Mixed Valency across Hydrogen Bonds

被引：38

作者：

Goeltz, John C. ^{[1
]}

Kubiak, Clifford P. ^{[1
]}

机构：

[1] Univ Calif San Diego, Dept Chem & Biochem, La Jolla, CA 92093 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2010年 / 132卷 / 49期

关键词：

COUPLED ELECTRON-TRANSFER; CHARGE-TRANSFER IVCT; RUTHENIUM CLUSTERS; COMPLEXES; COMMUNICATION; TRANSITIONS; TRINUCLEAR; MOLECULES; DYNAMICS; EXCHANGE;

D O I：

10.1021/ja108841k

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

An oxo-centered triruthenium cluster with one pyridine-4-carboxylic acid ligand forms a mixed valence monoanionic dicarboxylic acid dimer upon partial reduction. Dimerization is not observed in DMSO or in the deprotonated carboxylate complex. Infrared spectroscopy reveals the mixed valence dimer as a charge localized species, and UV/vis/NIR spectroscopy suggests a large stabilization of the ground state by mixed valency across hydrogen bonds, on the order of 2500 cm(-1), or 7 kcal/mol, relative to the hydrogen bonded but isovalent fully reduced dimer. The stabilization is a combination of hydrogen bonding and electronic coupling.

引用

页码：17390 / 17392

页数：3

共 50 条

[1] Mixed-valency across hydrogen bonds: The effects of electron delocalization
Kubiak, Clifford
Porter, Tyler
ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2017, 253
[2] Mixed valency and metal-metal quadruple bonds
Chisholm, Malcolm H.
COORDINATION CHEMISTRY REVIEWS, 2013, 257 (9-10) : 1576 - 1583
[3] Mixed valency in hydrogen bonded 'dimers of dimers'
Patmore, N.J. (n.patmore@sheffield.ac.uk), 1723, American Chemical Society (135):
[4] Mixed Valency in Hydrogen Bonded 'Dimers of Dimers'
Wilkinson, Luke A.
McNeill, Laura
Meijer, Anthony J. H. M.
Patmore, Nathan J.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2013, 135 (05) : 1723 - 1726
[5] Inorganic Electron Transfer: Sharpening a Fuzzy Border in Mixed Valency and Extending Mixed Valency across Supramolecular Systems
Kubiak, Clifford P.
INORGANIC CHEMISTRY, 2013, 52 (10) : 5663 - 5676
[6] Proton dependent mixed valency in hydrogen bonded assemblies
Canzi, Gabriele
Kubiak, Clifford P.
ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2013, 245
[7] Scalar couplings across hydrogen bonds
Grzesiek, S
Cordier, F
Dingley, AJ
NUCLEAR MAGNETIC RESONANCE OF BIOLOGICA MACROMOLECULES, PT A, 2001, 338 : 111 - 133
[8] Mixed-valency with hydrogen-bonded bimetallic systems
Calderon, Maripaz A.
Villagran, Dino A.
ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2013, 245
[9] Role of two-electron mixed valency in hydrogen production.
Nocera, DG
ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2002, 224 : U676 - U676
[10] MIXED VALENCY OF TMSE
WERTHEIM, GK
EIB, W
KALDIS, E
BULLETIN OF THE AMERICAN PHYSICAL SOCIETY, 1980, 25 (03): : 343 - 343

← 1 2 3 4 5 →