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-C₆H₂^tBu₃). 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)C₆H₂^tBu₂}(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-κ²_P,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-η²_P,C:κ¹_P-PR*CN(4-C₆H₄OMe)}(CO)₆{CN(4-C₆H₄OMe)}], which displays an azaphosphaallene ligand in a novel bridging coordination mode.

中文翻译：

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膦亚膦酸酯键合的Mo-Re配合物的高效合成和多中心反应性。结合亲核和亲电子功能的平台。

的异金属配合物[MoReCp（μ-PR *）（CO）₆ ]（3）中的溶液在60％的总收率制备从顺式- [MOCP（PHR *）（CO）₂ ]通过涉及复合物的三步骤过程顺式- [MoCp（PClR *）（CO）₂ ]和[MoReCp（μ-PR*）（CO）₇ ]作为中间物种（R * = 2,4,6-C ₆ H ₂ ^t Bu ₃）。所述PR *配体在3只显示与双金属中心一个新的不对称相互作用，包括用一个原子（Mo）和与其他一个（Re）的配价单键双键。化合物3进行热异构化涉及CH键断裂，得到氢化物[MoReCp（μ-H）{μ-P（CH ₂ CME ₂）C ₆ H ^ ₂^吨卜₂ }（CO）₆ ]和与I反应₂至得到[MoReCpI ₂（μ-PR*）（CO）₆ ]，该化合物显示出对称的次膦基桥。它与丙炔酸甲酯反应在293K与进行[2 + 2]的炔和脱羰，得到的环加成phosphapropenylidene桥连络合物[MoReCp {μ-κ ² _P，C：η ³ -PR * CHC（CO ₂ Me）的}（CO）₅]作为主要产物，而在273 K下与过量CN（4-C ₆ H ₄ OMe）的反应则进行了异氰酸酯的正式[2 + 1]环加成反应，并在Re位点进一步加了异氰化物，生成了复合物[MoReCp {μ-η ² _P，C：κ ¹ _P -PR * CN（4-C ₆ H ^ ₄ OME）}（CO）₆ {CN（4-C ₆ H ^ ₄ OME）}]，其显示一azaphosphaallene配体在一种新颖的桥接协调模式。