Synthese und reaktionen von (CO)5Mo[C(Aryl)H]

Fischer, Helmut; Reindl, David

doi:10.1016/0022-328x(90)85006-k

Cited by 15 publications

(3 citation statements)

References 22 publications

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“…Given the previously observed chemistry, it is reasonable to postulate initial H-abstraction, then subsequent chemistry derived from the 16-electron cationic carbenes 3a , b . Insertion of the alkyne into the MoC double bond would produce vinylcarbene complexes 5a − c , which could undergo nucleophilic attack by the phosphite to yield 2a − c .…”

Section: Resultsmentioning

confidence: 99%

Oxidation of Metal Carbynes in the Presence of Alkynes. Alkyne Addition vs H-Shift in the Carbene Intermediate

1998

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One-electron oxidation of the carbyne complex (η 5 -C 5 H 5 )(CO){P(OPh) 3 }MotCCH 2 CH 2 CH 2 -CH 3 (1a) in the presence of phenylacetylene results in H-abstraction and addition of the alkyne to the resulting metal carbene. The final product of the addition is the η 1 η 2 -allyl complex (η 5 -C 5 H 5 )(CO){P(OPh) 3 }Mo[η 1 :η 2 -CH{P(OPh) 3 }C(Ph)dCH(CH 2 CH 2 CH 2 CH 3 )] (2a), the structure of which was confirmed by X-ray crystallography.Supporting Information Available: Tables of bond distances, bond angles, positional parameters, and anisotropic displacement parameters for 2a (16 pages). See any current masthead page for ordering information and Web access instructions.OM980534X

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Section: Resultsmentioning

confidence: 99%

Oxidation of Metal Carbynes in the Presence of Alkynes. Alkyne Addition vs H-Shift in the Carbene Intermediate

1998

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“…For example, they can be trapped with phosphines to form zwitterionic adducts, such as 58-60. 26 2.2.3 Initiated by nucleophilic addition of enamines to Fischer alkoxy alkenyl carbene complexes. Zwitterionic metallate complexes 63 are isolated in excellent yields when Fischer alkenyl carbene complexes 62 and enamines 61 are mixed in hexane at room temperature.…”

Section: Nucleophilic Substitution Of Fischer Alkoxy Carbene Complexesmentioning

confidence: 99%

“…Insertion of selenium or sulphur into the MvC bond of a carbene complex has been observed by the reaction of benzylidene( pentacarbonyl) complexes of group 6 metals 50 with selenocyanates 158 26,47 or thiocyanates 159 at low temperature to form chalcogenobenzaldehyde ligand complexes 160 and 161, respectively (Scheme 33). 26,48 Thiobenzaldehyde complexes 161 may also be formed by the reaction of benzylidene( pentacarbonyl) complexes with elemental sulphur (Scheme 33). 48 In solution, the chalcogenobenzaldehyde ligand may be bonded to the metal either in complexes 160 and 161 in a η 1fashion or in a dynamic equilibrium between two η 1 -forms and one η 2 -isomeric form (Scheme 33; bottom).…”

Section: Insertion Of S or Sementioning

confidence: 99%