Structure, Bonding, and Reactivity of Binuclear Complexes Having Asymmetric Trigonal Phosphinidene Bridges: Addition of 16-Electron Metal Carbonyl Fragments to the Dimolybdenum Compounds [Mo<sub>2</sub>Cp(μ-κ<sup>1</sup>:κ<sup>1</sup>,η<sup>5</sup>-PC<sub>5</sub>H<sub>4</sub>)(CO)<sub>2</sub>L] and
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The phosphinidene-bridged complexes [Mo2Cp(μ-κ1:κ1,η5-PC5H4)(CO)2L] and [Mo2Cp2(μ-PH)(CO)2L] (Cp = η5-C5H5; L = η6-1,3,5-C6H3tBu3) react readily with [Fe2(CO)9] or the solvate complexes [M(CO)5(THF)] (M = Cr, Mo, W; THF = tetrahydrofuran) to give, as a result of the addition of the corresponding 16-electron M(CO)n fragments to their multiple Mo−P bonds, the trinuclear derivatives [FeMo2Cp(μ3-κ1:κ1:κ1,η5-PC5H4)(CO)6L], [MMo2Cp(μ3-κ1:κ1:κ1,η5-PC5H4)(CO)7L][FeMo2Cp2(μ3-PH)(CO)6L], and [MMo2Cp2(μ3-PH)(CO)7L]. The PH-bridged complexes display a distorted tetrahedral environment around their P atom, according to X-ray diffraction studies on the Fe, Cr, and W compounds, whereas the PC5H4-bridged ones display an unusual trigonal-pyramidal geometry around the P atoms (sum of M−P−M angles 359.6° for the Fe compound). The latter species were stable toward hydrolysis, whereas the trinuclear PH-bridged complexes underwent easy hydrolysis of their P−Mo(metallocene) bonds to give the corresponding PH2-bridged derivatives [FeMoCp(μ-PH2)(CO)6L] and [MMoCp(μ-PH2)(CO)7L] (M = Cr, Mo, W).
