Group 4 Half-Sandwich Tris(trimethylsilylmethyl) Complexes: Thermal Decomposition and Reactivity with N,N¿Dimethylamine-Borane.
Authors
Greño Ocariz, Maider; Horno Martín, Estefanía del; Mena Montoro, Miguel; Pérez Redondo, Adrián; Varela Izquierdo, Víctor; [et al.]Identifiers
Permanent link (URI): http://hdl.handle.net/10017/50004DOI: 10.1021/acs.inorgchem.7b01607
ISSN: 0020-1669
Date
2017-09-18Affiliation
Universidad de Alcalá. Departamento de Química Analítica, Química Física e Ingeniería Química; Universidad de Alcalá. Departamento de Química Orgánica y Química InorgánicaFunders
Ministerio de Economía y Competitividad de España, Universidad de Alcalá
Bibliographic citation
Inorganic Chemistry, 2017, v. 56, n. 18, p. 11220-11229
Description / Notes
Este artículo se publicó como open access article dentro de la revista, tras el pago que exigía la editorial.
Project
CTQ2013-44625-R, CCG2016/EXP-028
Document type
info:eu-repo/semantics/article
Version
info:eu-repo/semantics/publishedVersion
Rights
Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0)
Access rights
info:eu-repo/semantics/openAccess
Abstract
The thermal decomposition of group 4 trimethylsilylmethyl derivatives [M(eta5-C5Me5)(CH2SiMe3)3] (M = Ti (1), Zr (2), Hf (3)) in solution and their reactivity with N,N-dimethylamine-borane were investigated. Heating of hydrocarbon solutions of compounds 2 and 3 at 130?200 °C results in the elimination of SiMe4 and the clean formation of the singular alkylidene-alkylidyne zirconium and hafnium compounds [{M(eta5-C5Me5)}3{(mu-CH)3SiMe}(mu3-CSiMe3)] (M = Zr (4), Hf (5)). The reaction of 2 and 3 with NHMe2BH3 (?1 equiv) at room temperature affords the dialkyl(dimethylamidoborane) complexes [M(eta5-C5Me5)(CH2SiMe3)2(NMe2BH3)] (M = Zr (6), Hf (7)). Compounds 6 and 7 are unstable in solution and decompose with formation of the alkyl(dimethylamino)borane [B(CH2SiMe3)H(NMe2)] (8), SiMe4, and other minor byproducts, including the tetranuclear zirconium(III) octahydride complex [{Zr(eta5-C5Me5)}4(mu-H)8] (9) in the decomposition of 6. Addition of NHMe2BH3 to the titanium tris(trimethylsilylmethyl) derivative 1 gives the trinuclear mixed valence Ti(II)/Ti(III) tetrahydride complex [{Ti(eta5-C5Me5)(mu-H)}3(mu3-H)(mu3-NMe2BH2)] (10) at 45?65 °C. While the complete conversion of 1 under argon atmosphere requires excess NHMe2BH3 (up to 15 equiv), complex 10 is readily prepared with 3 equiv of NHMe2BH3 under a hydrogen atmosphere indicating that the formation of 10 involves hydrogenolysis of 1 in the presence of (NMe2BH2)2. In absence of amine?borane, the reaction of 1 with H2 leads to the tetranuclear titanium(III) octahydride [{Ti(eta5-C5Me5)}4(mu-H)8] (11), which upon addition of NHMe2BH3 and subsequent heating at 65 °C affords complex 10. The X-ray crystal structures of 2, 4, 5, 10, and 11 were determined.
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