The effect of titanium alkoxides in the synthesis of heterobimetallic complexes by titanocene(III) alkoxide-induced metal-metal bond cleavage of metal carbonyl dimers

Shota Niibayashi, Kaoru Mitsui, Yukihiro Motoyama, Hideo Nagashima

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

A series of titanocene(III) alkoxides L 2Ti(III)OR where L = Cp, R = Et(1b), tBu(1a), 2,6-Me 2C 6H 3(1c), 2,6- tBu 2-4-Me-C 6H 2(1d), or L = Cp*, R = Me(2e), tBu(2a), Ph(2f) was synthesized and subjected to reaction with [CpM(CO) 3] 2 [M = Mo, W], [CpRu(CO) 2] 2, and Co 2(CO) 8. The Ti(III) precursors 1a, 1c, 2a, 2e, and 2f reacted with [CpM(CO) 3] 2 [M = Mo, W] to form heterobimetallic complexes L 2Ti(OR)(μ-OC)(CO) 2MCp [M = Mo, W], of which Ti and M are linked by an isocarbonyl bridge. Reactions of these Ti(III) complexes with Co 2(CO) 8 resulted in formation of Ti-Co 1 heterobimetallic complexes, Cp 2*Ti(O tBu)(μ-OC) Co(CO) 3 from 2a, 2e, or 2f, or Ti-Co 3 tetrametallic complexes, Cp 2Ti(O tBu)(μ-OC)Co 3(CO) 9 from 1a, 1b, or 1c. The products were characterized by NMR, IR, and X-ray crystallography. Reaction mechanisms were proposed from these results, in particular, from steric/electronic effects of titanium alkoxides.

Original languageEnglish
Pages (from-to)276-285
Number of pages10
JournalJournal of Organometallic Chemistry
Volume690
Issue number2
DOIs
Publication statusPublished - Jan 17 2005

Fingerprint

X ray crystallography
alkoxides
Carbon Monoxide
Titanium
Dimers
cleavage
titanium
Metals
dimers
Nuclear magnetic resonance
synthesis
metals
crystallography
nuclear magnetic resonance
products
electronics
titanocene
X Ray Crystallography
x rays

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

The effect of titanium alkoxides in the synthesis of heterobimetallic complexes by titanocene(III) alkoxide-induced metal-metal bond cleavage of metal carbonyl dimers. / Niibayashi, Shota; Mitsui, Kaoru; Motoyama, Yukihiro; Nagashima, Hideo.

In: Journal of Organometallic Chemistry, Vol. 690, No. 2, 17.01.2005, p. 276-285.

Research output: Contribution to journalArticle

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abstract = "A series of titanocene(III) alkoxides L 2Ti(III)OR where L = Cp, R = Et(1b), tBu(1a), 2,6-Me 2C 6H 3(1c), 2,6- tBu 2-4-Me-C 6H 2(1d), or L = Cp*, R = Me(2e), tBu(2a), Ph(2f) was synthesized and subjected to reaction with [CpM(CO) 3] 2 [M = Mo, W], [CpRu(CO) 2] 2, and Co 2(CO) 8. The Ti(III) precursors 1a, 1c, 2a, 2e, and 2f reacted with [CpM(CO) 3] 2 [M = Mo, W] to form heterobimetallic complexes L 2Ti(OR)(μ-OC)(CO) 2MCp [M = Mo, W], of which Ti and M are linked by an isocarbonyl bridge. Reactions of these Ti(III) complexes with Co 2(CO) 8 resulted in formation of Ti-Co 1 heterobimetallic complexes, Cp 2*Ti(O tBu)(μ-OC) Co(CO) 3 from 2a, 2e, or 2f, or Ti-Co 3 tetrametallic complexes, Cp 2Ti(O tBu)(μ-OC)Co 3(CO) 9 from 1a, 1b, or 1c. The products were characterized by NMR, IR, and X-ray crystallography. Reaction mechanisms were proposed from these results, in particular, from steric/electronic effects of titanium alkoxides.",
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N2 - A series of titanocene(III) alkoxides L 2Ti(III)OR where L = Cp, R = Et(1b), tBu(1a), 2,6-Me 2C 6H 3(1c), 2,6- tBu 2-4-Me-C 6H 2(1d), or L = Cp*, R = Me(2e), tBu(2a), Ph(2f) was synthesized and subjected to reaction with [CpM(CO) 3] 2 [M = Mo, W], [CpRu(CO) 2] 2, and Co 2(CO) 8. The Ti(III) precursors 1a, 1c, 2a, 2e, and 2f reacted with [CpM(CO) 3] 2 [M = Mo, W] to form heterobimetallic complexes L 2Ti(OR)(μ-OC)(CO) 2MCp [M = Mo, W], of which Ti and M are linked by an isocarbonyl bridge. Reactions of these Ti(III) complexes with Co 2(CO) 8 resulted in formation of Ti-Co 1 heterobimetallic complexes, Cp 2*Ti(O tBu)(μ-OC) Co(CO) 3 from 2a, 2e, or 2f, or Ti-Co 3 tetrametallic complexes, Cp 2Ti(O tBu)(μ-OC)Co 3(CO) 9 from 1a, 1b, or 1c. The products were characterized by NMR, IR, and X-ray crystallography. Reaction mechanisms were proposed from these results, in particular, from steric/electronic effects of titanium alkoxides.

AB - A series of titanocene(III) alkoxides L 2Ti(III)OR where L = Cp, R = Et(1b), tBu(1a), 2,6-Me 2C 6H 3(1c), 2,6- tBu 2-4-Me-C 6H 2(1d), or L = Cp*, R = Me(2e), tBu(2a), Ph(2f) was synthesized and subjected to reaction with [CpM(CO) 3] 2 [M = Mo, W], [CpRu(CO) 2] 2, and Co 2(CO) 8. The Ti(III) precursors 1a, 1c, 2a, 2e, and 2f reacted with [CpM(CO) 3] 2 [M = Mo, W] to form heterobimetallic complexes L 2Ti(OR)(μ-OC)(CO) 2MCp [M = Mo, W], of which Ti and M are linked by an isocarbonyl bridge. Reactions of these Ti(III) complexes with Co 2(CO) 8 resulted in formation of Ti-Co 1 heterobimetallic complexes, Cp 2*Ti(O tBu)(μ-OC) Co(CO) 3 from 2a, 2e, or 2f, or Ti-Co 3 tetrametallic complexes, Cp 2Ti(O tBu)(μ-OC)Co 3(CO) 9 from 1a, 1b, or 1c. The products were characterized by NMR, IR, and X-ray crystallography. Reaction mechanisms were proposed from these results, in particular, from steric/electronic effects of titanium alkoxides.

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