Structure and bonding in trimetallic arrays containing a Cr-Cr quadruple bond: A challenge to density functional theory

被引：17

作者：

Arcisauskaite, Vaida ^{[1
]}

Spivak, Mariano ^{[2
]}

McGrady, John E. ^{[1
]}

机构：

[1] Univ Oxford, Dept Chem, Inorgan Chem Lab, Oxford OX1 3QR, England

[2] Univ Rovira & Virgili, Dept Quim Fis & Inorgan, E-43007 Tarragona, Spain

来源：

INORGANICA CHIMICA ACTA | 2015年 / 424卷

基金：

英国工程与自然科学研究理事会;

关键词：

Density functional theory; Metal-metal bonds; Chromium; LOCAL-SPIN-DENSITY; METAL-METAL BOND; TRANSITION-METAL; ELECTRONIC-STRUCTURE; BIMETALLIC SYSTEMS; BROKEN-SYMMETRY; QUINTUPLE BOND; AXIAL LIGAND; AB-INITIO; COMPLEXES;

D O I：

10.1016/j.ica.2014.08.061

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Structural trends within the series of trimetallics Cr2M(dpa)(4)Cl-2, M = Cr, Mn, Fe, Ni and Zn offer an important test bed for the theoretical treatment of the quadruple Cr-Cr bond. Cr-Cr bond lengths are dramatically functional dependent, reflecting the different treatment of exchange and correlation in each case. The presence of a paramagnetic heterometal in a Cr2M(dpa)(4)Cl-2 array has the effect of elongating the Cr-Cr bond by polarising the spin density in the Cr-Cr sigma bond, effectively seeding the localisation of the remaining pi and delta components. (C) 2014 Elsevier B.V. All rights reserved.

引用

页码：293 / 299

页数：7

共 53 条

[1] Synthesis, Structure Determination, and Magnetic Properties of the New Heterometallic Chain Compound CrCrNi(di-2,2′-pyridylamido)4Cl2•Et2O [J].

Aydin-Cantuerk, Dilahan ;

Nuss, Hanne .

ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE, 2011, 637 (05) :543-546

[2]

Baerends E.J., SCM, Theoretical Chemistry

[3] CR-2 REVISITED [J].

BAUSCHLICHER, CW ;

PARTRIDGE, H .

CHEMICAL PHYSICS LETTERS, 1994, 231 (2-3) :277-282

[4] LCAO LOCAL-SPIN-DENSITY AND X-ALPHA CALCULATIONS FOR CR-2 AND MO-2 [J].

BAYKARA, NA ;

MCMASTER, BN ;

SALAHUB, DR .

MOLECULAR PHYSICS, 1984, 52 (04) :891-905

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

BECKE, AD .

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

[6] Molecular and electronic structures by design: Tuning symmetrical and unsymmetrical linear trichromium chains [J].

Berry, JF ;

Cotton, FA ;

Lu, TB ;

Murillo, CA ;

Roberts, BK ;

Wang, XP .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (22) :7082-7096

[7] AB-INITIO CALCULATIONS OF DIRHENIUM COMPLEXES USING RELATIVISTIC EFFECTIVE CORE POTENTIALS [J].

BLAUDEAU, JP ;

ROSS, RB ;

PITZER, RM ;

MOUGENOT, P ;

BENARD, M .

JOURNAL OF PHYSICAL CHEMISTRY, 1994, 98 (29) :7123-7127

[8] Oxidative Stretching of Metal-Metal Bonds to Their Limits [J].

Brogden, David W. ;

Turov, Yevgeniya ;

Nippe, Michael ;

Li Manni, Giovanni ;

Hillard, Elizabeth A. ;

Clerac, Rodolphe ;

Gagliardi, Laura ;

Berry, John F. .

INORGANIC CHEMISTRY, 2014, 53 (09) :4777-4790

[9] A quantum chemical study of the quintuple bond between two chromium centers in [PhCrCrPh]:: trans-bent versus linear geometry [J].

Brynda, M ;

Gagliardi, L ;

Widmark, PO ;

Power, PP ;

Roos, BO .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2006, 45 (23) :3804-3807

[10] Oxalate Bridged Triangles Incorporating Mo24+ Units. Electronic Structure and Bonding [J].

Chisholm, Malcolm H. ;

Patmore, Nathan J. ;

Reed, Carly R. ;

Singh, Namrata .

INORGANIC CHEMISTRY, 2010, 49 (15) :7116-7122

← 1 2 3 4 5 6 →