Hydrosilylation of an Iron(IV) Nitride Complex

The nitride ligand in iron(IV) complex PhB(MesIm) 3 Fe≡N reacts with excess H 3 SiPh to afford PhB(MesIm) 3 Fe(μ-H) 3 (SiHPh) as the major product, which has been structurally and spectroscopically characterized. Bulkier silane H a SiPh 2 provides iron(II) amido complex PhB(MesIm) 3 FeN(H)(SiHPh 2 ) as the initial product of the reaction, with excess H 2 SiPh 2 affording diamagnetic PhB(MesIm) 3 Fe(μ-H) 3 (SiPh 2 ) as the major product. Unobserved iron(II) hydride PhB(MesIm) 3 Fe-H is implicated as an intermediate in this reaction, as suggested by the results of the reaction between iron(II) amido PhB(MesIm) 3 FeN(H) Bu and H 3 SiPh, which provides PhB(MesIm) 3 Fe(H)(μ-H) 2 (Si(NH Bu)Ph) as the sole product.