Amino-substituted butatrienes : Unusual η1 ligands formed by an unusual reaction

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The reaction of the bis(amino)allenylidene complex [(CO)5W═C═C═C(NMe2)2] with diethyldiazomethane yields two products, a cyclic carbene complex (2) by 1,2-addition of Et2C−N2 to the Cα−Cβ bond of the allenylidene ligand and the η1-butatriene complex [(CO)5W{C[C(NMe2)2]═C═CEt2}] (3). Complex 2 slowly eliminates N2 and rearranges into 3. In contrast, only η1-butatriene complexes, [(CO)5M{C[C(NMe2)XR]═C═C(R′)2}], are isolated from the reaction of diazoalkanes (R′)2C−N2 (R′ = Me, Et, nPr) with alkoxy(amino)allenylidene complexes [(CO)5M═C═C═C(NMe2)OR] (M = Cr, W; R = Me, Et, (−)-menthyl) or with the (alkylthio)(amino)allenylidene complex [(CO)5W═C═C═C(NMe2)SnPr]. These new η1-butatriene complexes are related to Cα phosphine adducts of allenylidene complexes such as [(CO)5W{C(PMe3)═C═C(NMe2)Ph}] (17) and might be regarded as Cα carbene adducts. However, the PMe3 substituent in 17 is not replaced when 17 is treated with an N-heterocyclic carbene. Vice versa, the “carbene” substituent “C(NMe2)OEt” in the η1-butatriene complex [(CO)5Cr{C[C(NMe2)OEt]═C═CEt2}] is not replaceable by PMe3. Free N-heterocyclic carbenes do not add to the Cα atom of the allenylidene complex [(CO)5W═C═C═C(C6H4NMe2-p)2] but instead to the Cγ atom, giving the dipolar neutral alkynyl complexes [(CO)5W−C≡CC(C6H4NMe2-p)2L] (L = SIMe, SIMes). DFT calculations on the reaction mechanism indicate that a cyclic carbene complex and two isomeric η2-butatriene complexes are intermediates in the reaction pathway to form η1-butatriene complexes. The structure of two representative examples of η1-butatriene complexes and of one Cγ carbene adduct has been established by X-ray structure analyses.

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ISO 690REICHMANN, Bernhard, Matthias DREXLER, Bernhard WEIBERT, Normen SZESNI, Tobias STRITTMATTER, Helmut FISCHER, 2011. Amino-substituted butatrienes : Unusual η1 ligands formed by an unusual reaction. In: Organometallics. 2011, 30(5), pp. 1215-1223. ISSN 0276-7333. Available under: doi: 10.1021/om101163j
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@article{Reichmann2011Amino-19739,
  year={2011},
  doi={10.1021/om101163j},
  title={Amino-substituted butatrienes : Unusual η<sup>1</sup> ligands formed by an unusual reaction},
  number={5},
  volume={30},
  issn={0276-7333},
  journal={Organometallics},
  pages={1215--1223},
  author={Reichmann, Bernhard and Drexler, Matthias and Weibert, Bernhard and Szesni, Normen and Strittmatter, Tobias and Fischer, Helmut}
}
