Untersuchungen zur Struktur und Kinetik von Zwischenstufen in Protonen‐induzierten Kupplungen von Alkylidin‐ und Isocyanidliganden

Bastos, Cecilia M.; Daubenspeck, Nancy; Mayr, Andreas

doi:10.1002/ange.19931050539

Cited by 5 publications

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References 15 publications

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“…Recently, evidence has been provided that the first step in these reactions involves the protonation of the metal-carbon triple bond, leading to a reactive cationic metallacarbene. 122 Ynediamine complexes have been prepared in a 40-80% yield from the reaction between the aminocarbyne [(EtNC)sM^C-NEt2]+ (M = Mo, W) and hydroiodic acid (eq 53). 123 The metallacarbyne is easily prepared in a two steps synthesis, starting from an isocyanide complex.…”

Section: \ Cpmentioning

confidence: 99%

Carbon-Carbon and Carbon-Heteroatom Coupling Reactions of Metallacarbynes

Engel¹,

Pfeffer²

1995

Chem. Rev.

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Philippus F, Engel was born in Utrecht, The Netherlands, in 1965. He was educated in the State University of Utrecht and specialized in Organometallic Chemistry with Professor G. van Koten in 1989. He then moved to Strasbourg where he obtained his These de I'Universile Louis Pasteur in 1993. The subject of his Ph.D. thesis was on the organometallic chemistry of "Fischer-type" melallacarbynes. He recently joined Shell Research in Amsterdam, The Netherlands, as an associate research chemist.Michel Pfeffer was bom in Alsace in 1948 and he received his Doctorat d'Etal from the Universite Louis Pasteur in 1975. In 1976 he spent one year wth Professor F. G. A. Stone at the University of Bristol. Since 1973 he has held a position in the CNRS at ULP Strasbourg where he became Directeur de Recherche in 1985. His main research interests are in the field of organomelallic chemistry with an emphasis on metalmediated syntheses of carbon-carbon and carbon-heteroatom bonds.

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Section: \ Cpmentioning

confidence: 99%

Carbon-Carbon and Carbon-Heteroatom Coupling Reactions of Metallacarbynes

Engel¹,

Pfeffer²

1995

Chem. Rev.

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Intramolecular Carbyne–Isocyanide Coupling to an Alkyne Ligand at a d4 Tungsten Center

Filippou¹,

Lungwitz

Kociok‐Köhn

1999

Eur. J. Inorg. Chem.

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Oxidative decarbonylation of Cp*(CO)2W≡CNEt2 (1) with PhICl2 affords the aminocarbyne complex cis‐Cp*(Cl)2(CO)W≡CNEt2 (2), which reacts with tBuNC to give the CO substitution product cis‐Cp*(Cl)2(tBuNC)W≡CNEt2 (3) (Cp* = C5Me5). Complex 3 undergoes a carbyne–isocyanide coupling reaction with HCl to yield the alkyne complex Cp*(Cl)3W[η2‐tBu(H)NC≡CNEt2] (4). In comparison, the reaction of cis‐Cp*(Cl)2[P(OMe)3]W≡CNEt2 (5) with HCl affords the 16e carbene complex Cp*(Cl)3W=C(H)NEt2 (6) after elimination of P(OMe)3. Complex 5 was obtained from the CO ligand‐exchange reaction of 2 with P(OMe)3. Treatment of 6 with tBuNC yields the cationic 18e carbene complex [Cp*(Cl)2(tBuNC)2W=C(H)NEt2]Cl (7). The mechanism of the C–C coupling reaction of 3 to give 4 is discussed and the crystal structures of 4 and 6 are described.

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