skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Molecular structures of tris(1- tert -butyl-2-mercaptoimidazolyl)hydroborate complexes of titanium, zirconium and hafnium

Abstract

Cyclopentadienyl and tris(pyrazolyl)hydroborate have found much use as supporting ligands in the chemistry of titanium, zirconium and hafnium, especially with respect to applications involving olefin polymerization catalysis. In contrast, closely related tris(1-alkyl-2-mercaptoimidazolyl)hydroborate, [Tm R], ligands have so far found little application to the chemistry of these elements, despite the fact that such ligands are currently used extensively in coordination chemistry. In view of the fact that a substituent in the 2-position exerts a direct influence on the steric environment of the metal center, we report here the application of the sterically demanding tris(1-tert-butyl-2-mercaptoimidazolyl)hydroborate [Tm^{{\rm Bu}^{\rm t}}] ligand to these metals. Dichlorido(η 5-cyclopentadienyl)[tris(1-tert-butyl-2-sulfanylidene-2,3-dihydro-1H-imidazol-3-yl)borato-κ 3S,S′,H]zirconium(IV) benzene hemisolvate, [Zr(C 21H 34BN 6S 3)(C 5H 5)Cl 2]·0.5C 6H 6, (I), dichlorido(η 5-cyclopentadienyl)[tris(1-tert-butyl-2-sulfanylidene-2,3-dihydro-1H-imidazol-3-yl)borato-κ 3S,S′,H]titanium(IV) benzene hemisolvate, [Ti(C 21H 34BN 6S 3)(C 5H 5)Cl 2]·0.5C 6H 6, (II), [bis(1-tert-butyl-2-sulfanylidene-2,3-dihydro-1H-imidazol-3-yl)borato-κ 3S,S′,H]dichlorido(η 5-cyclopentadienyl)zirconium(IV), [Zr(C 14H 24BN 4S 2)(C 5H 5)Cl 2], (III), (1-tert-butyl-2,3-dihydro-1H-imidazole-2-thione-κS)(1-tert-butyl-2-sulfanylidene-1H-imidazol-3-ido-κ 2N 3,S)dichlorido(η 5-cyclopentadienyl)zirconium(IV) benzene monosolvate, [Zr(C 7H 11N 2S)(C 7H 12N 2S)(C 5H 5)Cl 2]·C 6H 6, (IV), and tribenzyl[tris(1-tert-butyl-2-sulfanylidene-2,3-dihydro-1H-imidazol-3-yl)borato-κ 3S,S′,S′′]hafnium(IV) benzene tetrasolvate, [Hf(C 7H 7) 3(C 21H 34BN 6S 3)]·4C 6H 6, (V), have been structurally characterized by X-ray diffraction. The [Tm^{{\rm Bu}^{\rm t}}^{{\rm Bu}^{\rm t}}] ligand coordinates to Ti and Zr in Cp[κmore » 3S 2,H-Tm^{{\rm Bu}^{\rm t}}]MCl 2[M = Zr, (I), and Ti, (II)] in a κ 3S 2,Hmode, while the benzyl compounds [Tm^{{\rm Bu}^{\rm t}}]M(CH 2Ph) 3[M = Zr and Hf, (V)] exhibit κ 3S 3coordination.« less

Authors:
; ;
Publication Date:
Research Org.:
Columbia Univ., New York, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1536593
DOE Contract Number:  
FG02-93ER14339
Resource Type:
Journal Article
Journal Name:
Acta Crystallographica. Section C, Structural Chemistry (Online)
Additional Journal Information:
Journal Volume: 72; Journal Issue: 11; Journal ID: ISSN 2053-2296
Publisher:
International Union of Crystallography
Country of Publication:
United States
Language:
English
Subject:
Chemistry; Crystallography

