[Mn(S₂C₆H₃Me)2]ⁿ⁻: Mononuclear Manganese Complexes with Square‐Planar (n = 1) and Distorted Tetrahedral (n = 2) Sulfur Coordination

Abstract

The unusual planar manganese(III)‐sulfur complex [Mn(S2C6H3Me)2]−1 is formed on reaction of MnCl2·4H2O with toluene‐3,4‐dithiolate in methanol in the presence of atmospheric oxygen. A further product is the square‐pyramidal complex containing an additional apical MeOH group. Reaction under anaerobic conditions leads to formation of the manganese(II)‐sulfur complex [Mn(S2C6H3Me)2]2−, which differs from 1 through its strongly distorted tetrahedral coordination.

Artificial chemical and magnetic structure at the domain walls of an epitaxial oxide

“…Some exceptions to this rule exist, but are extremely rare in the case of manganese. As far as we can tell, Mn in a quasi-square-planar coordination has been reported four times for molecules [49][50][51][52] , and all those cases differ very clearly from the present case (diversity of ligands, significant asymmetry of the ligand fields and so on). For solidstate systems, we have not been able to find a single instance of square-planar MnO 4 group coordination.…”

Chelate complexes of cobalt(III) with bis(dithiolate) ligands: backbone influence on the electronic properties and the reactivity of the metal center

“…We synthesized tetradentate ligands with two benzene-1,2-dithiolate donors of type B in which the bidentate binding unit might retain some dithiolene character upon co-ordination. Our research was particularly prompted by the intriguing "non innocent" behaviour of dithiolene ligands 6 including the stability of their complexes in two or more oxidation states and the (minor 7 or major 8 ) dependence of the complex co-ordination geometry on the oxidation state of the metal. The geometry of [Mn(tdt) 2 ] nϪ (tdt 2Ϫ = toluene-3,4-dithiolate) for instance changes from planar (n = 1) to distorted tetrahedral (n = 2) upon reduction.…”

“…The geometry of [Mn(tdt) 2 ] nϪ (tdt 2Ϫ = toluene-3,4-dithiolate) for instance changes from planar (n = 1) to distorted tetrahedral (n = 2) upon reduction. 8 A suitably bridged bis(dithiolate) ligand of type B might not be able to accommodate both co-ordination geometries and thus can destabilize a specific oxidation state possibly generating an unprecedented reactivity. Thus, ligands of type B offer not only the opportunity for the preparation of new model complexes for the active sites in sulfur containing metalloenzymes but might also allow an investigation of how geometric constraints originating comparatively far from the metal centre in the organic backbone of the ligand affect the properties of the co-ordinated metal centre.…”

The first manganese trialkoxysilanethiolates: Formation, properties and structure of solvent ligated complexes – [Mn{SSi(OBut)3}2(MeCN)] and [Mn{SSi(OBut)3}2(MeOH)4]

“…Polymeric thiolate obtained with pyridine-2(1H)-thione [21], phenanthroline ligated complex prepared with 4,6-dimethylpyrimidine-2(1H)-thione [22] and mixed halide-thiolate complexes [Mn(SPh) 3 X] 2À where X = Cl, Br [23] show other possibilities. Finally we should mention the methanol ligated thiolate Mn(S 2 -3,4-C 6 H 3 Me) 2 (MeOH)] À [20]. The summary presented above is in sharp contrast to the only known Mn(II) silanethiolate complex -[Mn(SSiPh 3 ) 2 (T-MEDA)] -prepared in the presence of stabilizing chelating nitrogen ligand [24].…”

“…Manganese thiolates are known for Mn(II) and Mn(III) although their number, compared to the later 1 st row transition elements (Fe-Zn), is smaller. Neutral manganese thiolates, with such sterically encumbered thiophenolate ligands as -SC 6 H 3 -2,6-(SiMe 3 ) 2 [12], -SC 6 H 2 À 2; 4; 6 À Bu t 3 [13], -SC 6 H 2 -2,4,6-(CF 3 ) 3 [14] and -SC 6 H 3 À 2; 6 À ðC 6 H 2 À 2; 4; 6 À Pr i 3 Þ 2 [15] [16,19] or MnðS 2 À 3; 4 À C 6 H 3 MeÞ 2À 2 and MnðS 2 À 3; 4 À C 6 H 3 MeÞ À 2 , respectively [20]. Polymeric thiolate obtained with pyridine-2(1H)-thione [21], phenanthroline ligated complex prepared with 4,6-dimethylpyrimidine-2(1H)-thione [22] and mixed halide-thiolate complexes [Mn(SPh) 3 X] 2À where X = Cl, Br [23] show other possibilities.…”