Dinuclear niobium(III), tantalum(III) and tantalum(IV) complexes with thioether and selenoether ligands

Benjamin, S.L. ORCID: 0000-0002-5038-1599, Chang, Y., Huggon, M., Levason, W. and Reid, G., 2015. Dinuclear niobium(III), tantalum(III) and tantalum(IV) complexes with thioether and selenoether ligands. Polyhedron, 99, pp. 230-237. ISSN 0277-5387

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Abstract

Magnesium reduction of MCl5 (M = Nb or Ta) in the presence of R2S (R = Me or nBu) affords the complexes [M2Cl4(R2S)2(μ-Cl)2(μ-R2S)]. The X-ray structures of those complexes where M = Nb or Ta, R = nBu2S, and of a new polymorph of [Ta2Cl4(Me2S)2(μ-Cl)2(μ-Me2S)], show that they have confacial bi-octahedral structures with M=M double bonds. The reactions of [Nb2Cl4(R2S)2(μ-Cl)2(μ-R2S)] with MeSCH2CH2SMe, MeSeCH2CH2SeMe or MeSeCH2CH2CH2SeMe produce the edge-linked dimers [Nb2Cl4(MeSCH2CH2SMe)2(μ-Cl)2] and [Nb2Cl4{MeSe(CH2)nSeMe}2(μ-Cl)2], all with M=M double bonds (M26+). The tantalum diselenoether complex, [Ta2Cl4(MeSeCH2CH2SeMe)2(μ-Cl)2], is similar. Two “dimer of dimers”, [{Nb2Cl4(μ-Cl)2(μ-Me2S)}2(μ-MeSeCH2CH2CH2SeMe)2] and [{Ta2Cl4(μ-Cl)2(μ-Me2S)}2(μ-nBuSeCH2CH2CH2SenBu)2], containing confacial bi-octahedra linked by diselenoether bridges, were obtained as minor by-products and were identified via their X-ray crystal structures. The xylyl-linked diselenoether, o-C6H4(CH2SeMe)2, gave a complex mixture of products, including [Ta2Cl4{o-C6H4(CH2SeMe)2}2(μ-Se)2]. The complexes were characterised by microanalysis, IR and UV–visible spectroscopy. X-ray crystal structures are reported for [Nb2Cl6(nBu2S)3], [Ta2Cl6(nBu2S)3], [Ta2Cl8(Me2S)2], [Ta2Cl6(Me2S)3], [Ta2Cl4{o-C6H4(CH2SeMe)2}2(Se)2], [{Ta2Cl6(Me2S)(nBuSeCH2CH2CH2SenBu)}2] and [Ta2Cl4(Me2S)4(S)2].

Item Type: Journal article
Publication Title: Polyhedron
Creators: Benjamin, S.L., Chang, Y., Huggon, M., Levason, W. and Reid, G.
Publisher: Pergamon Press
Place of Publication: Oxford
Date: 2015
Volume: 99
ISSN: 0277-5387
Identifiers:
NumberType
10.1016/j.poly.2015.07.062DOI
Divisions: Schools > School of Science and Technology
Depositing User: EPrints Services
Date Added: 09 Oct 2015 09:46
Last Modified: 09 Jun 2017 13:10
URI: http://irep.ntu.ac.uk/id/eprint/2541

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