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N-O Bond Activation and Cleavage Reactions of the Nitrosyl-Bridged Complexes [M 2 Cp 2 (μ-PCy 2 )(μ-NO)(NO) 2 ] (M = Mo, W).

Inorganic Chemistry 2018 November 22
The title complexes (1a,b) were prepared in two steps by first reacting the hydrides [M2 Cp2 (μ-H)(μ-PCy2 )(CO)4 ] with [NO](BF4 ) in the presence of Na2 CO3 to give dinitrosyls [M2 Cp2 (μ-PCy2 )(CO)2 (NO)2 ](BF4 ), which were then fully decarbonylated upon reaction with NaNO2 at 323 K. An isomer of the Mo2 complex having a cisoid arrangement of the terminal ligands ( cis-1a) was prepared upon irradiation of toluene solutions of 1a with visible-UV light at 288 K. The structure of these trinitrosyl complexes was investigated using X-ray diffraction and density functional theory (DFT) calculations, these revealing a genuine pyramidalization of the bridging NO that might be associated in part to an increase of charge at the N atom and anticipated a weakening of the N-O bond upon reaction with bases or reducing reagents. Complexes 1a,b reacted with [FeCp2 ](BF4 ) to give first the radicals [M2 Cp2 (μ-PCy2 )(μ-NO)(NO)2 ](BF4 ) according to CV experiments, which then underwent H-abstraction to yield the nitroxyl-bridged complexes [M2 Cp2 (μ-PCy2 )(μ-κ1 :η2 -HNO)(NO)2 ](BF4 ), alternatively prepared upon protonation with HBF4 ·OEt2 . The novel coordination mode of the nitroxyl ligand in these products was thermodynamically favored over its tautomeric hydroximido form, according to DFT calculations, and similar nitrosomethane-bridged cations [M2 Cp2 (μ-PCy2 )( μ-κ1 :η2 -MeNO)(NO)2 ]+ were prepared by reacting 1a,b with CF3 SO3 Me or [Me3 O]BF4 . Complexes 1 reacted with M(Hg) (M = Zn, Na) in tetrahydrofuran to give the amido-bridged derivatives [M2 Cp2 (μ-PCy2 )(μ-NH2 )(NO)2 ] with retention of stereochemistry, a transformation also induced by using mild O atom scavengers such as CO and phosphites in the presence of water. In the absence of water, phosphites accomplished a deoxygenation of the bridging NO of the Mo2 complexes to yield the phosphoraniminato-bridged derivatives [Mo2 Cp2 (μ-PCy2 ){μ-NP(OR)3 }(NO)2 ] (R = Et, Ph), also with retention of stereochemistry.

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