[Mn(S₂C₆H₃Me)₂]ⁿ⁻: Schwefelsubstituierte planar (n=1) und verzerrt‐tetraedrisch koordinierte (n=2) einkernige Mangan‐Komplexe

Abstract

Der ungewöhnliche planare Mangan (III)‐Schwefel‐Komplex [Mn(S2C6H3Me)2]‐ 1 bildet sich bei der Umsetzung von MnCl2·4H2O mit Toluol‐3,4‐dithiolat in Methanol in Gegenwart von Luftsauerstoff. Außerdem entsteht der quadratisch‐pyramidale Komplex mit zusätzlicher apicaler meOH‐Gruppe. Unter anaeroben Bedingungen erhält man den Mangan(II)‐Schwefel‐Komplex [Mn(S2C6H3Me)2]2−, der sich von 1 durch stark verzerrte tetraedrische Koordination unterscheidet.

Dinuclear Complexes with Bis(benzenedithiolate) Ligands

“…Similar arguments hold for bis(benzenedithiolate) complexes that can adopt a square‐pyramidal or tetrahedral coordination geometry, depending on the oxidation state of the metal atom. This has already been demonstrated with Mn III and Mn II complexes 11…”

“…This is illustrated in Figure 2 for complex 14. It can be seen that the two [Ni(S 2 C 6 H 3 R) 2 ] (2), S1ÀC1 1.768(8), S2ÀC2 1.743(8), S3ÀC12 1.767 (7), S4ÀC13 1.766(8), S5ÀC17 1.742 (7), S6ÀC18 1.753(8), S7ÀC28 1.765 (7), S8ÀC29 1.749 (8); S1-Ni1-S2 91.31 (8), S1-Ni1-S5 90.45 (8), S1-Ni1-S6 172.34 (11), S2-Ni1-S5 174.10(9), S2-Ni1-S6 88.88 (8), S5-Ni1-S6 90.13 (8), S3-Ni2-S4 89.86 (8), S3-Ni2-S7 89.49 (8), S3-Ni2-S8 171.44(10), S4-Ni2-S7 174.84(9), S4-Ni2-S8 90.74 (8), S7-Ni2-S8 90.67 (8), C1-S1-Ni1 105.2(3), C2-S2-Ni1 106.3(3), C12-S3-Ni2 106.8(3), C13-S4-Ni2 105.5(3), C17-S5-Ni1 105.3(3), C18-S6-Ni1 108.4(3), C28-S7-Ni2 106.9(2), C29-S8-Ni2 105.3(3); 13: NiÀS1 2.140(3), NiÀS2 2.155(3), NiÀS3 2.151(3), NiÀS4 2.162(3), S1ÀC1 1.730(9), S2ÀC2 1.742(9), S3ÀC9 1.736(10), S4ÀC10 1.756(10); S1-Ni-S3 88.52(10), S1-Ni-S2 91.51(10), S1-Ni-S4 175.24 (12), S2-Ni-S3 174.84 (12), S2-Ni-S4 89.00(10), S3-Ni-S4 91.39(10), C1-S1-Ni 105.1(3), C2-S2-Ni 105.5(3), C9-S3-Ni 105.3(4), C10-S4-Ni 105.4(3).…”

“…This has already been demonstrated with Mn III and Mn II complexes. [11] We have recently reported the synthesis of chelate complexes with tripodal tris(benzenedithiolate) and bis(benzenedithiolate) ligands based on 2,3-dimercaptobenzoic acid. [12] To obtain dinuclear complexes, these ligands had to be substituted with shorter bridging units between the benzene-1,2dithiol units to disable chelate formation.…”

[Mn(SPh)3Cl]2-, [Mn(SPh)3Br]2-, [Mn(SePh)4]2-, [Mn(TePh)4]2-, and [Co4(SPh)6Cl4]2-: New Mixed Halide/Thiolate and Chalcogenolate Complexes of Manganese and Cobalt

“…In solution, the adam antane type spe cies is fluxional, but in the solid state the orienta tion of the phenyl groups is determined by the de tailed stereochemistry of the anion and packing forces o f the crystal lattice. For 5 the six phenyl groups attached to the S atoms of the four con densed C03S3 heterocycles exhibit the 2 -2 - [18]. The 'H N M R spec trum of 5 in acetonitrile solution presented in Fig.…”