Bis(cyclopentadienyl)titanium complexes of naphthalene-1,8-dithiolates, biphenyl 2,2 '-dithiolates, and related ligands

S M Aucott, P Kilian, H L Milton, S D Robertson, A M Z Slawin, J D Woollins

Research output: Contribution to journalArticle

36 Citations (Scopus)

Abstract

Titanocene 1,8-dithiolato-naphthalene and titanocene 2,2'-dithiolato biphenyl are produced by the reaction of naphtho[1,8-cd]-1,2-dithiole [or the biphenyl] with titanocene dicarbonyl (Ti(II)) in toluene at room temperature. The proligands 2,7-di(tert-butyl)naphtho[1,8-cd]-1,2-dithiole, 5,6-dihydroacenaphtho[5,6-cd]-1,2-dithiole, 4,5-dithioacephenanthrylene, and 13,14-dithiapicene have been used in similar reactions with titanocene dicarbonyl to investigate the effect of steric bulk and of varying the naphthalene backbone on the final complex. The resulting Cp2TiS2Ar complexes (Ar = naphthalene) have been shown by temperature-dependent H-1 NMR spectroscopy to exist in solution in an envelope conformation with the six-membered TiS2C3 rings undergoing inversion on the NMR time scale while the similar Cp2TiS2Ar complexes (Ar = biphenyl, binaphthalene) interconvert more rapidly. Titanocene 2,2'-disulfinato biphenyl has been synthesized by the salt elimination reaction of titanocene dichloride (Ti(IV)) and the disodium salt of biphenyl 2,2'-disulfinic acid. Finally, the effect of using pro-ligands where the sulfur atoms have been mono- or di-oxidized has been studied, and an interesting oxygen elimination reaction is observed for the S=O fragments but not for the SO2 groups. All complexes have been characterized spectroscopically and seven X-ray structures are reported.

Original languageEnglish
Pages (from-to)2710-2718
Number of pages9
JournalInorganic Chemistry
Volume44
Issue number8
DOIs
Publication statusPublished - 18 Apr 2005

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Titanium
naphthalene
titanium
Ligands
ligands
elimination
salts
nuclear magnetic resonance
Salts
dichlorides
toluene
Toluene
sulfur
envelopes
Sulfur
Nuclear magnetic resonance spectroscopy
fragments
Conformations
inversions
acids

Keywords

  • crystal structures
  • sulfur
  • atoms

Cite this

Aucott, S M ; Kilian, P ; Milton, H L ; Robertson, S D ; Slawin, A M Z ; Woollins, J D . / Bis(cyclopentadienyl)titanium complexes of naphthalene-1,8-dithiolates, biphenyl 2,2 '-dithiolates, and related ligands. In: Inorganic Chemistry. 2005 ; Vol. 44, No. 8. pp. 2710-2718.
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abstract = "Titanocene 1,8-dithiolato-naphthalene and titanocene 2,2'-dithiolato biphenyl are produced by the reaction of naphtho[1,8-cd]-1,2-dithiole [or the biphenyl] with titanocene dicarbonyl (Ti(II)) in toluene at room temperature. The proligands 2,7-di(tert-butyl)naphtho[1,8-cd]-1,2-dithiole, 5,6-dihydroacenaphtho[5,6-cd]-1,2-dithiole, 4,5-dithioacephenanthrylene, and 13,14-dithiapicene have been used in similar reactions with titanocene dicarbonyl to investigate the effect of steric bulk and of varying the naphthalene backbone on the final complex. The resulting Cp2TiS2Ar complexes (Ar = naphthalene) have been shown by temperature-dependent H-1 NMR spectroscopy to exist in solution in an envelope conformation with the six-membered TiS2C3 rings undergoing inversion on the NMR time scale while the similar Cp2TiS2Ar complexes (Ar = biphenyl, binaphthalene) interconvert more rapidly. Titanocene 2,2'-disulfinato biphenyl has been synthesized by the salt elimination reaction of titanocene dichloride (Ti(IV)) and the disodium salt of biphenyl 2,2'-disulfinic acid. Finally, the effect of using pro-ligands where the sulfur atoms have been mono- or di-oxidized has been studied, and an interesting oxygen elimination reaction is observed for the S=O fragments but not for the SO2 groups. All complexes have been characterized spectroscopically and seven X-ray structures are reported.",
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Bis(cyclopentadienyl)titanium complexes of naphthalene-1,8-dithiolates, biphenyl 2,2 '-dithiolates, and related ligands. / Aucott, S M ; Kilian, P ; Milton, H L ; Robertson, S D ; Slawin, A M Z ; Woollins, J D .

