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The coordination chemistry of the title diphosphine-borane adduct at heterometallic MoRe centers was examined through its reactions with the hydride complex [MoReCp(μ-H)(μ-PCy 2 )(CO) 5 (NCMe)] (Cp = η 5 -C 5 H 5 ). The latter reacted rapidly with stoichiometric amounts of dppm·BH 3 (dppm = Ph 2 PCH 2 PPh 2 ) in refluxing toluene solution, with displacement of the nitrile ligand, to give [MoReCp(μ-H)(μ-PCy 2 )(CO) 5 (κ 1  P -dppm·BH 3 )], with a P -bound diphosphine-borane ligand arranged rans o the PCy 2 group. Decarbonylation of the latter complex was accomplished rapidly upon irradiation with visible-UV light in toluene solution at 263 K, to give the agostic derivative [MoReCp(μ-H)(μ-PCy 2 )(CO) 4 (κ 1  P ,η 2 -dppm·BH 3 )] as major product (Mo-Re = 3.2075(5) Å), along with small amounts of the diphosphine-bridged complex [MoReCp(μ-H)(μ-PCy 2 )(CO) 4 (μ-dppm)]. Extended photolysis of the agostic complex at 288 K promoted an unprecedented dehydrogenation process involving the borane group and the hydride ligand, to give the diphosphine-boryl complex [MoReCp(μ-η 2 :κ 2  P,B -H 2 B·dppm)(μ-PCy 2 )(CO) 4 ] (Mo-Re = 3.075(1) Å). The latter displayed a boryl ligand in a novel bridging coordination mode, it being σ-bound to one of the metal atoms (B-Re = 2.38(2) Å) while interacting with the second metal atom via a strong side-on ricentric B-H-M interaction (B-Mo = 2.31(1); H-Mo = 1.9(1) Å). The overall dehydrogenation process was endergonic by 43 kJ/mol, according to density functional theory calculations.

inorganic chemistry

Coordination and Dehydrogenation of Diphosphine–Borane Ph2PCH2PPh2·BH3 at a Heterometallic MoRe Center to Give an Agostic Boryl-Bridged Derivative