Mild N–O Bond Cleavage Reactions of a Pyramidalized Nitrosyl Ligand Bridging a Dimolybdenum Center
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Complex [Mo2Cp2(μ-PCy2)(μ-NO)(NO)2] (1) was prepared by reacting [Mo2Cp2(μ-H)(μ-PCy2)(CO)4] with 2 equiv of [NO]BF4 and then treating the resulting product [Mo2Cp2(μ-PCy2)(CO)2(NO)2](BF4) with NaNO2 at 323 K, and it was shown to display a bridging nitrosyl ligand with significant pyramidalization at the N atom, a circumstance related to an unusual behavior concerning degradation of the bridging nitrosyl. Indeed, complex 1 reacts with HBF4·OEt2 to give the nitroxyl-bridged derivative [Mo2Cp2(μ-PCy2)(μ-κ1:η2-HNO)(NO)2](BF4), is reduced by Zn(Hg) in the presence of trace H2O to give the amido complex [Mo2Cp2(μ-PCy2)(μ-NH2)(NO)2], and reacts with excess P(OPh)3 to give the phosphoraniminato-bridged derivative [Mo2Cp2(μ-PCy2){μ-NP(OPh)3}(NO)2].
