ic5b02292_si_002.cif (135.76 kB)
Mild N–O Bond Cleavage Reactions of a Pyramidalized Nitrosyl Ligand Bridging a Dimolybdenum Center
dataset
posted on 2015-11-16, 00:00 authored by M. Angeles Alvarez, M. Esther García, Daniel García-Vivó, Miguel A. Ruiz, Adrián ToyosComplex
[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].