Citation Formats

Rong, Yi, Sambade, David, and Parkin, Gerard. Molecular structures of tris(1- tert -butyl-2-mercaptoimidazolyl)hydroborate complexes of titanium, zirconium and hafnium. United States: N. p., 2016. Web. doi:10.1107/s2053229616008925.
Rong, Yi, Sambade, David, & Parkin, Gerard. Molecular structures of tris(1- tert -butyl-2-mercaptoimidazolyl)hydroborate complexes of titanium, zirconium and hafnium. United States. doi:10.1107/s2053229616008925.
Rong, Yi, Sambade, David, and Parkin, Gerard. Wed . "Molecular structures of tris(1- tert -butyl-2-mercaptoimidazolyl)hydroborate complexes of titanium, zirconium and hafnium". United States. doi:10.1107/s2053229616008925.
@article{osti_1536593,
title = {Molecular structures of tris(1- tert -butyl-2-mercaptoimidazolyl)hydroborate complexes of titanium, zirconium and hafnium},
author = {Rong, Yi and Sambade, David and Parkin, Gerard},
abstractNote = {Cyclopentadienyl and tris(pyrazolyl)hydroborate have found much use as supporting ligands in the chemistry of titanium, zirconium and hafnium, especially with respect to applications involving olefin polymerization catalysis. In contrast, closely related tris(1-alkyl-2-mercaptoimidazolyl)hydroborate, [TmR], ligands have so far found little application to the chemistry of these elements, despite the fact that such ligands are currently used extensively in coordination chemistry. In view of the fact that a substituent in the 2-position exerts a direct influence on the steric environment of the metal center, we report here the application of the sterically demanding tris(1-tert-butyl-2-mercaptoimidazolyl)hydroborate [Tm^{{\rm Bu}^{\rm t}}] ligand to these metals. Dichlorido(η5-cyclopentadienyl)[tris(1-tert-butyl-2-sulfanylidene-2,3-dihydro-1H-imidazol-3-yl)borato-κ3S,S′,H]zirconium(IV) benzene hemisolvate, [Zr(C21H34BN6S3)(C5H5)Cl2]·0.5C6H6, (I), dichlorido(η5-cyclopentadienyl)[tris(1-tert-butyl-2-sulfanylidene-2,3-dihydro-1H-imidazol-3-yl)borato-κ3S,S′,H]titanium(IV) benzene hemisolvate, [Ti(C21H34BN6S3)(C5H5)Cl2]·0.5C6H6, (II), [bis(1-tert-butyl-2-sulfanylidene-2,3-dihydro-1H-imidazol-3-yl)borato-κ3S,S′,H]dichlorido(η5-cyclopentadienyl)zirconium(IV), [Zr(C14H24BN4S2)(C5H5)Cl2], (III), (1-tert-butyl-2,3-dihydro-1H-imidazole-2-thione-κS)(1-tert-butyl-2-sulfanylidene-1H-imidazol-3-ido-κ2N3,S)dichlorido(η5-cyclopentadienyl)zirconium(IV) benzene monosolvate, [Zr(C7H11N2S)(C7H12N2S)(C5H5)Cl2]·C6H6, (IV), and tribenzyl[tris(1-tert-butyl-2-sulfanylidene-2,3-dihydro-1H-imidazol-3-yl)borato-κ3S,S′,S′′]hafnium(IV) benzene tetrasolvate, [Hf(C7H7)3(C21H34BN6S3)]·4C6H6, (V), have been structurally characterized by X-ray diffraction. The [Tm^{{\rm Bu}^{\rm t}}^{{\rm Bu}^{\rm t}}] ligand coordinates to Ti and Zr in Cp[κ3S2,H-Tm^{{\rm Bu}^{\rm t}}]MCl2[M = Zr, (I), and Ti, (II)] in a κ3S2,Hmode, while the benzyl compounds [Tm^{{\rm Bu}^{\rm t}}]M(CH2Ph)3[M = Zr and Hf, (V)] exhibit κ3S3coordination.},
doi = {10.1107/s2053229616008925},
journal = {Acta Crystallographica. Section C, Structural Chemistry (Online)},
issn = {2053-2296},
number = 11,
volume = 72,
place = {United States},
year = {2016},
month = {10}
}