Supported organometallic complexes part 39: cationic diamine(ether–phosphine)ruthenium(II) complexes as precursors for the hydrogenation of trans-4-phenyl-3-butene-2-one
摘要:
Treatment of RuCl2(eta(1)-Ph2PCH2CH2OCH3)(2)(diamine) (1L(1)-1L(7)) with one equivalent of AgX (X = OTf, BF4) in CH2Cl2 results in the formation of the monocationic ruthenium(H) complexes [RuCl(eta(1)-Ph2PCH2CH2OCH3)(eta(2)-Ph2PCH2CH2OCH3)(diamine)]X-+(-) (2L(1)-2L(7)). These complexes were characterized by NMR, and mass spectroscopy as well as by elemental analyses, 2L(1) additionally by an X-ray structural analysis. Complex 2L(1) crystallizes in the monoclinic space group C2/c with Z = 8. The monocationic and neutral complexes were applied as catalysts in the selective hydrogenation of trans-4-phenyl-3-butene-2-one. With the exception of 1L(3)/1L(7) and 2L(3)/2L(7) all catalysts showed high activities and selectivities toward the hydrogenation of the carbonyl group under mild conditions. However, the activity of the cationic catalysts is only half of that of their neutral congeners. (C) 2003 Elsevier B.V. All rights reserved.
Supported organometallic complexes Part 34: synthesis and structures of an array of diamine(ether–phosphine)ruthenium(II) complexes and their application in the catalytic hydrogenation of trans-4-phenyl-3-butene-2-one
摘要:
The novel diamine-bis(ether-phosphine)ruthenium(II) complexes Cl2Ru(eta(1)-Ph2PCH2-CH2OCH3)(2)(diamine)(2)(3L(1)-3L(11)) have been obtained by reaction of equimolar amounts of Cl2Ru(P boolean AND O)(2) (2) with the respective diamines L-1-L-11 in good yields. X-ray structural investigations of 3L(2) and 3L(8) show monoclinic unit cells with the space group P2(1)/c. The octahedrally coordinated ruthenium atoms have each two trans-chlorides and cis-phosphines which is in agreement with NMR studies in solution. With the exception of 3L(4) all mentioned ruthenium complexes are highly catalytically active in the hydrogenation of the alpha,beta-unsaturated ketone trans-4-phenyl-3-butene-2-one. In most cases the conversions and selectivities toward the formation of the unsaturated alcohol trans-4-phenyl-3-butene-2-ol were 100% with high turnover frequencies under mild conditions. (C) 2003 Elsevier Science B.V. All rights reserved.