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Reactivity of κ( P )‐Alkenylphosphane Rhodium(III) and Iridium(III) Complexes toward Nucleophilic Reagents
Author(s) -
Martínez de Salinas Sara,
SánchezSordo Irene,
Díez Josefina,
Pilar Gamasa M.,
Lastra Elena
Publication year - 2016
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201601054
Subject(s) - chemistry , rhodium , iridium , reactivity (psychology) , nucleophile , cationic polymerization , medicinal chemistry , reagent , ligand (biochemistry) , halogen , stereochemistry , metal , oxidative addition , catalysis , polymer chemistry , alkyl , organic chemistry , medicine , biochemistry , alternative medicine , pathology , receptor
The reactivity of the complexes [RhCl 2 ( η 5 ‐C 5 Me 5 ){ κ ( P ) ‐ Ph 2 P(CH 2 ) 2 CH=CH 2 }] ( 1 ), [MCl 2 ( η 5 ‐C 5 Me 5 ){ κ ( P )‐R 2 PCH 2 CH=CH 2 }] (M=Rh, R=Ph ( 3 a ), i Pr ( 3 b ); M=Ir, R=Ph ( 4 a ), i Pr ( 4 b )) towards various nucleophilic reagents (carbon‐donor, nitrogen‐donor and phosphorus‐donor) in the presence of a halogen abstractor has been studied. The rhodium e iridium complexes undergo metal coordination of the ligand (L=CNR, CO, Py, P(OPh) 3 ) to give the new cationic complexes [MCl( η 5 ‐C 5 Me 5 )(L){ κ ( P )‐R 2 P(CH 2 ) n CH=CH 2 }][BPh 4 ] (M=Rh, Ir; L=CNR, CO, Py, P(OPh) 3 ) ( 5 ‐ 19 a,b ). However, the reaction with phosphanes follows a different way depending on the metal. While the rhodium complexes 3 a,b give the expected products [RhCl( η 5 ‐C 5 Me 5 )(L){ κ ( P )‐R 2 PCH 2 CH=CH 2 }][BPh 4 ] ( 20 a,b , 21 a and 22 a ), the iridium complex 4 a suffer addition of the phosphane to the C=C affording the complexes [IrCl(η 5 ‐C 5 Me 5 ){ κ 2 ( P,C )‐Ph 2 PCH 2 CH(PR ’Ph 2 )CH 2 }][BPh 4 ] (R ’ = Me ( 23 a ), Ph ( 24 a )).