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Complexes with diamino-substituted unsaturated C<sub>3</sub> and C<sub>5</sub> ligands :  First Group 6 Pentatetraenylidenes and New Allenylidene Complexes

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

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ROTH, Gerhard, Helmut FISCHER, 1996. Complexes with diamino-substituted unsaturated C3 and C5 ligands :  First Group 6 Pentatetraenylidenes and New Allenylidene Complexes. In: Organometallics. 15(4), pp. 1139-1145. ISSN 0276-7333. eISSN 1520-6041

@article{Roth1996Compl-23155, title={Complexes with diamino-substituted unsaturated C3 and C5 ligands :  First Group 6 Pentatetraenylidenes and New Allenylidene Complexes}, year={1996}, doi={10.1021/om950845x}, number={4}, volume={15}, issn={0276-7333}, journal={Organometallics}, pages={1139--1145}, author={Roth, Gerhard and Fischer, Helmut} }

2013-06-12T08:48:38Z Complexes with diamino-substituted unsaturated C<sub>3</sub> and C<sub>5</sub> ligands :  First Group 6 Pentatetraenylidenes and New Allenylidene Complexes deposit-license 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. Roth, Gerhard Roth, Gerhard 1996 eng Organometallics ; 15 (1996), 4. - S. 1139–1145 Fischer, Helmut 2013-06-12T08:48:38Z Fischer, Helmut

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