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CLUSTER-MEDIATED INTEGRATION SPLITTING OF C-S BONDS - SYNTHESIS OF CARBENE-SUBSTITUTED SULFUR-BRIDGED CARBONYLIRON CLUSTERS

JOURNAL OF ORGANOMETALLIC CHEMISTRY. Bd. 402. H. 2. 1991 S. 221 - 232

Erscheinungsjahr: 1991

ISBN/ISSN: 0022-328X

Publikationstyp: Zeitschriftenaufsatz

Doi/URN: 10.1016/0022-328X(91)83066-D

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Inhaltszusammenfassung


The clusters (mu-3-RP)Fe3(CO)10, 1, behave like coordinatively unsaturated compounds in many reactions; they add two electron donor ligands L via opening of one Fe-Fe edge. This reaction pattern presumably represents the initiation of a process, in which these clusters split thiocompounds R2C = S into sulfur and carbene ligands, both of which are integrated into the resulting product cluster. With thiourea, N,N'-dimethylthiourea and thioacetamide the compounds 1 react to give the clusters e...The clusters (mu-3-RP)Fe3(CO)10, 1, behave like coordinatively unsaturated compounds in many reactions; they add two electron donor ligands L via opening of one Fe-Fe edge. This reaction pattern presumably represents the initiation of a process, in which these clusters split thiocompounds R2C = S into sulfur and carbene ligands, both of which are integrated into the resulting product cluster. With thiourea, N,N'-dimethylthiourea and thioacetamide the compounds 1 react to give the clusters eta-4-[R activated P...Fe(CO)3...S...Fe(CO)2(CR' R")]Fe(CO)3, 2 and 3, in fair yields. The structure of the carbene-substituted clusters 2 and 3, the square pyramidal framework of which may be regarded as an eta-4-coordinated 4-pi-metallaheterocycle, is documented by two X-ray analyses. The dynamic behaviour of the clusters 2 and 3 is analysed by NMR-spectroscopy: the strongly hindered rotation of the amino groups around the C(carbene)-N-bond is characteristic in all cases. » weiterlesen» einklappen

Autoren


EBER, B (Autor)
HUTTNER, G (Autor)
ZSOLNAI, L (Autor)

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