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    <dcterms:abstract xml:lang="eng">The reaction of the bis(amino)allenylidene complex [(CO)&lt;sub&gt;5&lt;/sub&gt;W═C═C═C(NMe&lt;sub&gt;2&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;] with diethyldiazomethane yields two products, a cyclic carbene complex (2) by 1,2-addition of Et&lt;sub&gt;2&lt;/sub&gt;C−N&lt;sub&gt;2&lt;/sub&gt; to the C&lt;sub&gt;α&lt;/sub&gt;−C&lt;sub&gt;β&lt;/sub&gt; bond of the allenylidene ligand and the η&lt;sup&gt;1&lt;/sup&gt;-butatriene complex [(CO)&lt;sub&gt;5&lt;/sub&gt;W{C[C(NMe&lt;sub&gt;2&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;]═C═CEt&lt;sub&gt;2&lt;/sub&gt;}] (3). Complex 2 slowly eliminates N&lt;sub&gt;2&lt;/sub&gt; and rearranges into 3. In contrast, only η&lt;sup&gt;1&lt;/sup&gt;-butatriene complexes, [(CO)&lt;sub&gt;5&lt;/sub&gt;M{C[C(NMe&lt;sub&gt;2&lt;/sub&gt;)XR]═C═C(R′)&lt;sub&gt;2&lt;/sub&gt;}], are isolated from the reaction of diazoalkanes (R′)&lt;sub&gt;2&lt;/sub&gt;C−N&lt;sub&gt;2&lt;/sub&gt; (R′ = Me, Et, &lt;sup&gt;n&lt;/sup&gt;Pr) with alkoxy(amino)allenylidene complexes [(CO)&lt;sub&gt;5&lt;/sub&gt;M═C═C═C(NMe&lt;sub&gt;2&lt;/sub&gt;)OR] (M = Cr, W; R = Me, Et, (−)-menthyl) or with the (alkylthio)(amino)allenylidene complex [(CO)&lt;sub&gt;5&lt;/sub&gt;W═C═C═C(NMe&lt;sub&gt;2&lt;/sub&gt;)S&lt;sup&gt;n&lt;/sup&gt;Pr]. These new η&lt;sup&gt;1&lt;/sup&gt;-butatriene complexes are related to C&lt;sub&gt;α&lt;/sub&gt; phosphine adducts of allenylidene complexes such as [(CO)&lt;sub&gt;5&lt;/sub&gt;W{C(PMe&lt;sub&gt;3&lt;/sub&gt;)═C═C(NMe&lt;sub&gt;2&lt;/sub&gt;)Ph}] (17) and might be regarded as C&lt;sub&gt;α&lt;/sub&gt; carbene adducts. However, the PMe&lt;sub&gt;3&lt;/sub&gt; substituent in 17 is not replaced when 17 is treated with an N-heterocyclic carbene. Vice versa, the “carbene” substituent “C(NMe&lt;sub&gt;2&lt;/sub&gt;)OEt” in the η&lt;sup&gt;1&lt;/sup&gt;-butatriene complex [(CO)&lt;sub&gt;5&lt;/sub&gt;Cr{C[C(NMe&lt;sub&gt;2&lt;/sub&gt;)OEt]═C═CEt&lt;sub&gt;2&lt;/sub&gt;}] is not replaceable by PMe&lt;sub&gt;3&lt;/sub&gt;. Free N-heterocyclic carbenes do not add to the C&lt;sub&gt;α&lt;/sub&gt; atom of the allenylidene complex [(CO)&lt;sub&gt;5&lt;/sub&gt;W═C═C═C(C&lt;sub&gt;6&lt;/sub&gt;H&lt;sub&gt;4&lt;/sub&gt;NMe&lt;sub&gt;2&lt;/sub&gt;-p)&lt;sub&gt;2&lt;/sub&gt;] but instead to the C&lt;sub&gt;γ&lt;/sub&gt; atom, giving the dipolar neutral alkynyl complexes [(CO)&lt;sub&gt;5&lt;/sub&gt;W−C≡CC(C&lt;sub&gt;6&lt;/sub&gt;H&lt;sub&gt;4&lt;/sub&gt;NMe&lt;sub&gt;2&lt;/sub&gt;-p)&lt;sub&gt;2&lt;/sub&gt;L] (L = SIMe, SIMes). DFT calculations on the reaction mechanism indicate that a cyclic carbene complex and two isomeric η&lt;sup&gt;2&lt;/sup&gt;-butatriene complexes are intermediates in the reaction pathway to form η&lt;sup&gt;1&lt;/sup&gt;-butatriene complexes. The structure of two representative examples of η&lt;sup&gt;1&lt;/sup&gt;-butatriene complexes and of one C&lt;sub&gt;γ&lt;/sub&gt; carbene adduct has been established by X-ray structure analyses.</dcterms:abstract>
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    <dcterms:bibliographicCitation>Publ. in: Organometallics ; 30 (2011), 5. - pp. 1215-1223</dcterms:bibliographicCitation>
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