Complexes with diamino-substituted unsaturated C3 and C5 ligands :  First Group 6 Pentatetraenylidenes and New Allenylidene Complexes

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1996
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Roth, Gerhard
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Sequential reaction of [(CO)5M(THF)] (M = Cr (1a), W (1b)) with Li[CCC(NMe2)3] and BF3·OEt2 afforded the first diaminoallenylidene complexes [(CO)5MCCC(NMe2)2] (M = Cr (2a), W (2b)). These compounds are inert toward nucleophilic attack of HNMe2 at room temperature. 2b was characterized by an X-ray structural analysis. Treatment of 1 with the cumulogous acetylide Li[CCCCC(NMe2)3] and then with BF3·OEt2 produced the first group 6 pentatetraenylidene complexes, [(CO)5MCCCCC(NMe2)2] (M = Cr (3a), W (3b)). The X-ray structural analysis of 3b reveals a strong alternation of the CC bond lengths within the (CO)5MC5 unit. Although the compounds 3 are stable at room temperature, they quantitatively add HNMe2 within 30 min to give the alkenyl(amino)allenylidene complexes [(CO)5MCCC(NMe2)C(H)C(NMe2)2] (M = Cr (4a), W (4b)). Complex 4b was characterized by an X-ray structural analysis. 4b is the first example of an open chain metal alkenylallenylidene with an s-cis conformation. The complexes 4 are comparable in stability and inertness toward nucleophiles such as amines to the metal diaminoallenylidenes 2. The spectroscopic data and the X-ray structural analyses of 2b, 3b, and 4b indicate that these heteroatom-substituted compounds are best described as hybrids of metallacumulene and strongly polarized alkynyl structures.

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ISO 690ROTH, Gerhard, Helmut FISCHER, 1996. Complexes with diamino-substituted unsaturated C3 and C5 ligands :  First Group 6 Pentatetraenylidenes and New Allenylidene Complexes. In: Organometallics. 1996, 15(4), pp. 1139-1145. ISSN 0276-7333. eISSN 1520-6041. Available under: doi: 10.1021/om950845x
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@article{Roth1996Compl-23155,
  year={1996},
  doi={10.1021/om950845x},
  title={Complexes with diamino-substituted unsaturated C<sub>3</sub> and C<sub>5</sub> ligands :  First Group 6 Pentatetraenylidenes and New Allenylidene Complexes},
  number={4},
  volume={15},
  issn={0276-7333},
  journal={Organometallics},
  pages={1139--1145},
  author={Roth, Gerhard and Fischer, Helmut}
}
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