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Structural and Theoretical Studies of ortho ‐Substituted Triphenylphosphane Ligands and Their Rhodium(I) Complexes
Author(s) -
Suomalainen Pekka,
Jääskeläinen Sirpa,
Haukka Matti,
Laitinen Riitta H.,
Pursiainen Jouni,
Pakkanen Tapani A.
Publication year - 2000
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(200012)2000:12<2607::aid-ejic2607>3.0.co;2-r
Subject(s) - chemistry , rhodium , steric effects , denticity , ligand (biochemistry) , stereochemistry , chelation , ab initio , crystallography , crystal structure , catalysis , organic chemistry , biochemistry , receptor
The triarylphosphanes, ( o ‐thiomethylphenyl)diphenylphosphane (SP, 1 ), ( o ‐ N , N ′‐dimethylaminophenyl)diphenylphosphane (NP, 2 ), and ( o ‐methoxyphenyl)diphenylphosphane (OP, 3 ) have been structurally characterized. Detailed information on the stereochemistry of the ligands was gathered by spectroscopic ( 1 H, 31 P, 13 C NMR) and X‐ray crystallographic studies. Molecular modeling methods for investigation of the structures were also applied. It is shown that the geometrical optimization of the ligand can be performed accurately by the ab initio Hartree−Fock method. Furthermore, the steric contribution of the coordinated ligands can be estimated by studying the different conformational states of the free ligands. The coordination abilities of the ligands were studied in reactions with the rhodium compounds Rh 2 (CO) 4 Cl 2 and Rh(NO 3 ) 3 under different reaction conditions. The SP and NP ligands yielded mononuclear chelate complexes, while the OP ligand coordinated solely in a monodentate fashion through the phosphorus atom. The crystal structures of the ligands 1−3 and the rhodium(I) complexes [RhCl(CO)(NP)] ( 5 ) and [RhCl(CO)(OP) 2 ] ( 6 ) are reported.