Intervalence charge transfer in the stereoisomers of a dinuclear ruthenium complex containing the bridging ligand dibenzoeilatin

被引:15
作者
D'Alessandro, DM
Keene, FR [1 ]
Bergman, SD
Kol, M
机构
[1] James Cook Univ N Queensland, Dept Chem, Sch Pharm & Mol Sci, Townsville, Qld 4811, Australia
[2] Tel Aviv Univ, Raymond & Beverly Sackler Fac Exact Sci, Sch Chem, IL-69978 Tel Aviv, Israel
关键词
D O I
10.1039/b412489h
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The dinuclear species [{Ru(bpy)2}2(mu-dbneil)](4+) (bpy = 2,2'-bipyridine; dbneil = dibenzoeilatin) was separated into its three stereoisomeric forms by cation-exchange chromatographic techniques. The NMR characteristics of the two diastereoisomers (meso and rac) are very similar, consistent with the decreased anisotropic interactions between the terminal bpy ligands located on different ruthenium centres because of their large spatial separation. Spectroelectrochemical measurements of the IVCT transitions in the mixed valence (5+) species show the system to be in the class II-III regime with substantial electronic communication between the metal centres. There is no significant difference in IVCT behaviour between the two diastereoisomers.
引用
收藏
页码:332 / 337
页数:6
相关论文
共 49 条
[1]   Manipulating the properties of MLCT excited states [J].
Anderson, PA ;
Keene, FR ;
Meyer, TJ ;
Moss, JA ;
Strouse, GF ;
Treadway, JA .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 2002, (20) :3820-3831
[2]   DESIGNED SYNTHESIS OF MONONUCLEAR TRIS(HETEROLEPTIC) RUTHENIUM COMPLEXES CONTAINING BIDENTATE POLYPYRIDYL LIGANDS [J].
ANDERSON, PA ;
DEACON, GB ;
HAARMANN, KH ;
KEENE, FR ;
MEYER, TJ ;
REITSMA, DA ;
SKELTON, BW ;
STROUSE, GF ;
THOMAS, NC ;
TREADWAY, JA ;
WHITE, AH .
INORGANIC CHEMISTRY, 1995, 34 (24) :6145-6157
[3]  
Balzani V.S. F., 1991, Supramolecular Photochemistry
[4]   Mononuclear and dinuclear complexes of dibenzoeilatin: Synthesis, structure, and electrochemical and photophysical properties [J].
Bergman, SD ;
Goldberg, I ;
Barbieri, A ;
Barigelletti, F ;
Kol, M .
INORGANIC CHEMISTRY, 2004, 43 (07) :2355-2367
[5]   Dibenzoeilatin:: a novel ligand exhibiting remarkable complementary π-π stacking interactions [J].
Bergman, SD ;
Reshef, D ;
Groysman, S ;
Goldberg, I ;
Kol, M .
CHEMICAL COMMUNICATIONS, 2002, (20) :2374-2375
[6]   DOES MARCUS HUSH THEORY REALLY WORK - OPTICAL STUDIES OF INTERVALENCE TRANSFER IN ACETYLENE-BRIDGED BIFERROCENE MONOCATION AT INFINITE DILUTION AND AT FINITE IONIC STRENGTHS [J].
BLACKBOURN, RL ;
HUPP, JT .
JOURNAL OF PHYSICAL CHEMISTRY, 1990, 94 (05) :1788-1793
[7]   Optical transitions of symmetrical mixed-valence systems in the Class II-III transition regime [J].
Brunschwig, BS ;
Creutz, C ;
Sutin, N .
CHEMICAL SOCIETY REVIEWS, 2002, 31 (03) :168-184
[8]   Chemical redox agents for organometallic chemistry [J].
Connelly, NG ;
Geiger, WE .
CHEMICAL REVIEWS, 1996, 96 (02) :877-910
[9]   MIXED-VALENCE COMPLEXES OF D5-D6 METAL CENTERS [J].
CREUTZ, C .
PROGRESS IN INORGANIC CHEMISTRY, 1983, 30 :1-73
[10]   A cautionary warning on the use of electrochemical measurements to calculate comproportionation constants for mixed-valence compounds [J].
D'Alessandro, DM ;
Keene, FR .
DALTON TRANSACTIONS, 2004, (23) :3950-3954