Synthesis and reactivity of silyl iron hydride via Si H bond activation

Abstract The preligand pyridine-2-amino(methyl)-dimethylsilane ( 1 ) was used to synthesize silyl iron hydride. Iron(II) hydride FeH(N( κ N-C 5 H 4 N)Me(SiMe 2 ))(PMe 3 ) 3 ( 2 ) was obtained through the reaction of 1 and Fe(PMe 3 ) 4 via the activation of one Si H bond and the coordination of nitrogen atom of pyridine. The substitution reaction of complex 2 with haloalkane (CH 3 I and EtBr) delivered complexes FeX(N( κN -C 5 H 4  N)Me(SiMe 2 ))(PMe 3 ) 3 (X = I ( 3 ); Br ( 4 )). Complex 2 reacting with acetylacetone resulted in the formation of Fe(acac)(N( κN -C 5 H 4 N)Me(SiMe 2 ))(PMe 3 ) 3 ( 5 ). However, the insertion products Fe(η 3 -OCOH)(N( κ N-C 5 H 4 N)Me(SiMe 2 ))(PMe 3 ) 3 ( 6 ) and Fe(η 3 -Ph-NCOH)(N( κN -C 5 H 4 N)Me(SiMe 2 ))(PMe 3 ) 3 ( 7 ) were formed through the insertion of the unsaturated bonds into Fe H bond. Complex 6 could also be synthesized through the substitution reaction of 2 with HCOOH. The molecular structures of complexes 2 and 4 – 7 were determined by single crystal X-ray diffraction.