Rational Design of Rhodium Complexes Featuring [kappa]4-N,N,N,N- and [kappa]5-N,N,N,P,P-Bis(imino)pyridine Ligands

• Published in: European journal of inorganic chemistry 2013-09, Vol.2013 (25), p.4430
• Main Authors: Ben-Daat, Hagit, Hall, Gabriel B, Groy, Thomas L, Trovitch, Ryan J
• Format: Article
• Language: English
• Subjects: Crystals; Diffraction; Ligands
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.201300263

The addition of aminoalkyl-substituted 2,6-bis(imino)pyridine (or pyridine diimine, PDI) ligands to [(COD)RhCl]2 (COD = 1,5-cyclooctadiene) resulted in the formation of rhodium monochloride complexes with the general formula (NPDI)RhCl (NPDI = iPr2NEtPDI or Me2NPrPDI). The investigation of (iPr2NEtPDI)RhCl and (Me2NPrPDI)RhCl by single-crystal X-ray diffraction verified the absence of amine arm coordination and a pseudo square-planar geometry about rhodium. Replacement of the chloride ligand with an outer-sphere anion was achieved by adding AgBF4 directly to (iPr2NEtPDI)RhCl to form [(iPr2NEtPDI)Rh][BF4]. Alternatively, this complex was prepared by chelate addition following the salt metathesis reaction between AgBF4 and [(COD)RhCl]2. Using the latter method, both [(NPDI)Rh][BF4] complexes were isolated and found to exhibit [kappa]4-N,N,N,N-PDI coordination regardless of arm length or steric bulk. In contrast, the metallation of PPDI chelates featuring alkylphosphane imine substituents (PPDI = Ph2PEtPDI or Ph2PPrPDI) resulted in the formation of cationic complexes featuring [kappa]5-N,N,N,P,P-PDI coordination in all instances, [(PPDI)Rh][X] (X = Cl, BF4). Adjusting the metallation stoichiometry allowed the preparation of [(Ph2PPrPDI)Rh][(COD)RhCl2], as validated by multinuclear NMR spectroscopy and single-crystal X-ray diffraction. [PUBLICATION ABSTRACT]