Dataset Information

Synthesis, Characterization, Absorption Properties, and Electronic Structures of Paddlewheel-Type Dirhodium(II) Tetra-?-(n-naphthoate) Complexes: An Experimental and Theoretical Study.

ABSTRACT: The reactions of [Rh?(O?CCH?)?(OH?)?] with n-naphthalenecarboxylic acids (n = 1: 1-HNC, n = 2: 2-HNC) afford the dirhodium tetra-?-(n-naphthoate) complexes [Rh?(1-NC)?] (1) and [Rh?(2-NC)?] (2), respectively. Single crystal X-ray diffraction analyses of [1(OCMe?)?] and [2(OCMe?)?], which were obtained by recrystallization from acetone (OCMe?) solutions of 1 and 2, reveal that the dirhodium cores are coordinated by four equatorially bridging naphthoate ligands and two axial OCMe? ligands. Density functional theory (DFT) calculation confirmed that (i) the single Rh?Rh bond is formed between the two Rh ions and (ii) the electronic structures between two Rh ions in [1(OCMe?)?] and [2(OCMe?)?] are best described as ???²?²?*²?*? and ?²???²?*²?*?, respectively. Time-dependent DFT (TDDFT) calculations clarify the absorption band characters of [1(OCMe?)?] and [2(OCMe?)?]; the former shows the bands due to d?d and metal?to?metal-ligand charge transfer (MMLCT) excitations in the visible light region, whereas the latter shows the bands due to only d?d excitations in the same region. The electrochemical properties and thermal stabilities of [1(OCMe?)?] and [2(OCMe?)?] were also investigated in this study.

SUBMITTER: Kataoka Y

PROVIDER: S-EPMC6384905 | biostudies-literature | 2019 Jan

REPOSITORIES: biostudies-literature

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Publications

Synthesis, Characterization, Absorption Properties, and Electronic Structures of Paddlewheel-Type Dirhodium(II) Tetra-μ-(n-naphthoate) Complexes: An Experimental and Theoretical Study.

Kataoka Yusuke Y Fukumoto Raiki R Yano Natsumi N Atarashi Daiki D Tanaka Hidekazu H Kawamoto Tatsuya T Handa Makoto M

Molecules (Basel, Switzerland) 20190127 3

The reactions of [Rh₂(O₂CCH₃)₄(OH₂)₂] with n-naphthalenecarboxylic acids (n = 1: 1-HNC, n = 2: 2-HNC) afford the dirhodium tetra-μ-(n-naphthoate) complexes [Rh₂(1-NC)₄] (1) and [Rh₂(2-NC)₄] (2), respectively. Single crystal X-ray diffraction analyses of [1(OCMe₂)₂] and [2(OCMe₂)₂], which were obtained by recrystallization from acetone (OCMe₂) solutions of 1 and 2, reveal that the dirhodium cores are coordinated by four equatorially bridging ...[more]

PMID: 30691216

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Project description:Mn K-edge X-ray absorption spectroscopy (XAS) was used to gain insights into the geometric and electronic structures of [Mn(II)(Cl)2(Me2EBC)], [Mn(IV)(OH)2(Me2EBC)](2+), and [Mn(IV)(O)(OH)(Me2EBC)](+), which are all supported by the tetradentate, macrocyclic Me2EBC ligand (Me2EBC = 4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane). Analysis of extended X-ray absorption fine structure (EXAFS) data for [Mn(IV)(O)(OH)(Me2EBC)](+) revealed Mn-O scatterers at 1.71 and 1.84 Å and Mn-N scatterers at 2.11 Å, providing the first unambiguous support for the formulation of this species as an oxohydroxomanganese(IV) adduct. EXAFS-determined structural parameters for [Mn(II)(Cl)2(Me2EBC)] and [Mn(IV)(OH)2(Me2EBC)](2+) are consistent with previously reported crystal structures. The Mn pre-edge energies and intensities of these complexes were examined within the context of data for other oxo- and hydroxomanganese(IV) adducts, and time-dependent density functional theory (TD-DFT) computations were used to predict pre-edge properties for all compounds considered. This combined experimental and computational analysis revealed a correlation between the Mn-O(H) distances and pre-edge peak areas of Mn(IV)?O and Mn(IV)-OH complexes, but this trend was strongly modulated by the Mn(IV) coordination geometry. Mn 3d-4p mixing, which primarily accounts for the pre-edge intensities, is not solely a function of the Mn-O(H) bond length; the coordination geometry also has a large effect on the distribution of pre-edge intensity. For tetragonal Mn(IV)?O centers, more than 90% of the pre-edge intensity comes from excitations to the Mn?O ?* MO. Trigonal bipyramidal oxomanganese(IV) centers likewise feature excitations to the Mn?O ?* molecular orbital (MO) but also show intense transitions to 3dx(2)-y(2) and 3dxy MOs because of enhanced 3d-4px,y mixing. This gives rise to a broader pre-edge feature for trigonal Mn(IV)?O adducts. These results underscore the importance of reporting experimental pre-edge areas rather than peak heights. Finally, the TD-DFT method was applied to understand the pre-edge properties of a recently reported S = 1 Mn(V)?O adduct; these findings are discussed within the context of previous examinations of oxomanganese(V) complexes.

Dataset Information

Synthesis, Characterization, Absorption Properties, and Electronic Structures of Paddlewheel-Type Dirhodium(II) Tetra-?-(n-naphthoate) Complexes: An Experimental and Theoretical Study.

Publications

Synthesis, Characterization, Absorption Properties, and Electronic Structures of Paddlewheel-Type Dirhodium(II) Tetra-μ-(<i>n</i>-naphthoate) Complexes: An Experimental and Theoretical Study.

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