Iron and Manganese Complexes of 2‑Carbonyl Pyrrolyls: Scorpionate Sandwich Anions and Extended Structures

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 gi...

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Bibliographic Details
Published in:Organometallics 2015-06, Vol.34 (11), p.2543-2549
Main Authors: Li, Lihong, Clarkson, Guy J, Lees, Martin R, Howson, Suzanne E, Tan, Sze-yin, Turner, Scott S, Scott, Peter
Format: Article
Language:English
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Summary: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.
ISSN:0276-7333
1520-6041
DOI:10.1021/om501218a