MoCp(PClR*)(CO)2] and [MoReCp(μ-PR*)(CO)7] as intermediate species
(R* = 2,4,6-C6H2tBu3). The PR* ligand in 3 displays a novel
asymmetric interaction with the dimetal center, involving a double
bond with one atom (Mo) and a dative single bond with the other one
(Re). Compound 3 underwent thermal isomerization involving
a C–H bond cleavage to yield the hydride [MoReCp(μ-H){μ-P(CH2CMe2)C6H2tBu2}(CO)6] and reacted with I2 to give [MoReCpI2(μ-PR*)(CO)6], which displays a symmetrical phosphinidene bridge. Its reaction
with methyl propiolate at 293 K proceeded with [2 + 2] cycloaddition
of the alkyne and decarbonylation to yield the phosphapropenylidene-bridged
complex [MoReCp{μ-κ2P,C:η3-PR*CHC(CO2Me)}(CO)5] as the major product,
whereas its reaction with excess CN(4-C6H4OMe)
at 273 K proceeded with formal [2 + 1] cycloaddition of the isocyanide
and further isocyanide addition at the Re site to yield the complex
[MoReCp{μ-η2P,C:κ1P-PR*CN(4-C6H4OMe)}(CO)6{CN(4-C6H4OMe)}], which displays an azaphosphaallene
ligand in a novel bridging coordination mode.
创建时间：
2020-07-06
