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The title complexes (1a,b) were prepared in two steps by first reacting the hydrides [M 2 Cp 2 (μ-H)(μ-PCy 2 )(CO) 4 ] with [NO](BF 4 ) in the presence of Na 2 CO 3 o give dinitrosyls [M 2 Cp 2 (μ-PCy 2 )(CO) 2 (NO) 2 ](BF 4 ), which were then fully decarbonylated upon reaction with NaNO 2 at 323 K. An isomer of the Mo 2 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 [FeCp 2 ](BF 4 ) to give first the radicals [M 2 Cp 2 (μ-PCy 2 )(μ-NO)(NO) 2 ](BF 4 ) according to CV experiments, which then underwent H-abstraction to yield the nitroxyl-bridged complexes [M 2 Cp 2 (μ-PCy 2 )(μ-κ 1 :η 2 -HNO)(NO) 2 ](BF 4 ), alternatively prepared upon protonation with HBF 4 ·OE 2 . 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 [M 2 Cp 2 (μ-PCy 2 )( μ-κ 1 :η 2 -MeNO)(NO) 2 ] + were prepared by reacting 1a,b with CF 3 SO 3 Me or [Me 3 O]BF 4 . Complexes 1 reacted with M(Hg) (M = Zn, Na) in tetrahydrofuran to give the amido-bridged derivatives [M 2 Cp 2 (μ-PCy 2 )(μ-NH 2 )(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 Mo 2 complexes to yield the phosphoraniminato-bridged derivatives [Mo 2 Cp 2 (μ-PCy 2 ){μ-NP(OR) 3 }(NO) 2 ] (R = Et, Ph), also with retention of stereochemistry.

inorganic chemistry

N–O Bond Activation and Cleavage Reactions of the Nitrosyl-Bridged Complexes [M2Cp2(μ-PCy2)(μ-NO)(NO)2] (M = Mo, W)