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

doi:10.1016/j.jorganchem.2004.09.075

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

Department of Applied Molecular Chemistry

Research output: Contribution to journal › Article › peer-review

7 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 language	English
Pages (from-to)	276-285
Number of pages	10
Journal	Journal of Organometallic Chemistry
Volume	690
Issue number	2
DOIs	https://doi.org/10.1016/j.jorganchem.2004.09.075
Publication status	Published - Jan 17 2005

All Science Journal Classification (ASJC) codes

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/j.jorganchem.2004.09.075

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

Research output: Contribution to journal › Article › peer-review

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

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.",

author = "Shota Niibayashi and Kaoru Mitsui and Yukihiro Motoyama and Hideo Nagashima",

year = "2005",

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doi = "10.1016/j.jorganchem.2004.09.075",

language = "English",

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journal = "Journal of Organometallic Chemistry",

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T1 - The effect of titanium alkoxides in the synthesis of heterobimetallic complexes by titanocene(III) alkoxide-induced metal-metal bond cleavage of metal carbonyl dimers

AU - Niibayashi, Shota

AU - Mitsui, Kaoru

AU - Motoyama, Yukihiro

AU - Nagashima, Hideo

PY - 2005/1/17

Y1 - 2005/1/17

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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JO - Journal of Organometallic Chemistry

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IS - 2

ER -

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

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