Iron and Manganese Complexes of 2-Carbonyl Pyrrolyls: Scorpionate Sandwich Anions and Extended Structures
Iron and Manganese Complexes of 2-Carbonyl Pyrrolyls: Scorpionate Sandwich Anions and Extended Structures
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DOI：
10.1021/om501218a
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发表时间：
2015-05
期刊：
影响因子：
2.8
通讯作者：
Lihong Li;G. Clarkson;M. Lees;S. Howson;Sze-yin Tan;S. Turner;P. Scott
中科院分区：
文献类型：
--
作者：
Lihong Li;G. Clarkson;M. Lees;S. Howson;Sze-yin Tan;S. Turner;P. Scott
试图用2-氨基吡啶配体（N-O）合成Fe和Mn（II）的配合物是不成功的，只有少量的三价三联体配合物M(N-O)3被检测到，尽管在Fe（III）的情况下观察到不同寻常的面结构。相反，2-苯甲酰吡啶体系给出M（II）配合物，并且在迄今为止存在Na+的所有情况下，一个蝎子酸面-[MII(N-O)3] -单元自组装成夹心阴离子[MII(N-O)3Na(O-N)3MII] -，其中中心金属被芳基单元的交叉指化有效地包裹起来。扩展结构很容易通过使用2-（4-吡啶基）吡咯酰胺配体。当使用Li+时，蝎酸配体没有组装，而是[M(N-O)2]单元给出了菱形二维网格。铁系在120k时显示自旋交叉。
Attempts to synthesize complexes of Fe and Mn(II) with 2-amidopyrrolyl ligands (N–O) were unsuccessful, and only small amounts of the trivalent tris complexes M(N–O)3 were detected, although unusually in the case of Fe(III) a fac structure is observed. In contrast the 2-benzoylpyrrolyl systems give M(II) complexes, and in all instances thus far where Na+ is present, a scorpionate fac-[MII(N–O)3]− unit self-assembles into sandwich anions [MII(N–O)3Na(O–N)3MII]− in which the central metal is efficiently encapsulated by interdigitation of the aryl units. Extended structures are readily made through the use of a 2-(4-pyridinoyl)pyrrolylamide ligand. When Li+ is used, the scorpionate ligand is not assembled, and instead [M(N–O)2] units give rhombic 2D grids. The Fe system displays spin-crossover at 120 K.