In: Inorganic Chemistry, Vol. 44, No. 8, 18.04.2005, p. 2710-2718.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Bis(cyclopentadienyl)titanium complexes of naphthalene-1,8-dithiolates, biphenyl 2,2 '-dithiolates, and related ligands

AU - Aucott, S M

AU - Kilian, P

AU - Milton, H L

AU - Robertson, S D

AU - Slawin, A M Z

AU - Woollins, J D

PY - 2005/4/18

Y1 - 2005/4/18

N2 - Titanocene 1,8-dithiolato-naphthalene and titanocene 2,2'-dithiolato biphenyl are produced by the reaction of naphtho[1,8-cd]-1,2-dithiole [or the biphenyl] with titanocene dicarbonyl (Ti(II)) in toluene at room temperature. The proligands 2,7-di(tert-butyl)naphtho[1,8-cd]-1,2-dithiole, 5,6-dihydroacenaphtho[5,6-cd]-1,2-dithiole, 4,5-dithioacephenanthrylene, and 13,14-dithiapicene have been used in similar reactions with titanocene dicarbonyl to investigate the effect of steric bulk and of varying the naphthalene backbone on the final complex. The resulting Cp2TiS2Ar complexes (Ar = naphthalene) have been shown by temperature-dependent H-1 NMR spectroscopy to exist in solution in an envelope conformation with the six-membered TiS2C3 rings undergoing inversion on the NMR time scale while the similar Cp2TiS2Ar complexes (Ar = biphenyl, binaphthalene) interconvert more rapidly. Titanocene 2,2'-disulfinato biphenyl has been synthesized by the salt elimination reaction of titanocene dichloride (Ti(IV)) and the disodium salt of biphenyl 2,2'-disulfinic acid. Finally, the effect of using pro-ligands where the sulfur atoms have been mono- or di-oxidized has been studied, and an interesting oxygen elimination reaction is observed for the S=O fragments but not for the SO2 groups. All complexes have been characterized spectroscopically and seven X-ray structures are reported.

AB - Titanocene 1,8-dithiolato-naphthalene and titanocene 2,2'-dithiolato biphenyl are produced by the reaction of naphtho[1,8-cd]-1,2-dithiole [or the biphenyl] with titanocene dicarbonyl (Ti(II)) in toluene at room temperature. The proligands 2,7-di(tert-butyl)naphtho[1,8-cd]-1,2-dithiole, 5,6-dihydroacenaphtho[5,6-cd]-1,2-dithiole, 4,5-dithioacephenanthrylene, and 13,14-dithiapicene have been used in similar reactions with titanocene dicarbonyl to investigate the effect of steric bulk and of varying the naphthalene backbone on the final complex. The resulting Cp2TiS2Ar complexes (Ar = naphthalene) have been shown by temperature-dependent H-1 NMR spectroscopy to exist in solution in an envelope conformation with the six-membered TiS2C3 rings undergoing inversion on the NMR time scale while the similar Cp2TiS2Ar complexes (Ar = biphenyl, binaphthalene) interconvert more rapidly. Titanocene 2,2'-disulfinato biphenyl has been synthesized by the salt elimination reaction of titanocene dichloride (Ti(IV)) and the disodium salt of biphenyl 2,2'-disulfinic acid. Finally, the effect of using pro-ligands where the sulfur atoms have been mono- or di-oxidized has been studied, and an interesting oxygen elimination reaction is observed for the S=O fragments but not for the SO2 groups. All complexes have been characterized spectroscopically and seven X-ray structures are reported.

KW - crystal structures

KW - sulfur

KW - atoms

U2 - 10.1021/ic048483l

DO - 10.1021/ic048483l

M3 - Article

VL - 44

SP - 2710

EP - 2718

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 8

ER -