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Title: First-row transition metal complexes of ENENES ligands: the ability of the thioether donor to impact the coordination chemistry

Abstract

We report the reactions of two variants of ENENES ligands, E(CH 2) 2NH(CH) 2SR, where E = 4-morpholinyl, R = Ph (a), Bn (b) with MCl 2 (M = Mn, Fe, Co, Ni and Cu) in coordinating solvents (MeCN, EtOH) affords isolable complexes, whose magnetic susceptibility measurements suggest paramagnetism and a high-spin formulation. X-Ray diffraction studies of available crystals show that the ligand coordinates to the metal in either a bidentate κ 2[N,N'] or tridentate κ 3[N,N',S] fashion, depending on the nature of ligand and/or identity of the metal atom. In the case of a less basic SPh moiety, a bidentate coordination mode was identified for harder metals (Mn, Fe), whereas a tridentate coordination mode was identified in the case of a more basic SBn moiety with softer metals (Ni, Cu). In the intermediate case of Co, ligands a and b coordinate via κ 2[N,N'] and κ 3[N,N',S] coordination modes, which can be conveniently predicted by DFT calculations. Finally, for the softest metal (Cu), ligand a coordinates in a κ 3[N,N',S] fashion.

Authors:
 [1];  [1]; ORCiD logo [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC); USDOE Laboratory Directed Research and Development (LDRD) Program
OSTI Identifier:
1457264
Report Number(s):
LA-UR-15-27247
Journal ID: ISSN 1477-9226; ICHBD9
Grant/Contract Number:  
AC52-06NA25396; AC04-94AL85000
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Dalton Transactions
Additional Journal Information:
Journal Volume: 45; Journal Issue: 4; Journal ID: ISSN 1477-9226
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Dub, Pavel A., Scott, Brian L., and Gordon, John C. First-row transition metal complexes of ENENES ligands: the ability of the thioether donor to impact the coordination chemistry. United States: N. p., 2015. Web. doi:10.1039/C5DT03855C.
Dub, Pavel A., Scott, Brian L., & Gordon, John C. First-row transition metal complexes of ENENES ligands: the ability of the thioether donor to impact the coordination chemistry. United States. doi:10.1039/C5DT03855C.
Dub, Pavel A., Scott, Brian L., and Gordon, John C. Mon . "First-row transition metal complexes of ENENES ligands: the ability of the thioether donor to impact the coordination chemistry". United States. doi:10.1039/C5DT03855C. https://www.osti.gov/servlets/purl/1457264.
@article{osti_1457264,
title = {First-row transition metal complexes of ENENES ligands: the ability of the thioether donor to impact the coordination chemistry},
author = {Dub, Pavel A. and Scott, Brian L. and Gordon, John C.},
abstractNote = {We report the reactions of two variants of ENENES ligands, E(CH2)2NH(CH)2SR, where E = 4-morpholinyl, R = Ph (a), Bn (b) with MCl2 (M = Mn, Fe, Co, Ni and Cu) in coordinating solvents (MeCN, EtOH) affords isolable complexes, whose magnetic susceptibility measurements suggest paramagnetism and a high-spin formulation. X-Ray diffraction studies of available crystals show that the ligand coordinates to the metal in either a bidentate κ2[N,N'] or tridentate κ3[N,N',S] fashion, depending on the nature of ligand and/or identity of the metal atom. In the case of a less basic SPh moiety, a bidentate coordination mode was identified for harder metals (Mn, Fe), whereas a tridentate coordination mode was identified in the case of a more basic SBn moiety with softer metals (Ni, Cu). In the intermediate case of Co, ligands a and b coordinate via κ2[N,N'] and κ3[N,N',S] coordination modes, which can be conveniently predicted by DFT calculations. Finally, for the softest metal (Cu), ligand a coordinates in a κ3[N,N',S] fashion.},
doi = {10.1039/C5DT03855C},
journal = {Dalton Transactions},
issn = {1477-9226},
number = 4,
volume = 45,
place = {United States},
year = {2015},
month = {12}
}

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