| The Nature of Bond Critical Points in Dinuclear Copper(I) Complexes. | |
| | |
MedLine Citation:
|
PMID: 22290789 Owner: NLM Status: Publisher |
Abstract/OtherAbstract:
|
Closed-shell contacts between two copper(I) ions are expected to be repulsive. However, such contacts are quite frequent and are well documented. Crystallographic characterization of such contacts in unsupported and bridged multinuclear copper(I) complexes has repeatedly invited debates on the existence of cuprophilicity. Recent developments in the application of Bader's theory of atoms-in-molecules (AIM) to systems in which weak hydrogen bonds are involved suggests that the copper(I)-copper(I) contacts would benefit from a similar analysis. Thus the nature of electron-density distributions in copper(I) dimers that are unsupported, and those that are bridged, have been examined. A comparison of complexes that are dimers of symmetrical monomers and those that are dimers of two copper(I) monomers with different coordination spheres has also been made. AIM analysis shows that a bond critical point (BCP) between two Cu atoms is present in most cases. The nature of the BCP in terms of the electron density, ρ, and its Laplacian is quite similar to the nature of critical points observed in hydrogen bonds in the same systems. The ρ is inversely correlated to CuCu distance. It is higher in asymmetrical systems than what is observed in corresponding symmetrical systems. By examining the ratio of the local electron potential-energy density (V(c) ) to the kinetic energy density (G(c) ), |V(c) |/G(c) at the critical point suggests that these interactions are not perfectly ionic but have some shared nature. Thus an analysis of critical points by using AIM theory points to the presence of an attractive metallophilic interaction similar to other well-documented weak interactions like hydrogen bonding. |
| | |
Authors:
|
Shrabani Dinda; Ashoka G Samuelson |
Related Documents
:
|
2551379 - Cytochrome c at charged interfaces. 2. complexes with negatively charged macromolecular... 11941499 - Chemical shift-based constraints for solution structure determination of paramagnetic l... 12119039 - New insights into the heme cavity structure of catalase-peroxidase: a spectroscopic app... 15378409 - Nitrosylation of rabbit ferrous heme-hemopexin. 22590319 - 4-benzyl-8-phenyl-1-thia-4-aza-spiro-[4.5]decan-3-one. 1849479 - A spectroscopic analysis of the pro35----ala mutant of rhodobacter capsulatus cytochrom... 16821879 - Ab initio and empirical model md simulation studies of solvent effects on the propertie... 23292249 - The physico-chemical "anatomy" of the tautomerization through the dpt of the biological... 18646809 - Structure-property relationships of polyselenoethers [-(ch2)yse-]x (y=1, 2, and 3) and ... |
Publication Detail:
|
Type: JOURNAL ARTICLE Date: 2012-1-30 |
Journal Detail:
|
Title: Chemistry (Weinheim an der Bergstrasse, Germany) Volume: - ISSN: 1521-3765 ISO Abbreviation: - Publication Date: 2012 Jan |
Date Detail:
|
Created Date: 2012-1-31 Completed Date: - Revised Date: - |
Medline Journal Info:
|
Nlm Unique ID: 9513783 Medline TA: Chemistry Country: - |
Other Details:
|
Languages: ENG Pagination: - Citation Subset: - |
Copyright Information:
|
Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. |
Affiliation:
|
Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore 560012 (India), Fax: (+91) 80-2360-1552. |
Export Citation:
|
APA/MLA Format Download EndNote Download BibTex |
| MeSH Terms | |
Descriptor/Qualifier:
|
|
From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine
Previous Document: Brain iron deposition fingerprints in Parkinson's disease and progressive supranuclear palsy.
Next Document: Sporadic or familial head neck paragangliomas enrolled in a single center: Clinical presentation and...