STRONG METAL-METAL COUPLING IN A DINUCLEAR (TERPYRIDINE)(BIPYRIDINE)RUTHENIUM MIXED-VALENCE COMPLEX INCORPORATING THE BRIDGING LIGAND 1,4-DICYANAMIDOBENZENE DIANION

被引：43

作者：

REZVANI, AR ^{[1
]}

EVANS, CEB ^{[1
]}

CRUTCHLEY, RJ ^{[1
]}

机构：

[1] CARLETON UNIV,OTTAWA CARLETON CHEM INST,OTTAWA,ON K1S 5B6,CANADA

来源：

INORGANIC CHEMISTRY | 1995年 / 34卷 / 18期

关键词：

D O I：

10.1021/ic00122a016

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The complex, [{Ru(terpy)(bpy)}2(mu-dicyd)][PF6](2), where terpy = 2,2',2''-terpyridine, bpy = 2,2'-bipyridine, and dicyd(2-) = 1,4-dicyanamidobenzene dianion, has been synthesized and characterized by cyclic voltammetry and spectroelectrochemical methods. A quantitative absorption spectrum of the radical anion dicyd(.-) has also been determined. The mixed valence ion, [{Ru(terpy)(bpy)](2)(mu-dicyd)](3+) is strongly coupled with K-c = 2.7 x 10(7) and has an intervalence band at lambda = 1090 nm (epsilon(max) 3000 M(-1) cm(-1), <(nu)over bar>(1/2) = 1800 cm(-1)). The mixed-valence properties of this complex were compared to its ammine analogue [{(NH3)(5)Ru}(2)(mu-dicyd)](3+) and rationalized by the perturbation of spectator ligands on the interaction of ruthenium ions with the dicyd(2-) superexchange pathway. The dependence of intervalence oscillator strength on the nature of the mixed-valence complex was also discussed.

引用

页码：4600 / 4604

页数：5

共 27 条

[1] SUPEREXCHANGE METAL METAL COUPLING IN DINUCLEAR PENTAAMMINERUTHENIUM COMPLEXES INCORPORATING A 1,4-DICYANAMIDOBENZENE DIANION BRIDGING LIGAND [J].

AQUINO, MAS ;

LEE, FL ;

GABE, EJ ;

BENSIMON, C ;

GREEDAN, JE ;

CRUTCHLEY, RJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (13) :5130-5140

[2]

AUMULLER A, 1986, LIEBIGS ANN CHEM, P1842

[3] 3,3',5,5'-TETRAPYRIDYLBIPHENYL - A BISCYCLOMETALATING BRIDGING LIGAND WITH A HIGH COUPLING ABILITY IN RU(III),RU(II) MIXED-VALENCE SYSTEMS [J].

BELEY, M ;

COLLIN, JP ;

LOUIS, R ;

METZ, B ;

SAUVAGE, JP .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (22) :8521-8522

[4] LOCALIZED STATES IN REDUCED AND EXCITED-STATE RUTHENIUM(II) TERPYRIDYLS [J].

BERGER, RM ;

MCMILLIN, DR .

INORGANIC CHEMISTRY, 1988, 27 (23) :4245-4249

[5] SYNTHESIS, STRUCTURE, AND CHARACTERIZATION OF A MIXED-VALENCE MANGANESE(III) MANGANESE(IV) BIS(MU-OXO) COMPLEX WITH A MACROCYCLIC TETRAAZA LIGAND [J].

BREWER, KJ ;

CALVIN, M ;

LUMPKIN, RS ;

OTVOS, JW ;

SPREER, LO .

INORGANIC CHEMISTRY, 1989, 28 (25) :4446-4451

[6] SYNTHETIC AND MECHANISTIC INVESTIGATIONS OF THE REDUCTIVE ELECTROCHEMICAL POLYMERIZATION OF VINYL-CONTAINING COMPLEXES OF IRON(II), RUTHENIUM(II), AND OSMIUM(II) [J].

CALVERT, JM ;

SCHMEHL, RH ;

SULLIVAN, BP ;

FACCI, JS ;

MEYER, TJ ;

MURRAY, RW .

INORGANIC CHEMISTRY, 1983, 22 (15) :2151-2162

[7] MIXED-VALENCE COMPLEXES OF D5-D6 METAL CENTERS [J].

CREUTZ, C .

PROGRESS IN INORGANIC CHEMISTRY, 1983, 30 :1-73

[8] SOLVENT DEPENDENCES OF SPECTRAL AND REDOX PROPERTIES OF PYRAZINE (PZ) COMPLEXES OF RUTHENIUM AND OSMIUM PENTAAMMINES - RU(NH3)5PZCH33+, OS(NH3)5PZCH33+, AND [RU(NH3)5]2PZ5+ [J].

CREUTZ, C ;

CHOU, MH .

INORGANIC CHEMISTRY, 1987, 26 (18) :2995-3000

[9]

Crutchley R.J., 1994, ADV INORG CHEM, V41, P273, DOI DOI 10.1016/S0898-8838(08)60174-9

[10] THE DEPENDENCE OF LIGAND TO METAL CHARGE-TRANSFER OSCILLATOR STRENGTH ON THE NATURE OF THE RUTHENIUM(III)-CYANAMIDE BOND - OUTERSPHERE PERTURBATIONS [J].

CRUTCHLEY, RJ ;

SALEH, AA ;

MCCAW, K ;

AQUINO, MAS .

MOLECULAR CRYSTALS AND LIQUID CRYSTALS, 1991, 194 :93-101

← 1 2 3 →