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Supported Organometallic Complexes. XXXVIII [1] Bis(methoxyethyldimethylphosphine)ruthenium(II) Complexes as Transfer Hydrogenation Catalysts
Author(s) -
Lu ZhongLin,
Eichele Klaus,
Warad Ismail,
Mayer Hermann A.,
Lindner Ekkehard,
Jiang Zhengjing,
Schurig Volker
Publication year - 2003
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200300067
Subject(s) - ruthenium , chemistry , transfer hydrogenation , acetophenone , phosphine , catalysis , ligand (biochemistry) , medicinal chemistry , ether , metal , organometallic chemistry , dihydrogen complex , stereochemistry , polymer chemistry , hydride , organic chemistry , biochemistry , receptor
Diamineruthenium(II) complexes containing the hemilabile methoxyethyldimethylphosphine ligand, [Cl 2 Ru( L n )(η 1 ‐Me 2 PCH 2 CH 2 OMe) 2 ] ( 2L n ) (n = 1‐12, Scheme 1), have been synthesized from the starting materials Me 2 PCH 2 CH 2 OMe, [Ru(COD)Cl 2 ] n , and the respective diamines L 1 ‐ L 12 . The structure of complex 2L 5 reveals that two chlorides are in trans position, while in complex 2L 11 the two chlorides favor a cis configuration. Most of the complexes are highly catalytic active in the hydrogen transfer reduction of acetophenone. The experimental study indicates that the replacement of phenyl groups for methyl functions in the ether‐phosphine ruthenium(II) complexes resulted in a switch of the hydrogenation mechanism from direct hydrogenation to transfer hydrogenation. The reason is attributed to the better donor ability of methyl groups compared to phenyl substitutents. Thus the metal center becomes more electron‐rich and inhibits the binding of dihydrogen to the ruthenium(II) complex fragment.