New Bis(silyl)cyclopentadienidoniobium and ‐tantalum Complexes:X‐ray Crystal Structures of [NbCp∧Cl4] and [NbCp∧Cl4(CNAr)][Cp∧ = η5‐C5H3(SiClMe2)(SiMe3); Ar = 2,6‐Me2C6H3]

Gómez, Manuel; Gómez‐Sal, Pilar; Hernández, José Manuel

doi:10.1002/ejic.200600633

Cited by 9 publications

(1 citation statement)

References 43 publications

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“…Transition‐metal complexes containing nitrogen‐based ligands that can act as a reactive site, such as amido and imido ligands, continue to generate a great deal of interest on account of their crucial roles in many stoichiometric and catalytic reactions, such as olefin metathesis,, Ziegler–Natta polymerization, hydroamination reactions, and ring‐opening metathesis polymerization In addition, owing to their strong π‐donating capabilities and relative inertness, these groups have been used widely in suitable supporting ligands to stabilize high‐valent early transition‐metal complexes. The study of the organometallic chemistry of cyclopentadienyl (Cp) imido complexes of group 5 metals has been stimulated by the isoelectronic relationship between such complexes and the well‐known group 4 bent metallocenes, which are used extensively as α‐olefin polymerization catalysts …”

Section: Introductionmentioning

confidence: 99%

Suitable Approach to Prepare N‐Substituted Niobium Complexes – Study of the Factors Controlling the Process

et al. 2017

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The reactions of the chlorosilyl-substituted cyclopentadienyl niobium compound [Nb(η 5 -C 5 H 4 SiMe 2 Cl)Cl 4 ] (1) with 1 equiv. of 2-methoxyethylamine, 3-methoxypropylamine, and allylamine in toluene specifically afford the corresponding amine adducts [Nb(η 5 -C 5 H 4 SiMe 2 Cl){NH 2 (CH 2 ) n OMe}Cl 4 ] (n = 2, 2; 3, 3) and [Nb(η 5 -C 5 H 4 SiMe 2 Cl)(NH 2 CH 2 CH=CH 2 )Cl 4 ] (4). In contrast, a similar reaction with 1,2-phenylenediamine proceeds with the aminolysis of a Nb-Cl bond and the formation of the amido-amine compound [Nb(η 5 -C 5 H 4 SiMe 2 Cl)(NHC 6 H 4 -2-κNH 2 )Cl 3 ] (5). When such reactions are performed in the presence of 2 equiv. of an additional base, they progress through [a]

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Section: Introductionmentioning

confidence: 99%

Suitable Approach to Prepare N‐Substituted Niobium Complexes – Study of the Factors Controlling the Process

et al. 2017

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Monocyclopentadienyl(niobium) Compounds with Imido and Silsesquioxane Ligands: Synthetic, Structural and Reactivity Studies

et al. 2009

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Cyclopentadienyl–Silsesquioxane Titanium Catalysts: Factors Affecting Their Formation and Activity in Olefin Epoxidation with Aqueous Hydrogen Peroxide

Ventura¹,

Tabernero²,

Cuenca³

et al. 2016

Eur J Inorg Chem

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The reaction of titanium chlorosilyl‐substituted cyclopentadienyl (Cp) complexes, Ti(η5‐C5H3R′SiMe2Cl)Cl3 (R′ = H, 1b; SiMe3, 1c), with 1 equiv. of various silsesquioxane trisilanols, R7Si7O9(OH)3 (R = iBu, 2a; Ph, 2b), affords either corner‐capped Cp derivatives, Ti(η5‐C5H3R′SiMe2Cl)(R7Si7O12‐κ3O3) (R′ = H, R = iBu, 5a, Ph, 5b; R′ = SiMe3, R = iBu, 7a, Ph, 7b), or cyclopentadienyl–silsesquioxane complexes, Ti(η5‐C5H4SiMe2OR7Si7O11‐κ2O2)Cl (R′ = H, R = iBu, 6a, Ph, 6b; R′ = SiMe3, R = iBu, 8a, Ph, 8b), depending on the reaction conditions. In any case, upon heating, kinetic products 5 and 7 are transformed into the corresponding thermodynamic products 6 and 8, respectively. The electron‐donating ability of the Cp ring is a relevant controlling parameter: a strong π‐donor character facilitates the isomerization process. In addition, the nature of the silicon substituents in the silsesquioxane framework, the type of solvent, and the reaction temperature are also factors that significantly affect this process. Cyclopentadienyl–silsesquioxane complexes 6b and 8b are efficient and selective catalysts for epoxidation with aqueous hydrogen peroxide under mild conditions. Such a catalytic efficiency is attributed to the hydrophobic environment generated about the titanium atom by the Cp ring incorporated into the cyclopentadienyl–silsesquioxane ligand.

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New Bis(silyl)cyclopentadienidoniobium and ‐tantalum Complexes:X‐ray Crystal Structures of [NbCp∧Cl₄] and [NbCp∧Cl₄(CNAr)][Cp∧ = η⁵‐C₅H₃(SiClMe₂)(SiMe₃); Ar = 2,6‐Me₂C₆H₃]

Cited by 9 publications

References 43 publications

Suitable Approach to Prepare N‐Substituted Niobium Complexes – Study of the Factors Controlling the Process

Suitable Approach to Prepare N‐Substituted Niobium Complexes – Study of the Factors Controlling the Process

Monocyclopentadienyl(niobium) Compounds with Imido and Silsesquioxane Ligands: Synthetic, Structural and Reactivity Studies

Cyclopentadienyl–Silsesquioxane Titanium Catalysts: Factors Affecting Their Formation and Activity in Olefin Epoxidation with Aqueous Hydrogen Peroxide

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