A New General Method for the Preparation of Metal Carbene Complexes

Gandelman, Mark; Rybtchinski, Boris; Ashkenazi, Nissan; Gauvin, Régis M.; Milstein, David

doi:10.1021/ja0157393

Cited by 94 publications

(57 citation statements)

References 25 publications

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“…[3], [4] However, this metal-carbene chemistry is currently limited to insertion of X-H (X = N, O, S) bonds and cyclopropanation reactions. [5] Development of sulfur ylide-based metal carbene chemistry for a wider range of applications is highly desirable, [6] as it can offer some advantages over diazo carbenes.…”

mentioning

confidence: 99%

Synthesis of Indoles and Pyrroles Utilizing Iridium Carbenes Generated from Sulfoxonium Ylides

2017

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Sulfur (sulfonium and sulfoxonium) ylides are versatile synthetic precursors for a diverse range of chemical transformations [1] , e. g. they are widely used as methylene synthons in the formation of small rings such as epoxides, aziridines, and cyclopropanes from electrophilic substrates like aldehydes, imines, and enones. Recently, cycloadditions of sulfur ylides to a variety of electrophilic metal (Pd, Fe, Cu, Rh, or Au) associated intermediates have been explored for synthesis of heterocycles (Scheme 1; Type I). [2] Scheme 1. Sulfur ylide-based heterocycle synthesis via a metal-associated intermediate (Type I) or via a metal-carbene complex (Type II).

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confidence: 99%

Synthesis of Indoles and Pyrroles Utilizing Iridium Carbenes Generated from Sulfoxonium Ylides

2017

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“…[8,22] Intramolecular olefin metathesis was carried out catalytically on 3 by treatment with 10 mol % of the ''Grubbs catalyst'' benzylidenedichlorobis(tricyclohexylphosphane)ruthenium. [38,39] In dilute solution, with use of a syringe pump for addition of 3 in dichloromethane to the metathesis catalyst, the reaction can largely be kept in the intramolecular regime. Crystallization from toluene gave the ''large ansa-zirconocene dichloride complex'' as a white crystalline solid in 25% yield.…”

Section: Synthesis and Characterization Of The Ansa-metallocenesmentioning

confidence: 99%

Synthesis, Structural and Chemical Characterization of Unsaturated C4- and C10-Bridged Group-4 ansa-Metallocenes Obtained Through a Ring-Closing Olefin Metathesis Reaction

Hüerländer¹,

Kleigrewe²,

Kehr³

et al. 2002

Eur. J. Inorg. Chem.

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Bis [(5-hexenyl)cyclopentadienyl]zirconium dichloride (3) underwent ring-closure olefin metathesis with loss of ethylene when treated with 10 mol % of the [Cl 2 (PCy 3 ) 2 Ru=CHPh] catalyst in refluxing dichloromethane, to yield the large ansa-zirconocene complex [dec-5-ene-1,10-diylbis(η 5 -cyclopentadienyl)]ZrCl 2 (trans-4). Characterization by NMR and by X-ray diffraction revealed that the isolated complex contained a trans-C=C double bond inside the ansa bridge. Similarly, bis[(allyl)cyclopentadienyl]ZrCl 2 (7) gave the ansametallocene [but-2-ene-1,4-diylbis(η 5 -cyclopentadienyl)]zirconium dichloride (cis-8) when treated with the same ruthenium metathesis catalysts (10 mol %) under similar conditions, except that a cis-C=C double bond was now found to be present (shown by NMR and X-ray diffraction). The cis-8 complex was used as a homogeneous Ziegler−Natta catalyst

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“…So far, different types of organic radicals together with paramagnetic metal ions have been employed in the elaboration of molecular magnetic materials. [9,10] Beside the extensively studied family of nitroxidebased radicals, [8,[11][12][13] other organic radicals, such as verdazyl derivatives, [9,14] ortho-quinone ligands, [15] tetracyanoethylene (TCNE) [16] and tetracyanoquinodimethane (TCNQ) [17] radicals anions, and diphenyl carbenes [18] have been used. However, most of these molecules show limited coordination abilities towards metal ions, a factor that limits their use for the formation of multidimensional coordination polymers.…”

Section: Introductionmentioning

confidence: 99%

Three‐Dimensional Porous Metal–Radical Frameworks Based on Triphenylmethyl Radicals

Datcu

Roques

Jubera

et al. 2011

Chemistry A European J

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Lanthanide coordination polymers {[Ln(PTMTC)(EtOH)(2)H(2)O]·x H(2)O, y EtOH} [Ln=Tb (1), Gd (2), and Eu (3)] and {[Ln(αH-PTMTC)(EtOH)(2)H(2)O]·x H(2)O, y EtOH} [Ln=Tb (1'), Gd (2'), and Eu (3')] have been prepared by reacting Ln(III) ions with tricarboxylate-perchlorotriphenylmethyl/methane ligands that have a radical (PTMTC(3-)) or closed-shell (αH-PTMTC(3-)) character, respectively. X-ray diffraction analyses reveal 3D architectures that combine helical 1D channels and a fairly rare (6,3) connectivity described with the (4(2).8)·(4(4).6(2).8(5).10(4)) Schäfli symbol. Such 3D architectures make these polymers porous solids upon departure of the non-coordinated guest-solvent molecules as confirmed by the XRD structure of the guest-free [Tb(PTMTC)(EtOH)(2)H(2)O] and [Tb(αH-PTMTC)(EtOH)(2)H(2)O] materials. Accessible voids represent 40% of the cell volume. Metal-centered luminescence was observed in Tb(III) and Eu(III) coordination polymers 1' and 3', although the Ln(III)-ion luminescence was quenched when radical ligands were involved. The magnetic properties of all these compounds were investigated, and the nature of the {Ln-radical} (in 1 and 2) and the {radical-radical} exchange interactions (in 3) were assessed by comparing the behaviors for the radical-based coordination polymers 1-3 with those of the compounds with the diamagnetic ligand set. Whilst antiferromagnetic {radical-radical} interactions were found in 3, ferromagnetic {Ln-radical} interactions propagated in the 3D architectures of 1 and 2.

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A New General Method for the Preparation of Metal Carbene Complexes

Cited by 94 publications

References 25 publications

Synthesis of Indoles and Pyrroles Utilizing Iridium Carbenes Generated from Sulfoxonium Ylides

Synthesis of Indoles and Pyrroles Utilizing Iridium Carbenes Generated from Sulfoxonium Ylides

Synthesis, Structural and Chemical Characterization of Unsaturated C4- and C10-Bridged Group-4 ansa-Metallocenes Obtained Through a Ring-Closing Olefin Metathesis Reaction

Three‐Dimensional Porous Metal–Radical Frameworks Based on Triphenylmethyl Radicals

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