1,3-Heterobinuclear Cyclobutenylidene Complexes with an Exocyclic C=C bond — Synthesis, Structure, and Spectroscopic Properties

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1996
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Leroux, Frédéric
Stumpf, Rüdiger
Roth, Gerhard
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Chemische Berichte ; 129 (1996), 12. - pp. 1475-1482. - ISSN 0009-2940. - eISSN 1099-0682
Abstract
Pentacarbonyl(allenylidene)chromium and -tungsten, [(CO)5[BOND]M[DOUBLE BOND]C[DOUBLE BOND]C[DOUBLE BOND]CR2] (M=Cr, R=C6H4CH3-p(1a), C6H4OCH3 (1b); M=W, R=C6H4CH3-p (1c), react with the alkynyl complexes [Cp(CO)2Fe[BOND]C[TRIPLE BOND]CR′] (R′ = nBu (2), Ph (4)), [Cp*(CO)2Fe[BOND]C[TRIPLE BOND]CnBu] (6), [Cp(CO){P(OMe)3}-Fe[BOND]C[TRIPLE BOND]CnBu] (8) and [Cp(PPh3)Ni[BOND]C[TRIPLE BOND]CnBu] (10) by cycloaddition of the C[TRIPLE BOND]C bond of the alkynyl complexes to the Cα=Cβ bond of the allenylidene ligand to give chemical structure image3a–c), chemical structure image (5), chemical structure image (7), chemical structure image and chemical structure image respectively. The cycloaddition is highly selective. The spectroscopic data of these 1,3-heterobinuclear complexes indicate a delocalized π-system chemical structure image (M=Cr, W; Y=[Fe(CO)2Cp], [Fe(CO)(P{OMe}3)Cp], [Fe(CO)2Cp*], [Ni(PPh3)-Cp]). X-ray structural analyses of the compounds 3a, 9a, and 11c reveal a “butterfly” conformation of the four-membered ring. Its puckering angle is 142° (3a), 152° (9a), and 151° (11c). All Complexes exhibit a moderate to strong negative solvatochromic behavior. The extent of the solvatochromic effect depends on [(CO)5M] and Y and considerably decreases when C=CR2 is replaced by e.g. CMe2.
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ISO 690FISCHER, Helmut, Frédéric LEROUX, Rüdiger STUMPF, Gerhard ROTH, 1996. 1,3-Heterobinuclear Cyclobutenylidene Complexes with an Exocyclic C=C bond — Synthesis, Structure, and Spectroscopic Properties. In: Chemische Berichte. 129(12), pp. 1475-1482. ISSN 0009-2940. eISSN 1099-0682. Available under: doi: 10.1002/cber.19961291212
BibTex
@article{Fischer199613Het-23055,
  year={1996},
  doi={10.1002/cber.19961291212},
  title={1,3-Heterobinuclear Cyclobutenylidene Complexes with an Exocyclic C=C bond — Synthesis, Structure, and Spectroscopic Properties},
  number={12},
  volume={129},
  issn={0009-2940},
  journal={Chemische Berichte},
  pages={1475--1482},
  author={Fischer, Helmut and Leroux, Frédéric and Stumpf, Rüdiger and Roth, Gerhard}
}
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    <dcterms:abstract xml:lang="eng">Pentacarbonyl(allenylidene)chromium and -tungsten, [(CO)5[BOND]M[DOUBLE BOND]C[DOUBLE BOND]C[DOUBLE BOND]CR2] (M=Cr, R=C6H4CH3-p(1a), C6H4OCH3 (1b); M=W, R=C6H4CH3-p (1c), react with the alkynyl complexes [Cp(CO)2Fe[BOND]C[TRIPLE BOND]CR′] (R′ = nBu (2), Ph (4)), [Cp*(CO)2Fe[BOND]C[TRIPLE BOND]CnBu] (6), [Cp(CO){P(OMe)3}-Fe[BOND]C[TRIPLE BOND]CnBu] (8) and [Cp(PPh3)Ni[BOND]C[TRIPLE BOND]CnBu] (10) by cycloaddition of the C[TRIPLE BOND]C bond of the alkynyl complexes to the Cα=Cβ bond of the allenylidene ligand to give chemical structure image3a–c), chemical structure image (5), chemical structure image (7), chemical structure image and chemical structure image respectively. The cycloaddition is highly selective. The spectroscopic data of these 1,3-heterobinuclear complexes indicate a delocalized π-system chemical structure image (M=Cr, W; Y=[Fe(CO)2Cp], [Fe(CO)(P{OMe}3)Cp], [Fe(CO)2Cp*], [Ni(PPh3)-Cp]). X-ray structural analyses of the compounds 3a, 9a, and 11c reveal a “butterfly” conformation of the four-membered ring. Its puckering angle is 142° (3a), 152° (9a), and 151° (11c). All Complexes exhibit a moderate to strong negative solvatochromic behavior. The extent of the solvatochromic effect depends on [(CO)5M] and Y and considerably decreases when C=CR2 is replaced by e.g. CMe2.</dcterms:abstract>
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