Crystal structure of the novel neutral octahedral complex [(4 '-(4-tbutylphenyl)-2,2 ': 6 ',2 ''-terpyridine)Rh-III(Br)(acetonyl)(2)]

摘要

The synthesis and the crystal and molecular structure of a unique Rh(III) complex, [Rh-III(Br)(acetonyl)2(4'-(4-tbutylphenyl)-2,2':6',2"-terpyridine)] (1) are described. The yellow crystals separate from the acetone solution of the starting complex [Rh(Br)(COD)](2) and the ligand 4'-(4-tbutylphenyl)-2,2':6',2"-terpyridine after standing at room temperature for a prolonged period of time. The crystals are almost insoluble in all common organic solvents. The single-crystal X-ray structure determination shows that compound I is the first Rh-complex with a terdentate nitrogen ligand and two axially oriented, sigma-bound acetonyl groups. DFT-calculations on a model complex without the substituent on the terpyridine ligand were carried out and agree very well with the X-ray results, confirming the constitution and geometry of the molecule. (C) 2004 Elsevier B.V. All rights reserved.