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

Journal Article · Wed Oct 05 00:00:00 EDT 2016 · Acta Crystallographica. Section C, Structural Chemistry (Online)

DOI:https://doi.org/10.1107/s2053229616008925· OSTI ID:1536593

Rong, Yi; Sambade, David; Parkin, Gerard

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(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.

• Research Organization: Columbia Univ., New York, NY (United States)
• Sponsoring Organization: USDOE Office of Science (SC)
• DOE Contract Number: FG02-93ER14339
• OSTI ID: 1536593
• Journal Information: Acta Crystallographica. Section C, Structural Chemistry (Online), Vol. 72, Issue 11; ISSN 2053-2296
• Publisher: International Union of Crystallography
• Country of Publication: United States
• Language: English

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Crystallography