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Preparation of Trifluorophosphaneruthenium(II) Complexes from η 3 :η 3 ‐Cyclooctadienediylruthenium(IV) Compounds as Precursors
Author(s) -
Werner Helmut,
Stüer Wolfram,
Jung Stefan,
Weberndörfer Birgit,
Wolf Justin
Publication year - 2002
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(200205)2002:5<1076::aid-ejic1076>3.0.co;2-4
Subject(s) - chemistry , protonation , cationic polymerization , medicinal chemistry , nucleophile , ruthenium , ligand (biochemistry) , carbene , derivative (finance) , alkene , stereochemistry , ether , organic chemistry , ion , catalysis , biochemistry , receptor , financial economics , economics
The dinuclear cyclooctadienediylruthenium(IV) compound [{RuCl 2 (η 3 :η 3 ‐C 10 H 16 )} 2 ] ( 1 ) reacts with PCy 3 in 2‐propanol under an H 2 atmosphere to give the hydrido(dihydrogen) complex [RuHCl(H 2 )(PCy 3 ) 2 ] ( 2 ) in nearly quantitative yield. Treatment of 1 with PCy 3 , P i Pr 3 or P i Pr 2 Ph under argon affords the mononuclear products [RuCl 2 (η 3 :η 3 ‐C 10 H 16 )(PR 3 )] ( 3 − 5 ) by chloride‐bridge cleavage. The corresponding compound 6 with PF 3 as phosphane ligand reacts with PCy 3 by nucleophilic attack of PCy 3 at the carbon atom C3 of the dienediyl chain to give the zwitterionic η 2 :η 3 ‐alkene(allyl)ruthenium(II) complex [RuCl 2 {η 2 :η 3 ‐CH 2 =C(Me)−CH(PCy 3 )(CH 2 ) 2 CHC(Me)CH 2 }(PF 3 )] ( 7 ) the crystal and molecular structures of which have been determined. The reaction of 7 with excess PCy 3 in the presence of H 2 affords the five‐coordinate hydrido compound [RuHCl(PF 3 )(PCy 3 ) 2 ] ( 8 ), which upon treatment with acetylene gives the vinyl derivative [RuCl(CH=CH 2 )(PF 3 )(PCy 3 ) 2 ] ( 9 ). The related cationic carbene complex [RuCl(=CHCH 3 )(PF 3 )(PCy 3 ) 2 ]BF 4 ( 10 ) is obtained by protonation of 9 with HBF 4 in ether. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)