Double α,α CH bond insertion into sp CH moiety: synthesis of a Fe carbene bis-hydride dinitrogen complex.

Reduction of high spin paramagnetic complex [(κ2-P, P'-PCH2PCy)FeCl2] 2 by two electrons under N2 resulted in the formation of two isomeric low spin diamagnetic complexes 3trans and 3cis [Fe(κ3-P,C,P'-PCPCy)(H)2(N2)]. Cristallization allowed isolation of complex 3d [Fe(κ3-P,C,P'-PCPCy)(H)2]2(μ-N2), characterized by X-ray diffraction, Mössbauer and Raman spectroscopies. DFT calculations rationalized the facile double α,α CH bond insertion into a single sp3 CH2 moiety, as well as the fast exchange positions of the hydrides in the cis dihydride complex observed by NMR spectrocscopy.

Triphos-Fe dinitrogen and dinitrogen-hydride complexes: relevance to catalytic N reductions.

The two electron reduction of iron complexes [(PP)Fe(Cl)] (R = Ph or tBu) 2a-b afforded complexes [(PP)Fe(N)] 4a-b. Protonation of 4a at the metal center and subsequent reduction to Fe(i)-H species lead to complex [(PP)Fe(N)(H)] 6avia a spontaneous disproportionation reaction. Complex 4a behaves as one of the most efficient monometallic Fe-catalysts reported to date for N-to-N(SiMe) functionalization under atmospheric pressure.

Synthesis and Reactivity of an End-Deck cyclo-P Iron Complex.

Reduction of the Fe complex [( PP )FeCl ] (2) generated an electron-rich and unsaturated Fe species, which was reacted with white phosphorus. The resulting new complex, [( PP )Fe(η -P )] (3), is the first iron cyclo-P complex and the only known stable end-deck cyclo-P complex outside Group V. Complex 3 features an Fe center, as shown by Mössbauer spectroscopy, associated to a P fragment.

Direct Synthesis of Silylamine from N2 and a Silane: Mediated by a Tridentate Phosphine Molybdenum Fragment.

A homogeneous system which is able to yield silylamine from N2 and bis(silane) in one pot is reported. Mechanistically a {(triphosphine)molybdenum(I)} fragment, generated in situ, splits N2 into the corresponding nitrido complex at room temperature. Then, functionalization of the molybdenum nitrido is achieved by double Si-H addition under mild reaction conditions.