Alvarez M Angeles, García M Esther, García-Vivó Daniel, Ruiz Miguel A, Vega Patricia
Departamento de Química Orgánica e Inorgánica, Instituto de Quı́mica Organometálica Enrique Moles, Universidad de Oviedo, E33071 Oviedo, Spain.
Inorg Chem. 2020 Jul 20;59(14):9481-9485. doi: 10.1021/acs.inorgchem.0c01554. Epub 2020 Jul 6.
The heterometallic complex [MoReCp(μ-PR*)(CO)] () was prepared in 60% overall yield from -[MoCp(PHR*)(CO)] via a three-step procedure involving complexes -[MoCp(PClR*)(CO)] and [MoReCp(μ-PR*)(CO)] as intermediate species (R* = 2,4,6-CHBu). The PR* ligand in 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 underwent thermal isomerization involving a C-H bond cleavage to yield the hydride [MoReCp(μ-H){μ-P(CHCMe)CHBu}(CO)] and reacted with I to give [MoReCpI(μ-PR*)(CO)], 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-κ:η-PRCHC(COMe)}(CO)] as the major product, whereas its reaction with excess CN(4-CHOMe) 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-η:κ-PRCN(4-CHOMe)}(CO){CN(4-CHOMe)}], which displays an azaphosphaallene ligand in a novel bridging coordination mode.
异金属配合物[MoReCp(μ-PR*)(CO)] ()通过三步反应由-[MoCp(PHR*)(CO)]制备得到，总产率为60%，反应过程涉及中间体-[MoCp(PClR*)(CO)]和[MoReCp(μ-PR*)(CO)]（R* = 2,4,6-CHBu）。 中的PR配体与双金属中心存在一种新型不对称相互作用，涉及与一个原子（Mo）形成双键，与另一个原子（Re）形成配位单键。化合物 发生热异构化反应，涉及C-H键断裂，生成氢化物[MoReCp(μ-H){μ-P(CHCMe)CHBu}(CO)]，并与I反应生成[MoReCpI(μ-PR)(CO)]，该化合物具有对称的磷烯桥。它在293 K下与丙酸甲酯反应，炔烃进行[2 + 2]环加成和脱羰基反应，生成磷丙烯叉桥连配合物[MoReCp{μ-κ:η-PRCHC(COMe)}(CO)]作为主要产物，而它在273 K下与过量的CN(4-CHOMe)反应，异氰化物进行形式上的[2 + 1]环加成，并在Re位点进一步加成异氰化物，生成配合物[MoReCp{μ-η:κ-PRCN(4-CHOMe)}(CO){CN(4-CHOMe)}]，该化合物以新型桥连配位模式展示了氮杂磷丙二烯配体。
