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Solid‐State and Solution Structures of a Series of [(HBPz 3 Me2 )Rh(CO)(PR 3 )] and [(HBPz 3 Me2,4Cl )Rh(CO)(PR 3 )] Complexes
Author(s) -
Malbosc François,
Chauby Valérie,
SerraLe Berre Carole,
Etienne Michel,
Daran JeanClaude,
Kalck Philippe
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(200109)2001:10<2689::aid-ejic2689>3.0.co;2-u
Subject(s) - chemistry , rhodium , ligand (biochemistry) , crystal structure , crystallography , solid state , infrared , infrared spectroscopy , stereochemistry , catalysis , organic chemistry , biochemistry , physics , receptor , optics
Addition of 1 equiv. of a phosphane or phosphite ligand to the κ 3 ‐bonded [Tp Me2 Rh(CO) 2 ] and [Tp Me2,4Cl Rh(CO) 2 ] dicarbonyl precursors gives the monosubstituted complexes [TpRh(CO)L]. The X‐ray crystal structures show that the three complexes [Tp Me2 Rh(CO)(PMe 3 )], [Tp Me2 Rh(CO)(PMePh 2 )], and [Tp Me2,4Cl Rh(CO)(PMePh 2 )] adopt square‐planar geometries. The X‐ray crystal structure of [Tp Me2 Rh(CO){P(OPh) 3 }] is consistent with an interaction between the dangling pyrazolyl group and the rhodium centre, the Rh−N distance being 2.762(3) Å. Analysis of ν(BH) and ν(CO) stretching frequencies shows that all the phosphane‐containing complexes are square planar in solution as well as in the solid state. According to infrared analyses, the phosphite complexes [Tp Me2,4Cl Rh(CO){P(OPh) 3 }] and [Tp Me2,4Cl Rh(CO){P(OMe) 3 }] adopt a pentacoordinated geometry both in the solid state and in solution. However, the infrared data for [Tp Me2 Rh(CO){P(OPh) 3 }] and [Tp Me2 Rh(CO){P(OMe) 3 }] indicate that the Tp Me2 ligand is in a κ 3 coordination mode in the solid state, as already evidenced by the X‐ray crystal structure, but in a κ 2 mode in solution. We also describe an exchange phenomenon between dangling and coordinated pyrazolyl groups, as studied by NMR.