Ring Expansion of Spirocyclic Cyclobutenylidene Ligands in Pentacarbonylchromium Complexes to Tetrahydroindene Derivatives

Fischer, Helmut; Karl, Christoph C.; Roth, Gerhard

Ring Expansion of Spirocyclic Cyclobutenylidene Ligands in Pentacarbonylchromium Complexes to Tetrahydroindene Derivatives

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Datum

1996

Autor:innen

Fischer, Helmut

Karl, Christoph C.

Roth, Gerhard

Publikationstyp

Zeitschriftenartikel

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Chemische Berichte. 1996, 129(6), pp. 615-622. ISSN 0009-2940. Available under: doi: 10.1002/cber.19961290605

Zusammenfassung

Pentacarbonyl(pentamethylenevinylidene)chromium, [(CO)5Cr[DOUBLE BOND]C[DOUBLE BOND]C(CH2)5] (1), reacts with 1-methylthio-1-propyne (2a) and N-(1-propynyl)phenothiazine (2b) by regio-specific addition of the C[DOUBLE BOND]C bond of the alkyne to the C[DOUBLE BOND]C bond of the vinylidene ligand of 1. Initially, complexes with a spirocyclic cyclobutenylidene ligand are formed, [(CO)5Cr[DOUBLE BOND]chemical structure image(CH2)5] (3) and [(CO)5-Cr[DOUBLE BOND]chemical structure image(CH2)5] (10). Subsequent thermally initiated ring expansion affords the 2-methyl-4,5,6,7-tetrahydroindenyl(methyl)thioether complex [(CO)5-Cr–S(Me)(Me-C9H10)] (4) and the N-(2-methyl-4,5,6,7-tetrahydroindenyl)phenothiazine complex [(CO)5Cr–S(C6H4)2-N–(Me-C9H10)] (11), respectively. In both complexes, 4 and 11 the ligand is coordinated to the metal via the sulfur atom. The constitutions were established by (H,H)-, (H,C)- and NOE-correlated NMR spectroscopy. In the reaction of 1 with 2a, in addition to 3 and 4, the methyl(propynyl)thioether complex [(CO)5Cr–S(Me)C[TRIPLE BOND]CMe] (5) was formed. An isolable 3-methylthio-substituted cyclobutenylidene complex, [(CO)5Cr[DOUBLE BOND]chemical structure imagePh2] (9) was obtained from [(CO)5Cr[DOUBLE BOND]C[DOUBLE BOND]CPh2] (8) and 2a. The 4,5,6,7-tetrahydroindenylthioether ligand of 11 was cleaved from the metal by exposure of 11 adsorbed on silica gel to air or by treatment of 11 with [NEt4]Br in dichloromethane.

Fachgebiet (DDC)

540 Chemie

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ISO 690

FISCHER, Helmut, Christoph C. KARL, Gerhard ROTH, 1996. Ring Expansion of Spirocyclic Cyclobutenylidene Ligands in Pentacarbonylchromium Complexes to Tetrahydroindene Derivatives. In: Chemische Berichte. 1996, 129(6), pp. 615-622. ISSN 0009-2940. Available under: doi: 10.1002/cber.19961290605

BibTex

@article{Fischer1996Expan-23077,
  year={1996},
  doi={10.1002/cber.19961290605},
  title={Ring Expansion of Spirocyclic Cyclobutenylidene Ligands in Pentacarbonylchromium Complexes to Tetrahydroindene Derivatives},
  number={6},
  volume={129},
  issn={0009-2940},
  journal={Chemische Berichte},
  pages={615--622},
  author={Fischer, Helmut and Karl, Christoph C. and Roth, Gerhard}
}

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    <dcterms:abstract xml:lang="eng">Pentacarbonyl(pentamethylenevinylidene)chromium, [(CO)5Cr[DOUBLE BOND]C[DOUBLE BOND]C(CH2)5] (1), reacts with 1-methylthio-1-propyne (2a) and N-(1-propynyl)phenothiazine (2b) by regio-specific addition of the C[DOUBLE BOND]C bond of the alkyne to the C[DOUBLE BOND]C bond of the vinylidene ligand of 1. Initially, complexes with a spirocyclic cyclobutenylidene ligand are formed, [(CO)5Cr[DOUBLE BOND]chemical structure image(CH2)5] (3) and [(CO)5-Cr[DOUBLE BOND]chemical structure image(CH2)5] (10). Subsequent thermally initiated ring expansion affords the 2-methyl-4,5,6,7-tetrahydroindenyl(methyl)thioether complex [(CO)5-Cr–S(Me)(Me-C9H10)] (4) and the N-(2-methyl-4,5,6,7-tetrahydroindenyl)phenothiazine complex [(CO)5Cr–S(C6H4)2-N–(Me-C9H10)] (11), respectively. In both complexes, 4 and 11 the ligand is coordinated to the metal via the sulfur atom. The constitutions were established by (H,H)-, (H,C)- and NOE-correlated NMR spectroscopy. In the reaction of 1 with 2a, in addition to 3 and 4, the methyl(propynyl)thioether complex [(CO)5Cr–S(Me)C[TRIPLE BOND]CMe] (5) was formed. An isolable 3-methylthio-substituted cyclobutenylidene complex, [(CO)5Cr[DOUBLE BOND]chemical structure imagePh2] (9) was obtained from [(CO)5Cr[DOUBLE BOND]C[DOUBLE BOND]CPh2] (8) and 2a. The 4,5,6,7-tetrahydroindenylthioether ligand of 11 was cleaved from the metal by exposure of 11 adsorbed on silica gel to air or by treatment of 11 with [NEt4]Br in dichloromethane.</dcterms:abstract>
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