Double α,α CH bond insertion into sp3CH2moiety: synthesis of a Fe carbene bis-hydride dinitrogen complex

Abstract

Reduction of high spin paramagnetic complex [(κ2-P, P′-PCH2PCy)FeCl2]2by two electrons under N2resulted in the formation of two isomeric low spin diamagnetic complexes3transand3cis[Fe(κ3-P,C,P′-PCPCy)(H)2(N2)]. Cristallization allowed isolation of complex3d[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 sp3CH2moiety, as well as the fast exchange positions of the hydrides in thecisdihydride complex observed by NMR spectrocscopy.