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

BENJAMIN, S.L., 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: 23 Aug 2016 09:06
URI: http://irep.ntu.ac.uk/id/eprint/2541

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