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• W2313437574 endingPage "4667" @default.
• W2313437574 startingPage "4658" @default.
• W2313437574 abstract "We report here the syntheses, X-ray crystal structures, electrochemistry, and density functional theory (DFT) single-point calculations of three new complexes: tetrakis(monothiosuccinimidato)dimolybdenum(II) [Mo2(SNO5)4, 1a], tetrakis(6-thioxo-2-piperidinonato)dimolybdenum(II) [Mo2(SNO6)4, 1b], and chlorotetrakis(monothiosuccinimidato)pyridinelithiumdimolybdenum(II) [pyLiMo2(SNO5)4Cl, 2-py]. X-ray crystallography shows unusually short axial Mo2–Cl bond lengths in 2-py, 2.6533(6) Å, and dimeric 2-dim, 2.644(1) Å, which we propose result from an increased Lewis acidity of the Mo2 unit in the presence of the proximal Li+ ion. When 2-py is dissolved in MeCN, the lithium reversibly dissociates, forming an equilibrium mixture of (MeCNLiMo2(SNO5)4Cl) (2-MeCN) and [Li(MeCN)4]+[Mo2(SNO5)4Cl]− (3). Cyclic voltammetry was used to determine the equilibrium lithium binding constant (room temperature, Keq = 95 ± 1). From analysis of the temperature dependence of the equilibrium constant, thermodynamic parameters for the formation of 2-MeCN from 3 (ΔH° = −6.96 ± 0.93 kJ mol–1 and ΔS° = 13.9 ± 3.5 J mol–1 K–1) were extracted. DFT calculations indicate that Li+ affects the Mo–Cl bond length through polarization of metal–metal bonding/antibonding molecular orbitals when lithium and chloride are added to the dimolybdenum core." @default.
• W2313437574 created "2016-06-24" @default.
• W2313437574 creator A5019026939 @default.
• W2313437574 creator A5084896370 @default.
• W2313437574 date "2013-03-29" @default.
• W2313437574 modified "2023-09-23" @default.
• W2313437574 title "Lewis Acid Enhanced Axial Ligation of [Mo₂]⁴⁺ Complexes" @default.
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• W2313437574 doi "https://doi.org/10.1021/ic400275x" @default.
• W2313437574 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/23537011" @default.
• W2313437574 hasPublicationYear "2013" @default.

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