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Rhodium(I) Complexes with OPPy 2 Ph and OPPy 3 (Py = 2‐Pyridyl), and Their Behavior in Hydrogenation Reactions
Author(s) -
Casares Juan A.,
Espinet Pablo,
MartínAlvarez José M.,
Espino Gustavo,
PérezManrique Mercedes,
Vattier Florencia
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(20011)2001:1<289::aid-ejic289>3.0.co;2-j
Subject(s) - chemistry , diene , rhodium , cyclohexene , cationic polymerization , cyclohexanone , medicinal chemistry , ligand (biochemistry) , cyclooctadiene , norbornene , catalysis , stereochemistry , polymer chemistry , organic chemistry , polymerization , biochemistry , natural rubber , receptor , polymer
The reaction of [Rh 2 (µ‐Cl) 2 (COD) 2 ] (COD = 1,5‐cyclooctadiene) or [Rh 2 (µ‐Cl) 2 (TFB) 2 ] (TFB = tetrafluorobenzobicyclo[2.2.2]octatriene) with the N‐donor chelating ligand OPPy 2 Ph (Py = 2‐pyridyl) in the presence of TlBF 4 affords cationic complexes [Rh(diene)(OPPy 2 Ph)](BF 4 ) ( 1 , diene: COD; 2 , diene: TFB). Compounds 1 or 2 react with CO to give [Rh(CO) 2 (OPPy 2 Ph)](BF 4 ) ( 4 ), which is also obtained by treatment of [Rh 2 (µ‐Cl) 2 (CO) 4 ] with OPPy 2 Ph and TlBF 4 . In a similar way, the complexes [Rh(diene)(OPPy 3 )](BF 4 ) ( 5 , diene: COD; 6 , diene: TFB) are obtained when using OPPy 3 ; they react with CO to give [Rh 2 (µ‐CO) 3 (OPPy 3 ) 2 ](BF 4 ) 2 ( 9 ). The behavior of the complexes in solution is reported. The complexes with OPPy 3 , 5 and 6 , show equivalence of the three Py groups in their NMR spectra. Complex 5 is square‐planar in the solid state, and in solution, and the uncoordinated and coordinated Py groups undergo fast exchange in solution. Complex 6 is pentacoordinated in the solid state and in solution, and its Py groups exchange their coordination sites in a fast topomerization process. The single‐crystal X‐ray structures of 5 and 6 have been solved. The behavior of 1 and 5 as catalysts in hydrogenation reactions of cyclohexene, acetone, and cyclohexanone is also reported.