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Formation of Ruthenium(Ⅱ) Complexes with Unsymmetrical Terdentate Ligands
Jahng, Yurngdong,Thummel, Randolph P.,Bott, Simon G. 영남대학교 약품개발연구소 1997 영남대학교 약품개발연구소 연구업적집 Vol.7 No.-
Three unsymmetrical terdentate ligands, 2-(2'-quinolyl)-1.10-phenanthroline (4), 2-(1'-isquinolyl)-1.10-phenanthroline (5), and 3.3'-dimethylene-2-(2'-quinolyl)-1.10-phenanthroline (6), have been prepared by application of the Friedlander condensation. Ligand 4 forms predominantly a pentaaza-coordinated (N5) complex with Ru(Ⅱ), [Ru(4-N,N,N')(4-N,N)Cl](PF_(6), whose structure was determined by X-ray analysis (C₄₂H_(26)CIF_(6)N_(6)PRu: monoclinic, C2lc, a=29.308(3) A, b=15.295(2) A, c=19.505(2) A, β=107.312(8)˚, V=8298(Ⅰ) A³, Z=8). Ligand 5 forms predominantly a hexaaza-coordinated (N6) complex, [Ru(5-N,N,N')₂. The bridged species 6 shows intermediate behavior, and the rate for interconversion of the N5 to N6 complex has been measured. The stereochemical features of these two binding modes are examined, and both π-stacking and steric effects are invoked to explain the observed behavior, leading to the proposal of a backside displacement mechanism for their interconversion.
Synthesis and Properties of Terdentatee with Extra Pyridine Ring and Their Ru(Ⅱ) Complexes
Jahng, Yurngdong,Moon, Seung Wook,Thummel, Randolph P. 영남대학교 약품개발연구소 1997 영남대학교 약품개발연구소 연구업적집 Vol.7 No.-
The synthesis and electronic as well as redox properties of four Ru(Ⅱ) complexes based on the ligand 4'-(4-pyridyl)-3.3';5',3"-bis-dimethylene-2,2‘;6’,2“-terpyridine are reported. Each new complex is of the type [Ru(L)₂]^(??+) and [Ru(tpy)(L)]^(??+), where L is the terdentate ligand with extra pyridine ring at 4¹-position or is a N-methylated ligand and n=2, 3, or 4. Cyclic voltammetry indicates that the first electron added to the complex enters the viologen-type acceptor in N-methylated ligand.
Copper(Ⅰ) Complexes of 3,3'-Bridged 2,2'-Biquinoline-Synthesis, Properties, and Structure
Jahng, Yurngdong,Hazelrigg, John,Kimball, David,Riesgo, Elvira,Wu, Feiyue,Thummel, Randolph P. 영남대학교 약품개발연구소 1998 영남대학교 약품개발연구소 연구업적집 Vol.8 No.-
A series of 3, 3'-bridged derivatives of 2, 2'-biquinoline have been prepared where the bridge consists of one to four methylene units or a -CH=CH- moiety. The corresponding [CuL₂](ClO₄) complexes were also prepared and their structures analyzed and confirmed by ¹H NMR. Electronic absorption maxima for the metal-to-ligand transition were found to move to higher energy and oxidation potentials were found to increase as the ligands became more distorted from planarity. An X-ray analysis was carried out for the most distorted systcm having a 3, 3'-tetramethylene bridge (C_(44)H_(36)BCuF₄N₄: triclinic, P??, a = 11.605(2) Å, b = 12.622(3) Å, c = 14.524(3) Å, α = 106.05(1)˚, β = 109.06(1)˚, r = 105.37(1)˚, V = 1778 ų, Z = 2). A wide variation in Cu-N bond lengths, 1.98-2.23 Å, was observed, and the two more weakly complexed quinolines were seen to be arranged in an almost parallel fashion. Ligand exchange studies with neocuproine indicated that the strength of Cu(I) binding depends on the planarity of the system as well as the cisoid disposition of the quinoline nitrogens.