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. Moreover, the bis(silyl)amine product is decoordinated from the metal center.

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. The distinct reactivity of complex 3 was rationalized by analysis of the molecular orbitals. Reaction of complex 3 with H afforded the unstable complex [( PP )Fe(η -P )(H)] (4), whereas with CuCl and BCF, the complexes [( PP )Fe(η :η -P )(μ-CuCl)] (5) and [( PP )Fe(η :η -P )B(C F ) ] (6) were formed.

Mechanistic investigations of the catalyzed reduction of N2 with a rare (tridentate phosphine)Fe(0) bis dinitrogen complex.

Ah omogeneous system which is able to yield silylamine from N 2 and bis(silane) in one pot is reported. Mechanistically a{ (triphosphine)molybdenum(I)} fragment, generated in situ, splits N 2 into the corresponding nitrido complex at room temperature.T hen, functionalization of the molybdenum nitrido is achieved by double Si À Ha ddition under mild reaction conditions.M oreover,t he bis(silyl)amine product is decoordinated from the metal center.

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...

Reduction of the Fe II complex [( Ph PP 2 Cy )FeCl 2 ]( 2) generated an electron-rich and unsaturated Fe 0 species,w hich was reacted with white phosphorus.T he resulting new complex, [( Ph PP 2 Cy )Fe(h 4 -P 4 )] (3), is the first iron cyclo-P 4 complex and the only knownstable end-deckcyclo-P 4 complex outside Group V. Complex 3 features an Fe II center,asshown by Mçssbauer spectroscopy, associated to aP 4 2À fragment. The distinct reactivity of complex 3 was rationalized by analysis of the molecular orbitals.Reaction of complex 3 with H + afforded the unstable complex [( Ph PP 2 Cy )Fe(h 4 -P 4 )(H)] + (4), whereas with CuCl and BCF,t he complexes [( Ph PP 2 Cy )Fe(h 4 :h 1 -P 4 )(m-CuCl)] 2 (5)a nd [( Ph PP 2 Cy )Fe(h 4 :h 1 -P 4 )B(C 6 F 5 ) 3 ]( 6)w ere formed. Conflict of interestTheauthors declare no conflict of interest.