Synthesis and structures of monocyclopentadienylniobium complexes with bi- and tri-dentate dithiolate ligands

Roland K. Dersch, Henrik Jungclas, W. Edward Lindsell, Georgina M. Rosair

Research output: Contribution to journalArticle

Abstract

Reactions of cyclopentadienyl and methylcyclopentadienyl-tetrachloroniobium with thallium(I) 1, 3-propanedithiolate yield compounds [NbCpx(1,3-S2C 3H6)2] [1, Cpx = ?-C 5H5 (Cp); 2, Cpx = ?-C5H 4Me (Cp')]; similar reactions of the thallium(I) derivative of 2,2'-thiodiethanethiol afford [NbCpxCl2{(SC 2H4)2S}] (3, Cpx = Cp; 4, Cp x = Cp'). Reaction of [NbCp'Cl4] with thallium(I) 2,2'-oxydiethanethiolate produces both [NbCp'Cl 2{(SC2H2)2O}] 5 and [NbCp'O{(SC 2H4)2O}] 6. Products have been characterised analytically and by NMR spectroscopy; the solid-state structures of 1,3,5 and 6 have been established by XRD. Compound 1 is five-coordinate, with a distorted four-legged piano-stool geometry, compound 3 is six-coordinate with tridentate thiolate and cis-equatorial Cl ligands, compound 5 is also six-coordinate but with trans-equatorial Cl ligands, and compound 6 is five-coordinate, approximating to a trigonal bipyramidal geometry with an equatorial oxo ligand. Compounds 1 and 2 are fluxional in solution due to non-rigidity of the twist conformations of the six-membered chelate rings, as shown by VT 1H NMR spectroscopic studies with ?G‡ = 42.7 ± 1.4 kJ mol -1 (at 231 K) and ?G‡ = 43.1 ± 1.3 kJ mol -1 (at 233 K), respectively, for ring inversion in toluene solutions. Cyclic voltammetric studies on 1 and 2 showed two consecutive, quasi-reversible, reduction processes, attributable to the sequential formation of mono- and di-anionic derivatives; reductions of the other compounds showed less evidence for reversibility. ESR spectra of the initial products of chemical reduction of 1 and 2 in thf, using either a sodium film or cobaltocene as reductant, are typical of those from Nb(IV) species and assigned to the respective mono-anions. © The Royal Society of Chemistry 2003.

Original languageEnglish
Pages (from-to)126-133
Number of pages8
JournalDalton Transactions
Issue number1
DOIs
Publication statusPublished - 7 Jan 2003

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Thallium
Ligands
Derivatives
Geometry
Reducing Agents
Toluene
Nuclear magnetic resonance spectroscopy
Anions
Paramagnetic resonance
Conformations
Sodium
Nuclear magnetic resonance

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Dersch, Roland K. ; Jungclas, Henrik ; Lindsell, W. Edward ; Rosair, Georgina M. / Synthesis and structures of monocyclopentadienylniobium complexes with bi- and tri-dentate dithiolate ligands. In: Dalton Transactions. 2003 ; No. 1. pp. 126-133.
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abstract = "Reactions of cyclopentadienyl and methylcyclopentadienyl-tetrachloroniobium with thallium(I) 1, 3-propanedithiolate yield compounds [NbCpx(1,3-S2C 3H6)2] [1, Cpx = ?-C 5H5 (Cp); 2, Cpx = ?-C5H 4Me (Cp')]; similar reactions of the thallium(I) derivative of 2,2'-thiodiethanethiol afford [NbCpxCl2{(SC 2H4)2S}] (3, Cpx = Cp; 4, Cp x = Cp'). Reaction of [NbCp'Cl4] with thallium(I) 2,2'-oxydiethanethiolate produces both [NbCp'Cl 2{(SC2H2)2O}] 5 and [NbCp'O{(SC 2H4)2O}] 6. Products have been characterised analytically and by NMR spectroscopy; the solid-state structures of 1,3,5 and 6 have been established by XRD. Compound 1 is five-coordinate, with a distorted four-legged piano-stool geometry, compound 3 is six-coordinate with tridentate thiolate and cis-equatorial Cl ligands, compound 5 is also six-coordinate but with trans-equatorial Cl ligands, and compound 6 is five-coordinate, approximating to a trigonal bipyramidal geometry with an equatorial oxo ligand. Compounds 1 and 2 are fluxional in solution due to non-rigidity of the twist conformations of the six-membered chelate rings, as shown by VT 1H NMR spectroscopic studies with ?G‡ = 42.7 ± 1.4 kJ mol -1 (at 231 K) and ?G‡ = 43.1 ± 1.3 kJ mol -1 (at 233 K), respectively, for ring inversion in toluene solutions. Cyclic voltammetric studies on 1 and 2 showed two consecutive, quasi-reversible, reduction processes, attributable to the sequential formation of mono- and di-anionic derivatives; reductions of the other compounds showed less evidence for reversibility. ESR spectra of the initial products of chemical reduction of 1 and 2 in thf, using either a sodium film or cobaltocene as reductant, are typical of those from Nb(IV) species and assigned to the respective mono-anions. {\circledC} The Royal Society of Chemistry 2003.",
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Synthesis and structures of monocyclopentadienylniobium complexes with bi- and tri-dentate dithiolate ligands. / Dersch, Roland K.; Jungclas, Henrik; Lindsell, W. Edward; Rosair, Georgina M.

