C-C bond as shuttle of two electrons in intermolecular and intramolecular processes: A theoretical approach to molecular batteries

被引：0

作者：

Rosi, M

Sgamellotti, A

Franceschi, F

Floriani, C

机构：

[1] Univ Perugia, Ctr Studi Calcolo Intensivo Sci Mol, CNR, I-06123 Perugia, Italy

[2] Univ Perugia, Dipartimento Chim, I-06123 Perugia, Italy

[3] Univ Lausanne, BCH, Inst Chim Minerale & Analyt, CH-1015 Lausanne, Switzerland

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 1999年 / 5卷 / 10期

关键词：

density functional calculations; electron reservoirs; molecular batteries; porphyrinogens; Schiff bases; titanium;

D O I：

10.1002/(SICI)1521-3765(19991001)5:10<2914::AID-CHEM2914>3.0.CO;2-M

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Density functional calculations have been carried out on titanium Schiff base complexes and titanium porphyrinogen complexes in order to understand the behavior of these systems in redox processes. In titanium Schiff base complexes C-C sigma bonds are formed upon the acquisition of pairs of electrons, while in titanium porphyrinogen complexes C-C sigma bonds are formed upon the donation of pairs of electrons. In both systems, the formation or the breaking of C-C bonds avoids a variation in the oxidation state of the metal. These C-C bonds, therefore, act not only as electron reservoirs, but also as a buffer for the oxidation state of the metal.

引用

收藏

页码：2914 / 2920

页数：7

相关论文

共 30 条

[1] DENSITY-FUNCTIONAL EXCHANGE-ENERGY APPROXIMATION WITH CORRECT ASYMPTOTIC-BEHAVIOR [J].

BECKE, AD .

PHYSICAL REVIEW A, 1988, 38 (06) :3098-3100

[2] SELF-CONSISTENT MOLECULAR-ORBITAL METHODS .21. SMALL SPLIT-VALENCE BASIS-SETS FOR 1ST-ROW ELEMENTS [J].

BINKLEY, JS ;

POPLE, JA ;

HEHRE, WJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1980, 102 (03) :939-947

[3]

CARPENTER JE, 1988, J MOL STRUC-THEOCHEM, V46, P41, DOI 10.1016/0166-1280(88)80248-3

[4]

CHELINTZEV VV, 1916, J RUSS PHYS CHEM SOC, V48, P105

[5] EFFICIENT DIFFUSE FUNCTION-AUGMENTED BASIS SETS FOR ANION CALCULATIONS. III. THE 3-21+G BASIS SET FOR FIRST-ROW ELEMENTS, LI-F [J].

CLARK, T ;

CHANDRASEKHAR, J ;

SPITZNAGEL, GW ;

SCHLEYER, PV .

JOURNAL OF COMPUTATIONAL CHEMISTRY, 1983, 4 (03) :294-301

[6] Formation of carbon-carbon-bonded dimers in the reduction of [Co(II)salophen] [salophen equals N,N'-o-phenylenebis(salicylideneaminato)]: Their reactivity with electrophiles to form Co-C bonds [J].

DeAngelis, S ;

Solari, E ;

Gallo, E ;

Floriani, C ;

ChiesiVilla, A ;

Rizzoli, C .

INORGANIC CHEMISTRY, 1996, 35 (21) :5995-6003

[7] OXIDATION OF METAL-MESO-OCTAETHYLPORPHYRINOGEN COMPLEXES LEADING TO NOVEL OXIDIZED FORMS OF PORPHYRINOGEN OTHER THAN PORPHYRINS .1. THE REDOX CHEMISTRY OF NICKEL(II)- AND COPPER(II)-MESO-OCTAETHYLPORPHYRINOGEN COMPLEXES OCCURRING WITH THE FORMATION AND CLEAVAGE OF A CYCLOPROPANE UNIT [J].

DEANGELIS, S ;

SOLARI, E ;

FLORIANI, C ;

CHIESIVILLA, A ;

RIZZOLI, C .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (13) :5691-5701

[8] OXIDATION OF METAL-MESO-OCTAETHYLPORPHYRINOGEN COMPLEXES LEADING TO NOVEL OXIDIZED FORMS OF PORPHYRINOGEN OTHER THAN PORPHYRINS .2. THE REDOX CHEMISTRY OF IRON(II)-MESO-OCTAETHYLPORPHYRINOGEN AND COBALT(II)-MESO-OCTAETHYLPORPHYRINOGEN COMPLEXES OCCURRING WITH THE FORMATION AND CLEAVAGE OF 2 CYCLOPROPANE UNITS [J].

DEANGELIS, S ;

SOLARI, E ;

FLORIANI, C ;

CHIESIVILLA, A ;

RIZZOLI, C .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (13) :5702-5713

[9]

DENNSTEDT M, 1888, CHEM BER, V21, P1478

[10]

Dennstedt M., 1887, Chem. Ber, V20, P850