Titanocene – 1,4,6-tris(trimethylsilyl)hex-3-ene-1,5-diyne-3-yl complexes – crystal structures and their retro reaction

Horáček, Michal; Cı́sařová, Ivana; Kubišta, Jiřı́; Spannenberg, Anke; Dallmann, K.; Rosenthal, Uwe; Mach, Karel

doi:10.1016/j.jorganchem.2004.08.035

Cited by 11 publications

(3 citation statements)

References 42 publications

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“…Titanium analogues have also been studied [79][80][81]. Reaction of [TiCl 2 Cp 2 ] with two equivalents of Me 3 Si-C C-C C-SiMe 3 afforded the 2,4-diethynylmetallacycle 66 in 65% yield, the structure of which has also been determined by X-ray crystallography (Figs.…”

Section: Reductive Coupling Of Buta-13-diynesmentioning

confidence: 99%

Dibenzometallacyclopentadienes, boroles and selected transition metal and main group heterocyclopentadienes: Synthesis, catalytic and optical properties

Steffen

Ward

Jones

et al. 2010

Coordination Chemistry Reviews

113

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Section: Reductive Coupling Of Buta-13-diynesmentioning

confidence: 99%

Dibenzometallacyclopentadienes, boroles and selected transition metal and main group heterocyclopentadienes: Synthesis, catalytic and optical properties

Steffen

Ward

Jones

et al. 2010

Coordination Chemistry Reviews

113

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“…This effect has recently been demonstrated for the first stable vinyl cation stabilized by the presence of two silyl groups in positions β to the carbocation 21a methyl-substituted titanocene(III) diacetylide tweezer complexes,21b or butenyne derivatives, as well as for an easy silicon migration over cyclopentadiene systems …”

Section: Resultsmentioning

confidence: 88%

Nonclassical Bonding in Titanasilacyclohexadiene Compounds Resulting from Highly Methyl-Substituted Titanocene−Bis(trimethylsilyl)ethyne Complexes and Bis((trimethylsilyl)ethynyl)silanes

et al. 2005

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Reactions at elevated temperatures (150 °C) of titanocene−η2-bis(trimethylsilyl)ethyne (btmse) complexes [(η5-C5H5 - n Me n )2Ti(η2-btmse)] (n = 3−5; 1b−d) with bis((trimethylsilyl)ethynyl)dimethylsilane (2a) afford the unusual 1,1-bis(η5-cyclopentadienyl)-4,4-dimethyl-3,5-bis(trimethylsilyl)-1-titana-4-silacyclohexa-2,5-diene complexes [(η5-C5H5 - n Me n )2Ti{CC(SiMe3)}2SiMe2] (4b−d), whereas the nonmethylated precursor [(η5-C5H5)2Ti(η2-btmse)] (1a) gives under similar conditions the known dinuclear, acetylide-bridged complex [{(η5-C5H5)2Ti(μ-η1:η2-C⋮CSiMe3)}2] (3a). In contrast, analogous reactions with bis((trimethylsilyl)ethynyl)diphenylsilane (2b) give the product of simple ligand exchange [(η5-C5Me5)2Ti(η2-Me3SiC⋮CSiPh2C⋮CSiMe3)] (6d) from 1d and mixtures containing the similar complex [(η5-C5HMe4)2Ti(η2-Me3SiC⋮CSiPh2C⋮CSiMe3)] (6c) and the titanasilacyclohexadiene [Ti(η5-C5HMe4)2Ti{CC(SiMe3)}2SiPh2] (5c) from 1c. Hydrogenolysis of 5c (1 bar/3 h) affords 1,4-bis(trimethylsilyl)-5,5-diphenyl-5-silacyclopenta-1,3-diene (7). Compounds 4 and 5 possess a surplus of two bonding electrons at the titanium-bonded carbon atoms (Cα) with paired spins, whose presence is reflected by extremely short Ti−Cα bond lengths (1.981(4)−1.998(3) Å) and Cα−Cα contacts (1.821(4)−1.933(2) Å), the latter excluding the presence of a 3-silacyclopenta-1,4-diene moiety simply bonded to titanium via two σ bonds. DFT calculations showed that the two singly occupied p orbitals at Cα interact with the titanocene 1a1 orbital, giving rise to a three-center−two-electron, Δ-shaped bond.

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“…There is the corresponding titanocene dichloride that has been reported to form titanocyclopentadienes with Me 3 SiC≡CSiMe 3 (18). 30,38,39 Alternatively, Nishihara et al…”

Section: Alternative Metallocyclopentadienes For Stoichiometric or Catalytic Cycloaddition Reactions And Other Organic Reactionsmentioning

confidence: 99%

Investigation and Study of Monomers and Polymers Based on Known Metal Induced Couplings of Alkynes and Diynes

Quinn¹

2023

Preprint

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Titanocene – 1,4,6-tris(trimethylsilyl)hex-3-ene-1,5-diyne-3-yl complexes – crystal structures and their retro reaction

Cited by 11 publications

References 42 publications

Dibenzometallacyclopentadienes, boroles and selected transition metal and main group heterocyclopentadienes: Synthesis, catalytic and optical properties

Dibenzometallacyclopentadienes, boroles and selected transition metal and main group heterocyclopentadienes: Synthesis, catalytic and optical properties

Nonclassical Bonding in Titanasilacyclohexadiene Compounds Resulting from Highly Methyl-Substituted Titanocene−Bis(trimethylsilyl)ethyne Complexes and Bis((trimethylsilyl)ethynyl)silanes

Investigation and Study of Monomers and Polymers Based on Known Metal Induced Couplings of Alkynes and Diynes

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