Reactions of the titanium-carbide species CpTi(μ2-Me)(μ2-NPi-Pr3)(μ4-C)(AlMe2)3

Graham, Todd W.; Ong, Christopher M.; Wei, Pingrong; Stephan, Douglas W.

doi:10.1016/j.jorganchem.2007.03.011

Cited by 11 publications

(3 citation statements)

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“…Interestingly, when the [CpTi(NPR 3 )L 2 ] complexes react with excess of another Lewis acid, [AlMe 3 ], heterometallic μ 4 - and μ 5 -carbide complexes arise (Figure ). , Thus, the thiolate complex, [CpTi(NP i Pr 3 )(SPh) 2 ], reacts with 3 equiv of [AlMe 3 ] to furnish [CpTi(μ 4 -C)(μ-NP i Pr 3 )(μ-SPh) 2 (AlMe)(AlMe 2 ) 2 ], upon release of three equivalents of methane. , The related methyl complex, [CpTi(NP i Pr 3 )Me 2 ], reacts with 4 equiv of [AlMe 3 ]. This furnishes [CpTi(μ 5 -C)(μ-NP i Pr 3 )(μ-Me)(AlMe 2 ) 3 (AlMe 3 )], which expels [AlMe 3 ] upon recrystallization, thereby producing a μ 4 -carbide complex: [CpTi(μ 4 -C)(μ-NP i Pr 3 )(μ-Me)(AlMe 2 ) 3 ]. , In contrast to the i PrPN – complex, the Ph 3 PN – analogue resists expulsion of [AlMe 3 ], resulting in a stable μ 5 -carbide complex .…”

Section: Strategies Toward Bridging Carbide Complexesmentioning

confidence: 99%

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Transition Metal Carbide Complexes

Reinholdt

Bendix

2021

Chem. Rev.

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Carbide complexes remain a rare class of molecules. Their paucity does not reflect exceptional instability but is rather due to the generally narrow scope of synthetic procedures for constructing carbide complexes. The preparation of carbide complexes typically revolves around generating L n M−CE x fragments, followed by cleavage of the C−E bonds of the coordinated carbon-based ligands (the alternative being direct C atom transfer). Prime examples involve deoxygenation of carbonyl ligands and deprotonation of methyl ligands, but several other p-block fragments can be cleaved off to afford carbide ligands. This Review outlines synthetic strategies toward terminal carbide complexes, bridging carbide complexes, as well as carbide−carbonyl cluster complexes. It then surveys the reactivity of carbide complexes, covering stoichiometric reactions where the carbide ligands act as C 1 reagents, engage in cross-coupling reactions, and enact Fischer−Tropsch-like chemistry; in addition, we discuss carbide complexes in the context of catalysis. Finally, we examine spectroscopic features of carbide complexes, which helps to establish the presence of the carbide functionality and address its electronic structure.

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Section: Strategies Toward Bridging Carbide Complexesmentioning

confidence: 99%

“…161 Interestingly, when the [CpTi-(NPR 3 )L 2 ] complexes react with excess of another Lewis acid, [AlMe 3 ], heterometallic μ 4 -and μ 5 -carbide complexes arise (Figure 30). 162,163 Thus, the thiolate complex, [CpTi(…”

Section: Synthesis Of Bridging Carbide Complexes Upon C−h Bond Splittingmentioning

confidence: 99%

Transition Metal Carbide Complexes

Reinholdt

Bendix

2021

Chem. Rev.

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“…The recently reported Tebbe derivative (PNP)TiC t Bu(μ-Me)AlMe 2 (PNP = [2-{P(CHMe 2 ) 2 }-4-methylphenyl] 2 N − ) was prepared from (PNP)TiC t Bu(C t Bu 2 ) and AlMe 3 . A number of complexes with bridging carbon atom, CH 2 , or Me groups have been obtained by reaction of Cp*(R 3 PN)TiMe 2 (Cp* = Cp, indenyl; R = i Pr, Cy, Ph) or ( t Bu 3 PN) 2 TiMe 2 with an excess of AlMe 3 , affording for example Cp*Ti(μ-Me)(μ-NPR 3 )(μ 4 -C)(AlMe 2 ) 3 and CpTi(μ-Me)(μ-NPR 3 )(μ 5 -C)(AlMe 2 )·(AlMe 3 ), respectively . To the best of our knowledge only Cp*Ti(μ-Me)(μ-NP i Pr 3 )(μ 3 -CH)(AlMe 2 ) 2 contains a bridging CH group between the titanium and aluminum centers. , …”

