A New Family of Mono- and Dicarboxylic Ruthenium Complexes [Ru(DIP)2(L2)]2+ (DIP = 4,7-diphenyl-1,10-phenanthroline): Synthesis, Solution Behavior, and X-ray Molecular Structure of trans-[Ru(DIP)2(MeOH)2][OTf]2
- 14 April 2006
- journal article
- research article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 45 (10), 4071-4078
- https://doi.org/10.1021/ic0601236
Abstract
9 pagesA new family of ruthenium complexes of general formula [Ru(DIP)(2)(L-2)](2+), where DIP) 4,7-diphenyl-1,10-phenanthroline,a bidentate ligand with an extended aromatic system, was prepared and fully characterized. When L is a monodentate ligand, the following complexes were obtained: L = CF3SO3-1 (2), CH3CN (3), and MeOH (4). When L-2 is a bidentate ligand, the compounds [Ru(DIP)(2)(Hcmbpy)][Cl](2) (5) and [Ru(DIP)(2)(H(2)dcbpy)][Cl](2) ( 6) were prepared (Hcmbpy = 4-carboxy-4'-methyl-2,2-bipyridine, H(2)dcbpy = 4,4'-dicarboxy-2,2'-bipyridine). Complex [Ru(DIP)(2)(MeOH)(2)][OTf](2) (4) displayed a trans configuration of the DIP ligands, which is rare for octahedral complexes featuring DIP bidentate ligands. DFT calculations carried out on 4 showed that the cis isomer is more stable by 12.2 kcal/ mol relative to the trans species. The solution behaviors of monocarboxylic complex [ Ru( DIP) 2( Hcmbpy)][Cl](2) ( 5) and dicarboxylic complex [Ru(DIP)(2)(H(2)dcbpy)][Cl](2) (6) were investigated by H-1 NMR spectroscopy. VT-NMR, concentration dependence, and reaction with NaOD allowed us to suggest that aggregation of the cationic species in solution, especially for 6, originates mainly from hydrogen bonding interactionsKeywords
This publication has 15 references indexed in Scilit:
- Influence of L-type ligands on the relative stability and interconversion of cis–trans-[Ru(phen)2L2]n+ type complexes. A theoretical studyPolyhedron, 2000
- Synthesis, spectroscopic and a ZINDO study of cis - and trans -(X 2 )bis(4,4′-dicarboxylic acid-2,2′-bipyridine)ruthenium(II) complexes (X=Cl − , H 2 O, NCS − )Coordination Chemistry Reviews, 2000
- Synthesis and Structures of Organometallic Aqua Complexes of Ruthenium(II)Organometallics, 1999
- ONIOM: A Multilayered Integrated MO + MM Method for Geometry Optimizations and Single Point Energy Predictions. A Test for Diels−Alder Reactions and Pt(P(t-Bu)3)2 + H2 Oxidative AdditionThe Journal of Physical Chemistry, 1996
- A set of f-polarization functions for pseudo-potential basis sets of the transition metals ScCu, YAg and LaAuChemical Physics Letters, 1993
- Application of a universal force field to organic moleculesJournal of the American Chemical Society, 1992
- Approximate density functional theory as a practical tool in molecular energetics and dynamicsChemical Reviews, 1991
- Crystal and molecular structure of a chiral-specific DNA-binding agent: tris(4,7-diphenyl-1,10-phenanthroline)ruthenium(II)Inorganic Chemistry, 1986
- Six-coordinate complexes with 1,10-phenanthroline ligands in the trans configuration. Preparation of trans-bis(1,10-phenanthroline)ruthenium(II) complexes and crystal structure of trans-bis(1,10-phenanthroline)bis(pyridine)ruthenium(II) hexafluorophosphateInorganic Chemistry, 1983
- Molecular Structure of Nucleic Acids: Molecular Structure of Deoxypentose Nucleic AcidsNature, 1953