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Inorganics 2017, 5(3), 59;

Assembly of Mn(III) Schiff Base Complexes with Heptacyanorhenate (IV)

Nikolaev Institute of Inorganic Chemistry SB RAS, Novosibirsk 630090, Russia
Novosibirsk National Research State University, 630090 Novosibirsk, Russia
Author to whom correspondence should be addressed.
Received: 8 August 2017 / Revised: 28 August 2017 / Accepted: 29 August 2017 / Published: 1 September 2017
(This article belongs to the Special Issue Schiff-Base Metal Complexes)
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A pioneering research on a self-assembly of the magneto-anisotropic module [Re(CN)7]3− with the Mn(III) complexes involving Salen type (N,N′-ethylenebis(salicylideneiminate)) Schiff base (SB) ligands was performed using the known [Mn(3MeOSalen)(H2O)2]2(ClO4)2·H2O (1) and the firstly synthesized [Mn2(5MeSalen)2OAc]PF6 (2). In the case of 1, a slow diffusion of the component solutions led to the ionic compound Ph4P[Mn(3MeOSalen)(H2O)2]2[Re(CN)7]·6H2O (3). The direct mixing of the same solutions has resulted in the microcrystalline nearly insoluble solid [Mn(3MeOSalen)(H2O))4Re(CN)7]ClO4·1.5MeCN·6.5H2O, which is likely to comprise the pentanuclear clusters [(MnIII(SB)(H2O))4Re(CN)7]+. The use of 2 resulted in a 2D-network assembly of octanuclear clusters, [{(Mn(5MeSalen))6(H2O)2Re(CN)7}2Re(CN)7]Cl2(PF6)·H2O (4), incorporating one Re-center in a pentagonal bipyramid coordination environment, while another has strongly distorted capped trigonal prism as a coordination polyhedron. The latter was observed for the first time for Re(IV) complexes. A synthetic challenge to obtain the 0D assemblies with Re:Mn ≥ 3 has yielded a hexanuclear complex [Mn(5MeSalen)H2O(i-PrOH)][(Mn(5MeSalen))5H2O(i-PrOH)2Re(CN)7](PF6)2(OAc)·2i-PrOH (5) being 1D chain via a bridging phenoxyl group. Owing to a low solubility of the final product, an addition of a bulk anion Ph4B to the MeCN/MeOH solution of [Re(CN)7]3−and 1 in ratio 1:6 resulted in rhenium-free matter [Mn(3MeOSalen)(H2O)2][Mn(3MeOSalen)(H2O)MeCN](Ph4B)2·5MeCN (6). View Full-Text
Keywords: Mn(III) Schiff base complexes; heptacyanorhennate; Re(IV); salen type ligands Mn(III) Schiff base complexes; heptacyanorhennate; Re(IV); salen type ligands

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Sukhikh, T.S.; Vostrikova, K.E. Assembly of Mn(III) Schiff Base Complexes with Heptacyanorhenate (IV). Inorganics 2017, 5, 59.

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