Cleavage of the C-H Bond in Bu3MeP+ by Zinc Porphyrin Dianions: Formation of {ZnII(CH2PBu3)(TPyPH)}- Containing Zn-C(ylide) Bond and the (TPyPH)3- Macrocycle Showing Strong NIR Absorption.,Inorganic Chemistry

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Cleavage of the C-H Bond in Bu3MeP+ by Zinc Porphyrin Dianions: Formation of {ZnII(CH2PBu3)(TPyPH)}- Containing Zn-C(ylide) Bond and the (TPyPH)3- Macrocycle Showing Strong NIR Absorption.
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2020-01-09 , DOI: 10.1021/acs.inorgchem.9b02808
Dmitri V Konarev ₁ , Alexey V Kuzmin ₂ , Salavat S Khasanov ₂ , Alexander F Shestakov _{1,

3} , Alexey L Litvinov ₁ , Pavel A Sobov _{1,

3} , Akihiro Otsuka _{4,

5} , Hideki Yamochi _{4,

5} , Hiroshi Kitagawa ₄ , Rimma N Lyubovskaya ₁

Affiliation

Reduction of {ZnII(TPyP)} to the {ZnII(TPyP)}2- dianions (TPyP: tetra(4-pyridyl)porphyrin) in the presence of Bu3MeP+ allows one to observe the C-H bond cleavage in the methyl group of Bu3MeP+ to form (Bu3MeP+){ZnII(CH2PBu3)(TPyPH)}-·0.337C6H5CH3 (1). Salt 1 is the first coordination complex of neutral CH2PBu3 ylide and metalloporphyrin. The released hydrogen atom attacks the meso-carbon atom of TPyP4- forming a TPyPH3- macrocycle related to phlorins. Decreased symmetry of the TPyPH3- allows the observation of a strong NIR absorption. We discuss the molecular structure, optical, and magnetic properties of 1 together with its formation pathways.

中文翻译：

卟啉锌离子对Bu3MeP +中CH键的裂解：形成{ZnII（CH2PBu3）（TPyPH）}-含Zn-C（内酯）键和（TPyPH）3-大环化合物，具有很强的NIR吸收能力。

在Bu3MeP +存在下，将{ZnII（TPyP）}还原为{ZnII（TPyP）} 2-二价阴离子（TPyP：四（4-吡啶基）卟啉），可以观察到Bu3MeP +甲基中的CH键裂解为形式（Bu3MeP +）{ZnII（CH2PBu3）（TPyPH）}-·0.337C6H5CH3（1）。盐1是中性CH2PBu3内酯和金属卟啉的第一个配位化合物。释放的氢原子攻击TPyP4-的内消旋碳原子，形成与菲洛林有关的TPyPH3-大环。TPyPH3-的对称性降低，可以观察到强烈的近红外吸收。我们讨论1的分子结构，光学和磁性，以及其形成途径。

更新日期：2020-01-10

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