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Three novel selenophenolato hydrido iron(II) complexes [ cis -(H)(SeAr)Fe(PMe 3 ) 4 ] ( 4–6 ) (Ar=C 6 H 5 ( 4 ), p -MeOC 6 H 4 ( 5 ) and o -MeC 6 H 4 ( 6 )) were prepared through the reaction of Fe(PMe 3 ) 4 with selenophenols ArSeH ( 1–3 ) via Se–H activation. The iron hydrido complexes 4 , 5 and 6 could catalyze the hydrosilylation of aldehydes and ketones. Among them complex 5 is the best catalyst for this process. Furthermore, α,β-unsaturated alcohols could be obtained from the selective reduction reactions of the corresponding α,β-unsaturated carbonyls catalyzed by hydrido iron(II) complex 5 . This catalytic system has good tolerance for some common groups but it is easy to reduce the nitro group to an amino group. The experiments indicate that the chemoselectivity for this catalytic system is CHO> NO 2 > C( O)CH 3 . The crystal structure of 6 was determined by X-ray diffraction. [ABSTRACT FROM AUTHOR]

The hydrido silyl iron complex (o-Ph2PC6H4SiMe2)Fe(PMe3)3H (2) was obtained via the activation of the Si–H bond of the bidentate silyl ligand o-Ph2P(C6H4)SiMe2H (1) by Fe(PMe3)4. 2 showed good to excellent catalytic activity in both the reduction of aldehydes/ketones and the dehydration of benzamide. In addition, with complex 2 as a catalyst, α,β-unsaturated carbonyls could be selectively reduced to the corresponding α,β-unsaturated alcohols. The mechanisms of the formation of 2 and the catalytic dehydration process are proposed and partly experimentally verified. [ABSTRACT FROM AUTHOR]