Jing Yang1, Benjamin Mogesa2, Partha Basu2, Martin L Kirk1. 1. Department of Chemistry and Chemical Biology, The University of New Mexico , MSC03 2060, 1 University of New Mexico, Albuquerque, New Mexico 87131-0001, United States . 2. Department of Chemistry and Biochemistry, Duquesne University , Pittsburgh, Pennsylvania 15282, United States.
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.
Interligand charge transfer is examined in the novel metallo-dithiolene complex n class="Gene">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.
Authors: Franziska Frei; Ariana Rondi; Davide Espa; Maria Laura Mercuri; Luca Pilia; Angela Serpe; Ahmad Odeh; Frank Van Mourik; Majed Chergui; Thomas Feurer; Paola Deplano; Antonín Vlček; Andrea Cannizzo Journal: Dalton Trans Date: 2014-12-21 Impact factor: 4.390
Authors: Andrew J Millar; Christian J Doonan; Paul D Smith; Victor N Nemykin; Partha Basu; Charles G Young Journal: Chemistry Date: 2005-05-20 Impact factor: 5.236
Authors: Frank E Inscore; Sushilla Z Knottenbelt; Nick D Rubie; Hemant K Joshi; Martin L Kirk; John H Enemark Journal: Inorg Chem Date: 2006-02-06 Impact factor: 5.165
Authors: Kelly G Matz; Regina P Mtei; Rebecca Rothstein; Martin L Kirk; Sharon J Nieter Burgmayer Journal: Inorg Chem Date: 2011-09-06 Impact factor: 5.165
Authors: Benjamin Mogesa; Eranda Perera; Hannah M Rhoda; John K Gibson; Jos Oomens; Giel Berden; Michael J van Stipdonk; Victor N Nemykin; Partha Basu Journal: Inorg Chem Date: 2015-08-05 Impact factor: 5.165
Authors: Rebecca L McNaughton; Matthew E Helton; Michele Mader Cosper; John H Enemark; Martin L Kirk Journal: Inorg Chem Date: 2004-03-08 Impact factor: 5.165
Authors: Benjamin W Stein; Jing Yang; Regina Mtei; Nicholas J Wiebelhaus; Dominic K Kersi; Jesse LePluart; Dennis L Lichtenberger; John H Enemark; Martin L Kirk Journal: J Am Chem Soc Date: 2018-10-25 Impact factor: 15.419