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Atom Transfer Radical Additions with the Cationic Half‐Sandwich Complex [Cp*Ru(PPh 3 ) 2 (CH 3 CN)]OTf
Author(s) -
Quebatte Laurent,
Scopelliti Rosario,
Severin Kay
Publication year - 2005
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/ejic.200500321
Subject(s) - chemistry , ruthenium , cationic polymerization , catalysis , styrene , medicinal chemistry , zinc , ligand (biochemistry) , crystal structure , turnover number , stereochemistry , polymer chemistry , crystallography , organic chemistry , copolymer , biochemistry , polymer , receptor
The cationic ruthenium half‐sandwich complex [Cp*Ru(PPh 3 ) 2 (CH 3 CN)][OTf] ( 2 ) (Cp* = η 5 ‐C 5 Me 5 , OTf = SO 3 CF 3 ) was synthesized by reduction of [Cp*RuCl 2 ] 2 with zinc in the presence of NaOTf and subsequent reaction with PPh 3 . When NaOTf was omitted, the corresponding tetrachlorozincate salts were obtained. Complex 2 , as well as the salts [Cp*Ru(CH 3 CN) 3 ] 2 [ZnCl 4 ] ( 3 ) and [Cp*Ru(PPh 3 ) 2 (CH 3 CN)] 2 [ZnCl 4 ] ( 4 ), were characterized by single‐crystal X‐ray analysis. Complex 2 proved to be a potent catalyst for the atom transfer radical addition of CCl 4 and CHCl 3 to terminal olefins, displaying a performance superior to that of the previously described neutral catalyst [Cp*RuCl(PPh 3 ) 2 ]. For the addition of CHCl 3 to styrene, a total turnover number of 890 was achieved. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)