Synthesis and reactivity of alkynyl niobocene complexes

Antiñolo, Antonío; García‐Yebra, Cristina; Fajardo, Mariano; Hierro, Isabel del; López-Mardomingo, Carmen; López‐Solera, Isabel; Otero, Antonío; Pérez, Yolanda; Prashar, Sanjiv

doi:10.1016/s0022-328x(02)02150-2

Cited by 8 publications

(2 citation statements)

References 29 publications

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“…Thus, derivatization with lithium phenylacetylide and lithium (trimethylsilyl)acetylide was also tested. Very few niobium (trimethylsilyl)acetylide complexes are known (none have been structurally characterized), − and only one niobium phenylacetylide complex has been previously characterized by X-ray diffraction . Both reactions were performed in ether, resulting in brown solutions.…”

Section: Resultsmentioning

confidence: 99%

Derivatization of Niobium Complexes Bearing Imido and Acetophenone Imine Ligands

Neshat

Schmidt

2010

Organometallics

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The successful isolation and characterization of derivatization reaction products of the niobium imido complex L 2 NbCl(NAr) (L = ortho-metalated acetophenone imine, Ar = 2,6-i Pr 2 C 6 H 3 ) with carbon and oxygen donor ligands such as Me, Me 3 SiCH 2 , PhCC, Me 3 SiCC, CF 3 SO 3 , and MeO are described. These more reactive σ-donor ligands were readily installed in place of the chloride ligand through salt metathesis reactions. The (trimethylsilyl)methyl complex showed significant R-agostic interactions between the methylene group and the niobium center. Similar strategies to derivatize the chloride complex utilizing lithiated amides (LiNMe 2 , LiNEt 2 , LiN i Pr 2 , and LiNC 5 H 10 ) resulted in the production of a niobium hydride species due to β-hydrogen elimination processes. All of the resulting C 1 -symmetric complexes were formed as predominantly a single isomer and were fully characterized using a combination of 1 H and 13 C NMR spectroscopy, elemental analyses, and X-ray crystallography, when possible.

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Section: Resultsmentioning

confidence: 99%

Derivatization of Niobium Complexes Bearing Imido and Acetophenone Imine Ligands

Neshat

Schmidt

2010

Organometallics

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“…[139] Oxidation of 30-CO in dichloromethane at -30°C rapidly results in the formation of the vinylidene complex 32-CO ( amount of radical character, decomposition to the analogous metal carbonyl is commonly observed during attempts to prepare and isolate radicals derived from ruthenium σ-alkynyl complexes. [12,19,97,141,142] As noted above, the formation of vinylidene complexes by hydrogen abstraction is a commonly observed reaction of alkynyl radical cations.…”

Section: Cp]mentioning

confidence: 99%

Ligand Redox Non‐Innocence in Transition‐Metal σ‐Alkynyl and Related Complexes

Schauer

Low

2011

Eur J Inorg Chem

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Transition-metal σ-alkynyl complexes are valuable functional materials that have found application as sructural units in the assembly of polymetallic arrays and large molecular structures, reagents for the transfer, oligomerisation or functionalisation of alkynes, magnetic or optical materials and putative components for use in a future molecular-based electronics platform. Many σ-alkynyl complexes are redoxactive, undergoing facile oxidation (reduction) at moderate potentials to generate radical cations (anions) in which the

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