Section: Introductionmentioning

confidence: 99%

Formation of a Titanium Complex with a Ti═CHAl₂Structural Unit from LTiMe₃and Trimethylaluminum

et al. 2008

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The reaction of LTiCl3 (1) (L = HC(CMeN(2,6-iPr2C6H3))2, nacnac) with MeLi·(Et2O)0.14 in toluene afforded the stable Ti(IV) alkyl complex LTiMe3 (1). Reaction of 1 with 2 equiv of AlMe3 in toluene resulted in the formation of LTi(Me)CH(Al2Me5) (2) in high yield. Compounds 1 and 2 were characterized by X-ray structural analysis, NMR, IR, mass spectrometry, and elemental analysis. The Ti−CH bond length (1.880(2) Å) of 2 is in the range of a short Ti−C bond. This was additionally supported by NMR and DFT calculations. Compound 2 polymerized ethylene without adding any cocatalyst, although activity is low; the best TOF value was 2.4 × 104 g(polymer)/mol catalyst·h·bar.

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Hydroalumination of a Chlorotrialkynylsilane: Spontaneous Stepwise 1,3‐Dyotropic Rearrangement via an Intermediate Silyl Cation

Uhl

Bohnemann

Layh

et al. 2014

Chemistry A European J

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A new functionalised alkynylsilane, Cl-Si(CC-CMe3 )3 (3), was obtained by a facile multistep synthesis. Treatment of 3 with equimolar quantities of the hydrides H-M(CMe3 )2 (M=Al, Ga) gave the mixed alkenyl-di(alkynyl)silanes, in which the chlorine atom adopts a bridging position between the aluminium and silicon atoms. Dual hydrogallation of 3 resulted in the formation of a di(alkenyl)-alkynylsilane containing two gallium atoms, one of which is coordinated to the chlorine atom, and the second is bonded to the α-carbon atom of the remaining alkynyl group. A tert-butylsilane was unexpectedly formed by a unique 1,3-dyotropic chlorine-tert-butyl exchange for the corresponding dialuminium compound. One aluminium atom is bonded to a tert-butyl group, a terminal chlorine atom and the α-carbon atom of the ethynyl moiety; the second is coordinatively unsaturated, with two terminal tert-butyl substituents. High-level quantum-chemical calculations favour a stepwise dyotropic rearrangement with an intermediate cationic silicon species over a simultaneous tert-butyl-chlorine migration via a five-coordinate silicon atom in the transition state.

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Reactions of the titanium-carbide species CpTi(μ2-Me)(μ2-NPi-Pr3)(μ4-C)(AlMe2)3

Cited by 11 publications

References 33 publications

Transition Metal Carbide Complexes

Transition Metal Carbide Complexes

Formation of a Titanium Complex with a Ti═CHAl₂Structural Unit from LTiMe₃and Trimethylaluminum

Hydroalumination of a Chlorotrialkynylsilane: Spontaneous Stepwise 1,3‐Dyotropic Rearrangement via an Intermediate Silyl Cation

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Reactions of the titanium-carbide species CpTi(μ2-Me)(μ2-NPi-Pr3)(μ4-C)(AlMe2)3

Cited by 11 publications

References 33 publications

Transition Metal Carbide Complexes

Transition Metal Carbide Complexes

Formation of a Titanium Complex with a Ti═CHAl2Structural Unit from LTiMe3and Trimethylaluminum

Hydroalumination of a Chlorotrialkynylsilane: Spontaneous Stepwise 1,3‐Dyotropic Rearrangement via an Intermediate Silyl Cation

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Formation of a Titanium Complex with a Ti═CHAl₂Structural Unit from LTiMe₃and Trimethylaluminum