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

• Published in: Inorganica Chimica Acta 2005-01, Vol.358 (2), p.431-436
• Main Authors: de Pater, Boke C., Frühauf, Hans-Werner, Goubitz, Kees, Fraanje, Jan, Budzelaar, Peter H.M., Gal, Anton W., Vrieze, Kees
• Format: Article
• Language: English
• Subjects: Bis-acetonyl complex; DFT calculations; Rhodium; X-ray structure
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/j.ica.2004.08.019

The synthesis and single-crystal X-ray structure of the first Rh(I)-complex with a terdentate nitrogen ligand (Tpy*) and two axially oriented, σ-bound acetonyl groups is described. 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 1 is the first Rh-complex with a terdentate nitrogen ligand and two axially oriented, σ-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.