om501218a_si_001.pdf (511.48 kB)
Iron and Manganese Complexes of 2‑Carbonyl Pyrrolyls: Scorpionate Sandwich Anions and Extended Structures
journal contribution
posted on 2015-06-08, 00:00 authored by Lihong Li, Guy J. Clarkson, Martin
R. Lees, Suzanne E. Howson, Sze-yin Tan, Scott S. Turner, Peter ScottAttempts 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.