In: Dalton Transactions, No. 1, 07.01.2003, p. 126-133.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Synthesis and structures of monocyclopentadienylniobium complexes with bi- and tri-dentate dithiolate ligands

AU - Dersch, Roland K.

AU - Jungclas, Henrik

AU - Lindsell, W. Edward

AU - Rosair, Georgina M.

PY - 2003/1/7

Y1 - 2003/1/7

N2 - Reactions of cyclopentadienyl and methylcyclopentadienyl-tetrachloroniobium with thallium(I) 1, 3-propanedithiolate yield compounds [NbCpx(1,3-S2C 3H6)2] [1, Cpx = ?-C 5H5 (Cp); 2, Cpx = ?-C5H 4Me (Cp')]; similar reactions of the thallium(I) derivative of 2,2'-thiodiethanethiol afford [NbCpxCl2{(SC 2H4)2S}] (3, Cpx = Cp; 4, Cp x = Cp'). Reaction of [NbCp'Cl4] with thallium(I) 2,2'-oxydiethanethiolate produces both [NbCp'Cl 2{(SC2H2)2O}] 5 and [NbCp'O{(SC 2H4)2O}] 6. Products have been characterised analytically and by NMR spectroscopy; the solid-state structures of 1,3,5 and 6 have been established by XRD. Compound 1 is five-coordinate, with a distorted four-legged piano-stool geometry, compound 3 is six-coordinate with tridentate thiolate and cis-equatorial Cl ligands, compound 5 is also six-coordinate but with trans-equatorial Cl ligands, and compound 6 is five-coordinate, approximating to a trigonal bipyramidal geometry with an equatorial oxo ligand. Compounds 1 and 2 are fluxional in solution due to non-rigidity of the twist conformations of the six-membered chelate rings, as shown by VT 1H NMR spectroscopic studies with ?G‡ = 42.7 ± 1.4 kJ mol -1 (at 231 K) and ?G‡ = 43.1 ± 1.3 kJ mol -1 (at 233 K), respectively, for ring inversion in toluene solutions. Cyclic voltammetric studies on 1 and 2 showed two consecutive, quasi-reversible, reduction processes, attributable to the sequential formation of mono- and di-anionic derivatives; reductions of the other compounds showed less evidence for reversibility. ESR spectra of the initial products of chemical reduction of 1 and 2 in thf, using either a sodium film or cobaltocene as reductant, are typical of those from Nb(IV) species and assigned to the respective mono-anions. © The Royal Society of Chemistry 2003.

AB - Reactions of cyclopentadienyl and methylcyclopentadienyl-tetrachloroniobium with thallium(I) 1, 3-propanedithiolate yield compounds [NbCpx(1,3-S2C 3H6)2] [1, Cpx = ?-C 5H5 (Cp); 2, Cpx = ?-C5H 4Me (Cp')]; similar reactions of the thallium(I) derivative of 2,2'-thiodiethanethiol afford [NbCpxCl2{(SC 2H4)2S}] (3, Cpx = Cp; 4, Cp x = Cp'). Reaction of [NbCp'Cl4] with thallium(I) 2,2'-oxydiethanethiolate produces both [NbCp'Cl 2{(SC2H2)2O}] 5 and [NbCp'O{(SC 2H4)2O}] 6. Products have been characterised analytically and by NMR spectroscopy; the solid-state structures of 1,3,5 and 6 have been established by XRD. Compound 1 is five-coordinate, with a distorted four-legged piano-stool geometry, compound 3 is six-coordinate with tridentate thiolate and cis-equatorial Cl ligands, compound 5 is also six-coordinate but with trans-equatorial Cl ligands, and compound 6 is five-coordinate, approximating to a trigonal bipyramidal geometry with an equatorial oxo ligand. Compounds 1 and 2 are fluxional in solution due to non-rigidity of the twist conformations of the six-membered chelate rings, as shown by VT 1H NMR spectroscopic studies with ?G‡ = 42.7 ± 1.4 kJ mol -1 (at 231 K) and ?G‡ = 43.1 ± 1.3 kJ mol -1 (at 233 K), respectively, for ring inversion in toluene solutions. Cyclic voltammetric studies on 1 and 2 showed two consecutive, quasi-reversible, reduction processes, attributable to the sequential formation of mono- and di-anionic derivatives; reductions of the other compounds showed less evidence for reversibility. ESR spectra of the initial products of chemical reduction of 1 and 2 in thf, using either a sodium film or cobaltocene as reductant, are typical of those from Nb(IV) species and assigned to the respective mono-anions. © The Royal Society of Chemistry 2003.

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