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Synthesis, properties and crystal structures of 6-, 7- and 8-coordinate Zr(IV) and Hf(IV) complexes involving thioether and selenoether ligands

Synthesis, properties and crystal structures of 6-, 7- and 8-coordinate Zr(IV) and Hf(IV) complexes involving thioether and selenoether ligands
Synthesis, properties and crystal structures of 6-, 7- and 8-coordinate Zr(IV) and Hf(IV) complexes involving thioether and selenoether ligands
A series of 6-,7- and 8-coordinate complexes of the form [MCl4(L-L)] (M = Zr, Hf; L-L = MeE(CH2)(2)EMe), [ZrCl4([9]aneS(3))] and [MCl4{MeE(CH2)(2)EMe}(2)] (E = S or Se) has been obtained in moderate to high yield by reaction of [MCl4(Me2S)(2)] with one (or three for the 1 : 2 M : L-L species) molar equivalents of L-L in rigorously anhydrous CH2Cl2. The poorly soluble products have been characterised by far IR spectroscopy, diffuse reflectance UV-Vis spectroscopy and microanalyses. H-1 NMR data are reported for certain systems, although in the majority of cases the very poor solubility prevented useful NMR experiments. The crystal structures of six representative examples, the distorted octahedral [ZrCl4(Me2S)(2)] and [HfCl4{MeSe(CH2)(2)SeMe}], the metallocyclic [(ZrCl4)(2){mu-MeS(CH2)(3)-SMe}(2)], the flattened dodecahedral [ZrCl4{MeS(CH2)(2)SMe}(2)] and [HfCl4{MeS(CH2)(2)SMe}(2)] and the 7-coordinate [ZrCl4([9]aneS(3))] are also described. The crystal structure of [Me2SCH2Cl](2)[Zr2Cl10], formed during reaction of [ZrCl4(Me2S)(2)] with MeSe(CH2)(2)SeMe in CH2Cl2 is also presented.
nuclear-magnetic-resonance, coordination chemistry, titanium tetrachloride, dithioether complexes, tin(iv) halides, zirconium, adducts, chloride, films
1472-7773
3153-3159
Hart, Richard
4908bfee-deb5-4bc7-b05c-220ac8ea2948
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Patel, Bhavesh
d08a7519-a670-4a58-9155-0810d9c85f7a
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Hart, Richard
4908bfee-deb5-4bc7-b05c-220ac8ea2948
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Patel, Bhavesh
d08a7519-a670-4a58-9155-0810d9c85f7a
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037

Hart, Richard, Levason, William, Patel, Bhavesh and Reid, Gillian (2002) Synthesis, properties and crystal structures of 6-, 7- and 8-coordinate Zr(IV) and Hf(IV) complexes involving thioether and selenoether ligands. Journal of the Chemical Society, Dalton Transactions, 2002 (16), 3153-3159. (doi:10.1039/b201080c).

Record type: Article

Abstract

A series of 6-,7- and 8-coordinate complexes of the form [MCl4(L-L)] (M = Zr, Hf; L-L = MeE(CH2)(2)EMe), [ZrCl4([9]aneS(3))] and [MCl4{MeE(CH2)(2)EMe}(2)] (E = S or Se) has been obtained in moderate to high yield by reaction of [MCl4(Me2S)(2)] with one (or three for the 1 : 2 M : L-L species) molar equivalents of L-L in rigorously anhydrous CH2Cl2. The poorly soluble products have been characterised by far IR spectroscopy, diffuse reflectance UV-Vis spectroscopy and microanalyses. H-1 NMR data are reported for certain systems, although in the majority of cases the very poor solubility prevented useful NMR experiments. The crystal structures of six representative examples, the distorted octahedral [ZrCl4(Me2S)(2)] and [HfCl4{MeSe(CH2)(2)SeMe}], the metallocyclic [(ZrCl4)(2){mu-MeS(CH2)(3)-SMe}(2)], the flattened dodecahedral [ZrCl4{MeS(CH2)(2)SMe}(2)] and [HfCl4{MeS(CH2)(2)SMe}(2)] and the 7-coordinate [ZrCl4([9]aneS(3))] are also described. The crystal structure of [Me2SCH2Cl](2)[Zr2Cl10], formed during reaction of [ZrCl4(Me2S)(2)] with MeSe(CH2)(2)SeMe in CH2Cl2 is also presented.

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Published date: 2002
Keywords: nuclear-magnetic-resonance, coordination chemistry, titanium tetrachloride, dithioether complexes, tin(iv) halides, zirconium, adducts, chloride, films

Identifiers

Local EPrints ID: 19764
URI: http://eprints.soton.ac.uk/id/eprint/19764
ISSN: 1472-7773
PURE UUID: 41e0869f-8d85-4156-b6ba-850b347f42de
ORCID for William Levason: ORCID iD orcid.org/0000-0003-3540-0971
ORCID for Gillian Reid: ORCID iD orcid.org/0000-0001-5349-3468

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Date deposited: 20 Feb 2006
Last modified: 08 Jan 2022 02:38

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Contributors

Author: Richard Hart
Author: William Levason ORCID iD
Author: Bhavesh Patel
Author: Gillian Reid ORCID iD

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