Metal complexes with terminal dicyanomethylenecarbene ligands formed by chlorine migration reactions

King, R. B.; Saran, M. S.

doi:10.1039/c39720001053

Cited by 34 publications

(30 citation statements)

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“…Complex 9 can be observed in solution at −50 • C [52]. The only mononuclear manganese complex with the parent vinylidene stable at RT is (Me 3 SiC C)Mn C CH 2 (dmpe) 2 (11), synthesized by Berke and co-workers [53].…”

Section: Formation Of Manganese and Rhenium Vinylidene Complexes Frommentioning

confidence: 97%

“…King obtained the first vinylidene complex containing a linear metalla-allene system, viz. Cp[P(OMe) 3 ] 2 (Cl)Mo C C(CN) 2 (A type) [11] from Cl 2 C C(CN) 2 . The same olefin was a precursor for Cp 2 (CO) 2 Fe 2 [-C C(CN) 2 ](-CO) (B type) [11c,12].…”

Section: Introductionmentioning

confidence: 99%

“…However, when we obtained our first vinylidene complexes Cp(CO) 2 Mn C CHPh (1) and [Cp(CO) 2 Mn] 2 (-C CHPh) (2) and determined their structures [6][7][8][9], only four crystallographically characterized complexes with C CR 2 ligands were known [10][11][12][13], and all had been prepared from organic compounds including C C bonds, namely ketene and olefins. Thus, starting from Ph 2 C C O, Pauson and Bagga synthesized the first vinylidene complex Fe 2 ( 2 -C CPh 2 )(CO) 8 , the structure of which (B type) was determined by Mills and Redhouse [10].…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Use of the MnCC system in organometallic and organic synthesis

Antonova

2007

Coordination Chemistry Reviews

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Section: Formation Of Manganese and Rhenium Vinylidene Complexes Frommentioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Use of the MnCC system in organometallic and organic synthesis

Antonova

2007

Coordination Chemistry Reviews

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“…The synthesis and stoichiometric reactivity of these unsaturated ligands have been broadly developed but are still under active investigation, and several aspects have already led to reviews. [1][2][3][4][5][6][7][8][9][10][11][12][13][14] Since the first mononuclear vinylidene complexes reported in 1972, [15] the most straightforward routes to vinylidene and allenylidene complexes is the direct activation of terminal alkynes and propargylic alcohols, respectively, thus allowing the involvement of these species in catalytic reactions from accessible acetylenic substrates.…”

Section: Introductionmentioning

confidence: 99%

Metal Vinylidenes and Allenylidenes in Catalysis: Applications in Anti‐Markovnikov Additions to Terminal Alkynes and Alkene Metathesis

2006

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The involvement of a catalytic metal vinylidene species was proposed for the first time in 1986 to explain the regioselective formation of vinyl carbamates directly from terminal alkynes, carbon dioxide, and amines. Since this initial report, various metal vinylidenes and allenylidenes, which are key activation intermediates, have proved extremely useful for many alkyne transformations. They have contributed to the rational design of new catalytic reactions. This 20th anniversary is a suitable occasion to present the advancement of organometallic vinylidenes and allenylidenes in catalysis.

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“…The first well-recognized vinylidene complex MCl(C 5 H 5 )(L) 2 (C=C(CN) 2 ) (M=Mo, W) was obtained by R. B. King by chloride migration of an a-chloroalkenyl ligand [3]. Cationic (M=C=CHR ?…”

Section: Ruthenium-catalyzed Synthesis Of Vinyl-carbamatesmentioning

confidence: 99%

Early Steps of Homogeneous Catalysis in Rennes: Carbon Dioxide Incorporation, Alkyne Activation and Ruthenium Catalysis

Dixneuf

2014

Catal Lett

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This review reports the first discoveries in homogeneous catalysis in Rennes. Ruthenium(II) catalysts are shown to promote the activation of terminal alkynes and the synthesis of vinylcarbamates on addition of CO 2 and amines. The ruthenium-vinylidene are the key catalytic species. Applications to the addition of carboxylic acids to alkynes have opened the access to various enolesters and dienylesters via controlled catalyzed Markovnikov or anti-Markonikov additions. The catalytic synthesis of a-methylene cyclic carbonates and oxazolidinones from propargylic alcohols and CO 2 is presented and shown to lead to allene derivatives via palladium catalysis. Cp*RuX(COD) catalyst promote the head to tail oxidative couplings of alkene with alkyne, and the synthesis of functional dienes via 1,4 addition of H-nucleophiles to the biscarbene-ruthenium intermediate arising from head to head couplings of alkynes, whereas Cp*RuL 2 ? catalysts favour activation of alkynes via vinylidene intermediate.

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Metal complexes with terminal dicyanomethylenecarbene ligands formed by chlorine migration reactions

Cited by 34 publications

References 0 publications

Use of the MnCC system in organometallic and organic synthesis

Use of the MnCC system in organometallic and organic synthesis

Metal Vinylidenes and Allenylidenes in Catalysis: Applications in Anti‐Markovnikov Additions to Terminal Alkynes and Alkene Metathesis

Early Steps of Homogeneous Catalysis in Rennes: Carbon Dioxide Incorporation, Alkyne Activation and Ruthenium Catalysis

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