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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Tautomerisation and hydrogen-bonding interactions in four-coordinate metal halide and azide complexes of N-donor-extended dipyrromethanes
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Tautomerisation and hydrogen-bonding interactions in four-coordinate metal halide and azide complexes of N-donor-extended dipyrromethanes

机译：N-供体扩展的二吡咯甲烷四配位金属卤化物和叠氮化物配合物中的互变异构和氢键相互作用

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摘要

The synthesis and structures of Fe, Co, and Zn halide complexes [MX2(H2L)] (M = Fe, X = Br; M = Co, Zn, X = Cl) of the N-donor extended dipyrromethane ligand H2L are described, from which it is clear that bond rearrangements from imine-pyrrole to amine-azafulvene tautomers occur on metal co-ordination, both in the solid state and in solution. In the structure of [FeBr2(H2L)], this H-migration results in a pendant amine that is involved in both inter-and intramolecular hydrogen bonds to the bromide ligands, so forming a dimer. As the tautomerisation renders the N-H protons less acidic, metal-based ligand substitution reactions can occur in favour of deprotonation. As such, the reaction between [MCl2(H2L)] (M = Co, Zn) and NaN3 results in the formation of the bis(azide) complexes [M(N-3)(2)(H2L)] which for Co displays both inter-and intramolecular N-H center dot center dot center dot N-3-Co hydrogen bonds in the solid state. In contrast, reactions of the dihalides with the lithium bases LiNMe2 or LiMe (M = Fe), or reduction reactions with C8K (M = Fe, Co) result in the formation of the known dinuclear helicates [M-2(L)(2)].
机译：描述了N供体扩展的二吡咯甲烷配体H2L的Fe，Co和Zn卤化物配合物[MX2（H2L）]（M = Fe，X = Br; M = Co，Zn，X = Cl）的合成和结构，从中很明显，在金属配位过程中，无论是在固态还是在溶液中，都从亚胺-吡咯到胺-氮杂富烯的互变异构体发生键重排。在[FeBr2（H2L）]的结构中，这种H迁移导致侧链胺参与与溴化物配体的分子间和分子内氢键，从而形成二聚体。由于互变异构作用使N-H质子的酸性降低，可以发生金属基配体取代反应，从而有利于去质子化。这样，[MCl2（H2L）]（M = Co，Zn）与NaN3之间的反应导致形成双（叠氮化物）配合物[M（N-3）（2）（H2L）]，用于Co展示分子内和分子内NH中心点中心点中心点N-3-Co氢键均处于固态。相反，二卤化物与锂碱LiNMe2或LiMe（M = Fe）的反应，或与C8K的还原反应（M = Fe，Co）的反应会形成已知的双核螺旋[M-2（L）（2 ）]。

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