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Vinylidene, Vinyl, and Carbene Ruthenium Complexes with Chelating Diphosphanes as Ligands
Author(s) -
Werner Helmut,
Jung Stefan,
GonzálezHerrero Pablo,
Ilg Kerstin,
Wolf Justin
Publication year - 2001
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(200108)2001:8<1957::aid-ejic1957>3.0.co;2-e
Subject(s) - carbene , ruthenium , chemistry , denticity , hydride , cationic polymerization , protonation , chelation , ligand (biochemistry) , medicinal chemistry , crystal structure , stereochemistry , catalysis , crystallography , ion , polymer chemistry , organic chemistry , metal , biochemistry , receptor
The ruthenium vinylidenes [RuCl 2 (=C=CHR)(PR′ 3 ) 2 ] ( 1 , 2 ) react with 1,2‐C 2 H 4 (PCy 2 ) 2 ( 3 ) to give the chelate complexes [RuCl 2 (=C=CHR)(κ 2 ‐ 3 )] ( 4 , 5 ) by displacement of the two monodentate phosphane ligands. In contrast, the reaction of the hydrido compound [RuHCl(=C=CH 2 )(PCy 3 ) 2 ] ( 6 ) with excess 3 proceeds by migration of the hydride to the Cα carbon atom of the vinylidene unit and affords the six‐coordinate vinyl complex trans ‐[RuCl(CH=CH 2 )(κ 2 ‐ 3 ) 2 ] ( 7 ). Protonation of 7 , followed by addition of NH 4 PF 6 , yields the cationic ruthenium carbene trans ‐[RuCl(=CHCH 3 )(κ 2 ‐ 3 ) 2 ]PF 6 ( 8 ), together with small quantities of the hydrido compound [RuH(κ 2 ‐ 3 ) 2 ]PF 6 ( 9 ). The Grubbs catalyst [RuCl 2 (=CHPh)(PCy 3 ) 2 ] ( 10 ) reacts with both 3 and [Fe(η 5 ‐C 5 H 4 PPh 2 ) 2 ] ( 11 ), also by ligand substitution, to give the corresponding chelate complexes [RuCl 2 (=CHPh)(κ 2 ‐ 3 )] ( 12 ) and [RuCl 2 (=CHPh)(κ 2 ‐ 11 )] ( 13 ); the latter has been characterized by X‐ray crystal structure analysis.