@article{Drexler2005Bisam-22837,
  year={2005},
  doi={10.1016/j.jorganchem.2005.03.070},
  title={Bis(amino)allenylidene complexes by displacement of the MeO group in methoxy allenylidene complexes of chromium and tungsten : Synthesis, DFT calculations and solid-state structures of new bis(amino)allenylidene complexes},
  number={16},
  volume={690},
  issn={0022-328X},
  journal={Journal of Organometallic Chemistry},
  pages={3700--3713},
  author={Drexler, Matthias and Haas, Thomas and Yu, Sze-Man and Beckmann, Henning and Weibert, Bernhard and Fischer, Helmut}
}

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    <dcterms:abstract xml:lang="eng">Pentacarbonyl dimethylamino(methoxy)allenylidene tungsten, [(CO)5Wdouble bond; length as m-dashCdouble bond; length as m-dashCdouble bond; length as m-dashC(OMe)NMe2] (1b), reacts with one equivalent of primary amines, H2NR, by selectively replacing the methoxy group to give dimethylamino(amino)allenylidene complexes, [(CO)5Wdouble bond; length as m-dashCdouble bond; length as m-dashCdouble bond; length as m-dashC(NHR)NMe2]. When the amine is used in excess both terminal groups, OMe as well as NMe2, are replaced by the primary amino group giving [(CO)5Wdouble bond; length as m-dashCdouble bond; length as m-dashCdouble bond; length as m-dashC(NHR)2 ]. The NHR substituent in these complexes may be modified by deprotonation with LDA followed by alkylation. The replacement of the methoxy group in 1b by a secondary amino group, NR2, can be achieved by a stepwise process. Addition of Li[NR2] to the Cγ atom of 1b affords an alkynyl tungstate. Subsequent OMe− elimination induced by TMS-Cl/SiO2 yields the allenylidene complexes [(CO)5Wdouble bond; length as m-dashCdouble bond; length as m-dashCdouble bond; length as m-dashC(NR2)NMe2]. When bidentate diamines are used instead of monoamines both substituents, OMe and NMe2, are replaced and allenylidene complexes are formed in which Cγ constitutes part of a 5-, 6-, or 7-membered heterocycle. The reaction of [(CO)5Crdouble bond; length as m-dashCdouble bond; length as m-dashCdouble bond; length as m-dashC(OMe)NMe2] (1a) with diethylene triamine affords an allenylidene complex with a heterocyclic endgroup carrying a dangling CH2CH2NH2 substituent. All reactions follow a strict regioselective attack of the nucleophile at Cγ and proceed with good to excellent yields. The addition of N–H to the Cαdouble bond; length as m-dashCβ bond is not observed. By applying either one of these routes nearly any substitution pattern in bis(amino)allenylidene complex can be realized.</dcterms:abstract>
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    <dc:contributor>Fischer, Helmut</dc:contributor>
    <dcterms:title>Bis(amino)allenylidene complexes by displacement of the MeO group in methoxy allenylidene complexes of chromium and tungsten : Synthesis, DFT calculations and solid-state structures of new bis(amino)allenylidene complexes</dcterms:title>
    <dcterms:issued>2005</dcterms:issued>
    <dc:creator>Beckmann, Henning</dc:creator>
    <dc:contributor>Yu, Sze-Man</dc:contributor>
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    <dc:creator>Yu, Sze-Man</dc:creator>
    <dc:contributor>Weibert, Bernhard</dc:contributor>
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    <dc:contributor>Haas, Thomas</dc:contributor>
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    <dc:creator>Haas, Thomas</dc:creator>
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    <dcterms:bibliographicCitation>Journal of Organometallic Chemistry ; 690 (2005), 16. - S. 3700-3713</dcterms:bibliographicCitation>
    <dc:creator>Drexler, Matthias</dc:creator>
    <dc:contributor>Drexler, Matthias</dc:contributor>
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