Kationische η2-Thiocarbenkomplexe von Molybdän und Wolfram

Ostermeier, J.; Schütt, Wolfgang; Stegmair, Claudia M.; Ullrich, Norbert; Kreißl, F. R.

doi:10.1016/0022-328x(94)87012-8

Cited by 8 publications

(2 citation statements)

References 31 publications

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“…Similar examples involve a metallacarbyne with a pyrazolyl ligand (eq 18). [68][69][70]72 [SMe]+ HB(Pz)3(CO)2MsC-R Me S /\ HB(Pz)3(CO)2M=C, (18) The resulting cationic products may react with a second equivalent of "SMe+" to give a (dithiomethyl)alkyl complex. These reactions are described in the section devoted to other metallacyclic complexes (section X.C).…”

Section: Ocn-(66%)mentioning

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: Ocn-(66%)mentioning

confidence: 99%

Carbon-Carbon and Carbon-Heteroatom Coupling Reactions of Metallacarbynes

Engel¹,

Pfeffer²

1995

Chem. Rev.

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“…Reactions of (alkyl)thiocarbene complexes studied so far, include addition of phosphines, isocyanides, 6b,c alkynes, 6d, and hydrogen bromide, condensation with aromatic aldehydes,6b and insertion into carbon−hydrogen and metal−carbene bonds and η 2 -thiocarbene complexes 12,13 with amines, alkyl phosphines, and azides have also been reported, as well as the addition of hydrides and thiolates, alkyl- and arylsulfonium salts, trifluoroacetic acid, and thiocyanate salts …”

Section: Introductionmentioning

confidence: 99%

Strikingly Different Reactivity Patterns of Fischer Alkoxycarbene and Thiocarbene Complexes in Experimental and Theoretical Studies

2007

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Striking differences in the reactions of alkoxycarbene and thiocarbene complexes of chromium and tungsten are observed. Thus, (β-imino)ethoxycarbene complexes 10a−e, generated in situ from [(OC)5WC(OEt)CH2R] (7a−c; R = n-Pr, Me, c-C7H7) and imidoyl chlorides R1ClCNCHR2R3 (9a−f; R1 = t-Bu, Ph, 2-furyl; R2 = H, Me; R3 = Me, Et, Ph), undergo a metalla(di-π-methane) rearrangement to (N-enamino)ethoxycarbene complexes 12a−e, while the corresponding (β-imino)thiocarbene complexes 11a−l, derived from [(OC)5MC(SEt)CH2R] (8a−e; M = W, Cr; R = n-Pr, Me, c-C7H7, c-C6H7Fe(CO)3) and imidoyl chlorides under similar conditions, form pyrroles 16a−h and 17k,l by α-cyclization. On the basis of the calculated DFT/BP86 potential energy surfaces of the particular reaction channels it is shown that (β-imino)alkoxycarbene compounds 10 prefer a metalla(di-π-methane) rearrangement due to the kinetic stability of the (N-enamino)ethoxycarbene products, while formation of pyrroles is not favored due to the presence of high energetic stationary structures in the α-cyclization pathway. For (β-imino)thiocarbene compounds 11, on the other hand, rearranged products are kinetically unstable, and α-cyclization reactions are strongly favored on thermodynamic grounds.

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7. Tungsten 1994

WONG¹

1996

Coordination Chemistry Reviews

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Kationische η2-Thiocarbenkomplexe von Molybdän und Wolfram

Cited by 8 publications

References 31 publications

Carbon-Carbon and Carbon-Heteroatom Coupling Reactions of Metallacarbynes

Carbon-Carbon and Carbon-Heteroatom Coupling Reactions of Metallacarbynes

Strikingly Different Reactivity Patterns of Fischer Alkoxycarbene and Thiocarbene Complexes in Experimental and Theoretical Studies

7. Tungsten 1994

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