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Title: Electronic Structure of Neutral And Monoanionic Tris(Benzene-1,2-Dithiolato) Metal Complexes of Molybdenum And Tungsten

Abstract

The reaction of 3 equiv of the ligand 2-mercapto-3,5-di-tert-butylaniline, H{sub 2}[L{sub N,S}], or 3,5-di-tert-butyl-1,2-benzenedithiol, H{sub 2}[L{sub S,S}], with 1 equiv of [MoO{sub 2}(acac){sub 2}] or WCl{sub 6} (acac = acetonylacetate(1-)) in methanol or CCl{sub 4} afforded the diamagnetic neutral complexes [MoV(L{sub N,S}){sub 2}(L{sup {center_dot}}{sub N,S})]{sup 0} (1), [MoV(L{sub S,S}){sub 2}(L{sup {center_dot}}{sub S,S})] (2), and [W{sup V}(L{sub S,S}){sub 2}(L{sup {center_dot}}{sub S,S})] (3), where (L{sup {center_dot}}{sub N,S}){sup -} and (L{sup {center_dot}}{sub S,S}){sup -} represent monoanionic {pi}-radical ligands (S{sub rad} = 1/2), which are the one-electron oxidized forms of the corresponding closed-shell dianions (L{sub N,S}){sup 2-} and (L{sub S,S}){sup 2-}. Complexes 1-3 are trigonal-prismatic members of the electron-transfer series [ML{sub 3}]{sup z} (z = 0, 1-, 2-). Reaction of 2 and 3 with [N(n-Bu){sub 4}](SH) in CH{sub 2}Cl{sub 2} under anaerobic conditions afforded paramagnetic crystalline [N(n-Bu){sub 4}][Mo{sup V}(L{sub S,S}){sub 3}] (4) and [N(n-Bu){sub 4}][W{sup V}(L{sub S,S}){sub 3}] (5). Complexes 1-5 have been characterized by X-ray crystallography. S K-edge X-ray absorption and infrared spectroscopy prove that a {pi}-radical ligand (L{sup {center_dot}}{sub S,S}){sup -} is present in neutral 2 and 3, whereas the monoanions [M{sup V}(L{sub S,S}){sub 3}]{sup -} contain only closed-shell dianionic ligands. These neutral species have previously been incorrectly described as [M{sup VI}(L){submore » 3}]{sup 0} complexes with a Mo{sup VI} or W{sup VI} (d{sup 0}) central metal ion; they are, in fact M{sup V} (d{sup 1}) (M = Mo, W) species: [Mo{sup V}(L{sub S,S}){sub 2}(L{sup {center_dot}}{sub S,S})] and [W{sup V}(L{sub S,S}){sub 2}(L{sup {center_dot}}{sub S,S})] with a diamagnetic ground state S{sub t} = 0, which is generated by intramolecular, antiferromagnetic coupling between the M{sup V} (d{sup 1}) central ion (S{sub M} = 1/2) and a ligand radical (L{sup {center_dot}}{sub S,S}){sup -} (S{sub rad} = 1/2).« less

Authors:
; ; ; ;
Publication Date:
Research Org.:
Stanford Linear Accelerator Center (SLAC)
Sponsoring Org.:
USDOE
OSTI Identifier:
915364
Report Number(s):
SLAC-REPRINT-2007-190
Journal ID: ISSN 0020-1669; INOCAJ; TRN: US200817%%481
DOE Contract Number:  
AC02-76SF00515
Resource Type:
Journal Article
Journal Name:
Inorg.Chem.46:5642-5650,2007
Additional Journal Information:
Journal Volume: 46; Journal ID: ISSN 0020-1669
Country of Publication:
United States
Language:
English
Subject:
10 SYNTHETIC FUELS; ABSORPTION; ANAEROBIC CONDITIONS; CRYSTALLOGRAPHY; ELECTRON TRANSFER; ELECTRONIC STRUCTURE; GROUND STATES; METHANOL; MOLYBDENUM; RADICALS; SPECTROSCOPY; TUNGSTEN; Other,OTHER

