Coordination bonding in dicopper and dichromium tetrakis(μ‐acetato)‐diaqua complexes: Nature, strength, length, and topology. Issue 7 (5th December 2019)

• Record Type: Journal Article
• Authors: Malček, Michal; Vénosová, Barbora; Puškárová, Ingrid; Kožíšek, Jozef; Gall, Marián; Bučinský, Lukáš
• Is Part Of: Journal of computational chemistry. Volume 41:Issue 7(2020)
• Page Start: 698
• Page End: 714
• Publication Date: 2019-12-05
• Subjects: electronic structure -- metal–metal interaction -- paddle‐wheel -- population analysis -- QTAIM analysis; Chemistry -- Data processing -- Periodicals; 542.85
• DOI: 10.1002/jcc.26121
• Languages: English
• ISSNs: 0192-8651

Abstract

Abstract : Geometry optimization, energetics, electronic structure, and topology of electron density of dicopper (I ) and dichromium (II ) tetrakis(μ‐acetato)‐diaqua complexes are studied focusing on the metal–metal interactions. The performance of broken symmetry (BS) single‐determinant ab initio (Hartree–Fock, Møller–Plesset perturbation theory to the second and third orders, coupled clusters singles and doubles) and density functional theory (BLYP, B3LYP, B3LYP‐D3, B2PLYP, MPW2PLYP) methods is compared to multideterminant ab initio (CASSCF, NEVPT2) methods as well as to the multipole model of charge density from a single‐crystal X‐ray diffraction experiment (Herich et al., Acta Cryst. 2018, B74, 681–692). In vacuo DFT geometry optimizations (improper axial water ligand orientation) are compared against the periodic ones. The singlet state is found to be energetically preferred. J coupling of (I ) becomes underestimated for all ab initio methods used, when compared to experiment. It is concluded that the strength of the direct M─M interactions correlates closely with the J coupling magnitude at a given level of theory. The double potential well character of (II) and of the dehydrated form of (II) are considered with respect to the Cr─Cr distance. The physical effective bond order of the metal–metal interaction is small (below 0.1 e ) in (I ) and moderate (0.4 e ) in (II ). The CASSCF results overestimate the electron density of the metal–metal bond critical point by 20% and 50% in (I ) and (II ), respectively, when compared to the multipole model. © 2019 Wiley Periodicals, Inc. Abstract : Geometry optimization, energetics, electronic structure and topology of electron density of di‐copper (I) and di‐chromium (II) tetrakis (μ‐acetato) diaqua complexes are studied focusing on the metal‐metal interactions. The performance of broken symmetry (BS) single determinant ab initio (HF, MP2, MP3, CCSD) and DFT (BLYP, B3LYP, B3LYP‐D3, B2PLYP, MPW2PLYP) methods is compared to multi determinant ab initio (CASSCF, NEVPT2) methods aswell as to themultipolemodel of charge density from X‐ray diffraction single crystal experiment (Herich et al., Acta Cryst. 2018;B74(6):681–692.).