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Activation of Ligand Reaction on an Iron Complex: H/D Exchange Reaction of a Low-Spin Bis[2-(Pyridylmethylidene)-1-(2-pyridyl)methylamine]iron(II) Complex.
Chemical & Pharmaceutical Bulletin ( IF 1.7 ) Pub Date : 2020-08-01 , DOI: 10.1248/cpb.c20-00383
Masanori Imai 1 , Koichi Kato 1 , Yoshihiro Yamaguchi 2 , Mikako Fujita 3 , Masami Otsuka 3, 4 , Hiromasa Kurosaki 1
Affiliation  

With the aim of shedding some light on the still scarcely investigated mechanism of transformation of imines in metal complexes, this study describes the investigation of the hydrogen–deuterium (H/D) exchange reaction of a bis[2-(pyridylmethylidene)-1-(2-pyridylmethylamine]iron(II) complex ([Fe(PMAP)2]2+), following our previous work on a low-spin iron(II) complex bearing two molecules of S-2-pyridylmethylidene-1-(2-pyridyl)ethylamine. This complex has been proven to undergo successive transiminations in acetonitrile, yielding a bis[1-(2-pyridyl)ethylidene-2-pyridylmethylamine]iron(II) complex. In the analogous [Fe(PMAP)2]2+ complex, a 1,3-hydrogen rearrangement occurs in a 10% deuterium oxide-acetonitrile-d3 (D2O–CD3CN) solution. The H/D exchange reaction of [Fe(PMAP)2]2+ was examined in the presence of various concentrations of 2,6-dimethylpyridine as a base in a 10% D2O–CD3CN solution at 45 °C, and the reaction mechanism was investigated.

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中文翻译:

铁络合物上配体反应的活化:低旋转双[2-(吡啶基亚甲基)-1-(2-吡啶基甲胺)铁(II)络合物的H / D交换反应。

为了阐明仍很少研究的金属络合物中亚胺的转化机理,本研究描述了对双[2-(吡啶基甲基亚甲基)-1-的氢-氘(H / D)交换反应的研究。 (2-吡啶基甲基胺]铁(II)配合物([Fe(PMAP)2 ] 2+),是我们先前对带有两个S -2-吡啶基甲基亚甲基-1-(2分子)的低旋转铁(II)配合物的研究-吡啶基)乙胺已证明该络合物在乙腈中进行连续的氨基转移,生成双[1-(2-吡啶基)亚乙基-2-吡啶基甲胺]铁(II)络合物,类似物[Fe(PMAP)2 ]。2+络合物在10%氧化氘-乙腈-中发生1,3-氢重排d 3(D 2 O–CD 3 CN)解决方案。的[Fe(PMAP)的H / d交换反应2 ] 2+是在不同浓度的2,6-二甲基吡啶作为在10%d碱的存在下检查2 -O-CD 3 CN溶液在45 ° C,并研究了反应机理。

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更新日期:2020-08-23
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