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Reactivity of Cyclopentadienyl Molybdenum Compounds towards Formic Acid: Structural Characterization of CpMo(PMe 3 )(CO) 2 H, CpMo(PMe 3 ) 2 (CO)H, [CpMo(μ-O)(μ-O 2 CH)] 2 , and [Cp*Mo(μ-O)(μ-O 2 CH)] 2 .

Inorganic Chemistry 2017 Februrary 7
The molecular structures of CpMo(PMe3 )(CO)2 H and CpMo(PMe3 )2 (CO)H have been determined by X-ray diffraction, thereby revealing four-legged piano-stool structures in which the hydride ligand is trans to CO. However, in view of the different nature of the four basal ligands, the geometries of CpMo(PMe3 )(CO)2 H and CpMo(PMe3 )2 (CO)H deviate from that of an idealized four-legged piano stool, such that the two ligands that are orthogonal to the trans H-Mo-CO moiety are displaced towards the hydride ligand. While CpR Mo(PMe3 )3-x (CO)x H (CpR = Cp, Cp*; x = 1, 2, 3) are catalysts for the release of H2 from formic acid, the carbonyl derivatives, CpR Mo(CO)3 H, are also observed to form dinuclear formate compounds, namely, [CpR Mo(μ-O)(μ-O2 CH)]2 . The nature of the Mo···Mo interactions in [CpMo(μ-O)(μ-O2 CH)]2 and [Cp*Mo(μ-O)(μ-O2 CH)]2 have been addressed computationally. In this regard, the two highest occupied molecular orbitals of [CpMo(μ-O)(μ-O2 CH)]2 correspond to metal-based δ* (HOMO) and σ (HOMO-1) orbitals. The σ2 δ*2 configuration thus corresponds to a formal direct Mo-Mo bond order of zero. The preferential occupation of the δ* orbital rather than the δ orbital is a consequence of the interaction of the latter orbital with p orbitals of the bridging oxo ligands. In essence, lone-pair donation from oxygen increases the electron count so that the molybdenum centers can achieve an 18-electron configuration without the existence of a Mo-Mo bond, whereas a Mo═Mo double bond is required in the absence of lone-pair donation.

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