Synthesis, crystal structure and heterometallic derivatives of [Mo2Cp2(μ-σ,π-CNtBu)(PPh2CH2PPh2-P)(CO)3] (tBu = C(CH3)3, Cp = η-C5H5)

https://doi.org/10.1016/0022-328X(90)80218-OGet rights and content

Abstract

The dppm ligand (Ph2PCH2PPh2) in [Mo2Cp2(CO)4(μ-dppm)] (Cp = η-C5H5) undergoes ring-opening upon reaction with NCMe or CNtBu (tBu = C(CH3)3), to give [MoCp(CO)(NCMe)(dppm)][MoCp(CO)3] or [Mo2Cp2(μ-σ,π-CNtBu)(dppm-P)(CO)3], respectively. The crystal structure of the latter complex is described as well as its reactions with sources of the metal fragments MLn [MLn: Fe(CO)4, Mo(CO)5, MnBr(CO)4, CuCl] to give the heterometallic species [MLn(μ-dppm)MoCp(CO)(μ-σ,π-CNtBu)MoCp(CO)2].

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    Citation Excerpt :

    Moreover we assume a transoid positioning of the CO ligands with respect to the P atom based on the absence of detectable P–C coupling (hence a large C–Mo–P angle) in the 13C NMR carbonyl resonance of 2b [22]. We finally note that the C–N stretches appear at frequencies a bit lower than expected for linear-terminal ligands [25], particularly in the case of the CNXyl derivative (2026 and 1993 cm−1), and this might denote a significant bending of the C–N–C chain in solution, perhaps due to steric constraints derived from the presence of the bulky R∗ group in the bridging region. In the same line, the isocyanide 13C NMR resonance of 2b (δ 200.2 ppm) appears more deshielded than expected for a linear-terminal isocyanide, also suggesting significant bending in solution.

  • Dinuclear Metal-Metal Bonded Systems

    2004, Comprehensive Coordination Chemistry II
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