Large Ligand Folding Distortion in an Oxomolybdenum Donor-Acceptor Complex

Overview

Journal Inorg Chem

Specialty Chemistry

Date 2015 Dec 23

PMID 26692422

Citations 11

Authors

Jing Yang

Benjamin Mogesa

Partha Basu

Martin L Kirk

Affiliations

Soon will be listed here.

Abstract

Interligand charge transfer is examined in the novel metallo-dithiolene complex MoO(SPh)2((i)Pr2Dt(0)) (where (i)Pr2Dt(0) = N,N'-isopropyl-piperazine-2,3-dithione). The title complex displays a remarkable 70° "envelope"-type fold of the five-membered dithiolene ring, which is bent upward toward the terminal oxo ligand. A combination of electronic absorption and resonance Raman spectroscopies have been used to probe the basic electronic structure responsible for the large fold-angle distortion. The intense charge transfer transition observed at ∼18 000 cm(-1) is assigned as a thiolate → dithione ligand-to-ligand charge transfer (LL'CT) transition that also possesses Mo(IV) → dithione charge transfer character. Strong orbital mixing between occupied and virtual orbitals with Mo(x(2)-y(2)) orbital character is derived from a strong pseudo Jahn-Teller effect, which drives the large fold-angle distortion to yield a double-well potential in the electronic ground state.

Citing Articles

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Influence of the ligand-field on EPR parameters of cis- and trans-isomers in Mo systems relevant to molybdenum enzymes: Experimental and density functional theory study.

Nemykin V, Sabin J, Kail B, Upadhyay A, Hendrich M, Basu P J Inorg Biochem. 2023; 245:112228.

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Protonation and Non-Innocent Ligand Behavior in Pyranopterin Dithiolene Molybdenum Complexes.

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