Citation Formats

Kapre, R R, Bothe, E, Weyhermuller, T, George, S D, Wieghardt, K, and /Max Planck Inst., Mulheim /SLAC, SSRL. Electronic Structure of Neutral And Monoanionic Tris(Benzene-1,2-Dithiolato) Metal Complexes of Molybdenum And Tungsten. United States: N. p., 2007. Web. doi:10.1021/ic700600r.
Kapre, R R, Bothe, E, Weyhermuller, T, George, S D, Wieghardt, K, & /Max Planck Inst., Mulheim /SLAC, SSRL. Electronic Structure of Neutral And Monoanionic Tris(Benzene-1,2-Dithiolato) Metal Complexes of Molybdenum And Tungsten. United States. doi:10.1021/ic700600r.
Kapre, R R, Bothe, E, Weyhermuller, T, George, S D, Wieghardt, K, and /Max Planck Inst., Mulheim /SLAC, SSRL. Tue . "Electronic Structure of Neutral And Monoanionic Tris(Benzene-1,2-Dithiolato) Metal Complexes of Molybdenum And Tungsten". United States. doi:10.1021/ic700600r.
@article{osti_915364,
title = {Electronic Structure of Neutral And Monoanionic Tris(Benzene-1,2-Dithiolato) Metal Complexes of Molybdenum And Tungsten},
author = {Kapre, R R and Bothe, E and Weyhermuller, T and George, S D and Wieghardt, K and /Max Planck Inst., Mulheim /SLAC, SSRL},
abstractNote = {The reaction of 3 equiv of the ligand 2-mercapto-3,5-di-tert-butylaniline, H{sub 2}[L{sub N,S}], or 3,5-di-tert-butyl-1,2-benzenedithiol, H{sub 2}[L{sub S,S}], with 1 equiv of [MoO{sub 2}(acac){sub 2}] or WCl{sub 6} (acac = acetonylacetate(1-)) in methanol or CCl{sub 4} afforded the diamagnetic neutral complexes [MoV(L{sub N,S}){sub 2}(L{sup {center_dot}}{sub N,S})]{sup 0} (1), [MoV(L{sub S,S}){sub 2}(L{sup {center_dot}}{sub S,S})] (2), and [W{sup V}(L{sub S,S}){sub 2}(L{sup {center_dot}}{sub S,S})] (3), where (L{sup {center_dot}}{sub N,S}){sup -} and (L{sup {center_dot}}{sub S,S}){sup -} represent monoanionic {pi}-radical ligands (S{sub rad} = 1/2), which are the one-electron oxidized forms of the corresponding closed-shell dianions (L{sub N,S}){sup 2-} and (L{sub S,S}){sup 2-}. Complexes 1-3 are trigonal-prismatic members of the electron-transfer series [ML{sub 3}]{sup z} (z = 0, 1-, 2-). Reaction of 2 and 3 with [N(n-Bu){sub 4}](SH) in CH{sub 2}Cl{sub 2} under anaerobic conditions afforded paramagnetic crystalline [N(n-Bu){sub 4}][Mo{sup V}(L{sub S,S}){sub 3}] (4) and [N(n-Bu){sub 4}][W{sup V}(L{sub S,S}){sub 3}] (5). Complexes 1-5 have been characterized by X-ray crystallography. S K-edge X-ray absorption and infrared spectroscopy prove that a {pi}-radical ligand (L{sup {center_dot}}{sub S,S}){sup -} is present in neutral 2 and 3, whereas the monoanions [M{sup V}(L{sub S,S}){sub 3}]{sup -} contain only closed-shell dianionic ligands. These neutral species have previously been incorrectly described as [M{sup VI}(L){sub 3}]{sup 0} complexes with a Mo{sup VI} or W{sup VI} (d{sup 0}) central metal ion; they are, in fact M{sup V} (d{sup 1}) (M = Mo, W) species: [Mo{sup V}(L{sub S,S}){sub 2}(L{sup {center_dot}}{sub S,S})] and [W{sup V}(L{sub S,S}){sub 2}(L{sup {center_dot}}{sub S,S})] with a diamagnetic ground state S{sub t} = 0, which is generated by intramolecular, antiferromagnetic coupling between the M{sup V} (d{sup 1}) central ion (S{sub M} = 1/2) and a ligand radical (L{sup {center_dot}}{sub S,S}){sup -} (S{sub rad} = 1/2).},
doi = {10.1021/ic700600r},
journal = {Inorg.Chem.46:5642-5650,2007},
issn = {0020-1669},
number = ,
volume = 46,
place = {United States},
year = {2007},
month = {9}
}