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

Dinuclear niobium(III), tantalum(III) and tantalum(IV) complexes with thioether and selenoether ligands
Dinuclear niobium(III), tantalum(III) and tantalum(IV) complexes with thioether and selenoether ligands
Magnesium reduction of MCl5 (M = Nb or Ta) in the presence of R2S (R = Me or nBu) affords the complexes [M2Cl4(R2S)2(?-Cl)2(?-R2S)]. The X-ray structures of those complexes where M = Nb or Ta, R = nBu2S, and of a new polymorph of [Ta2Cl4(Me2S)2(?-Cl)2(?-Me2S)], show that they have confacial bi-octahedral structures with Mdouble bond; length as m-dashM double bonds. The reactions of [Nb2Cl4(R2S)2(?-Cl)2(?-R2S)] with MeSCH2CH2SMe, MeSeCH2CH2SeMe or MeSeCH2CH2CH2SeMe produce the edge-linked dimers [Nb2Cl4(MeSCH2CH2SMe)2(?-Cl)2] and [Nb2Cl4{MeSe(CH2)nSeMe}2(?-Cl)2], all with Mdouble bond; length as m-dashM double bonds (M26+). The tantalum diselenoether complex, [Ta2Cl4(MeSeCH2CH2SeMe)2(?-Cl)2], is similar. Two “dimer of dimers”, [{Nb2Cl4(?-Cl)2(?-Me2S)}2(?-MeSeCH2CH2CH2SeMe)2] and [{Ta2Cl4(?-Cl)2(?-Me2S)}2(?-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. Under similar conditions the xylyl-linked diselenoether, o-C6H4(CH2SeMe)2, gave a complex mixture of products, including [Ta2Cl4{o-C6H4(CH2SeMe)2}2(?-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].
niobium, tantalum, thioether, selenoether, x-ray structure
0277-5387
230-237
Benjamin, Sophie L.
33433a1a-691e-439e-a277-e7577bde3a1a
Chang, Yao-Pang
9516eba3-1424-411c-8f13-c564cae63407
Huggon, Michelle
3a5a3597-7407-40db-b61d-d22aaea8038c
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Benjamin, Sophie L.
33433a1a-691e-439e-a277-e7577bde3a1a
Chang, Yao-Pang
9516eba3-1424-411c-8f13-c564cae63407
Huggon, Michelle
3a5a3597-7407-40db-b61d-d22aaea8038c
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037

Benjamin, Sophie L., Chang, Yao-Pang, Huggon, Michelle, Levason, William and Reid, Gillian (2015) Dinuclear niobium(III), tantalum(III) and tantalum(IV) complexes with thioether and selenoether ligands. Polyhedron, 99, 230-237. (doi:10.1016/j.poly.2015.07.062).

Record type: Article

Abstract

Magnesium reduction of MCl5 (M = Nb or Ta) in the presence of R2S (R = Me or nBu) affords the complexes [M2Cl4(R2S)2(?-Cl)2(?-R2S)]. The X-ray structures of those complexes where M = Nb or Ta, R = nBu2S, and of a new polymorph of [Ta2Cl4(Me2S)2(?-Cl)2(?-Me2S)], show that they have confacial bi-octahedral structures with Mdouble bond; length as m-dashM double bonds. The reactions of [Nb2Cl4(R2S)2(?-Cl)2(?-R2S)] with MeSCH2CH2SMe, MeSeCH2CH2SeMe or MeSeCH2CH2CH2SeMe produce the edge-linked dimers [Nb2Cl4(MeSCH2CH2SMe)2(?-Cl)2] and [Nb2Cl4{MeSe(CH2)nSeMe}2(?-Cl)2], all with Mdouble bond; length as m-dashM double bonds (M26+). The tantalum diselenoether complex, [Ta2Cl4(MeSeCH2CH2SeMe)2(?-Cl)2], is similar. Two “dimer of dimers”, [{Nb2Cl4(?-Cl)2(?-Me2S)}2(?-MeSeCH2CH2CH2SeMe)2] and [{Ta2Cl4(?-Cl)2(?-Me2S)}2(?-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. Under similar conditions the xylyl-linked diselenoether, o-C6H4(CH2SeMe)2, gave a complex mixture of products, including [Ta2Cl4{o-C6H4(CH2SeMe)2}2(?-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].

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Accepted/In Press date: 27 July 2015
e-pub ahead of print date: 31 July 2015
Published date: 15 October 2015
Keywords: niobium, tantalum, thioether, selenoether, x-ray structure
Organisations: Chemistry

Identifiers

Local EPrints ID: 382864
URI: http://eprints.soton.ac.uk/id/eprint/382864
ISSN: 0277-5387
PURE UUID: 1a9fe03d-e20f-4824-b967-237651697337
ORCID for William Levason: ORCID iD orcid.org/0000-0003-3540-0971
ORCID for Gillian Reid: ORCID iD orcid.org/0000-0001-5349-3468

Catalogue record

Date deposited: 21 Oct 2015 10:47
Last modified: 03 Dec 2019 02:07

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