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Inorganics 2017, 5(3), 59; https://doi.org/10.3390/inorganics5030059

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

1
Nikolaev Institute of Inorganic Chemistry SB RAS, Novosibirsk 630090, Russia
2
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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Abstract

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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