Preparation, structure, and properties of manganese toluene-3,4-dithiolate complexes in different oxidation states

Greiwe, Klaus; Krebs, Bernt; Henkel, Gerald

doi:10.1021/ic00318a021

Cited by 19 publications

(6 citation statements)

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“…The small angles are due to the ligand's bite angle {89.6(1)°} so that their counterparts become large {123.7(1) and 116.8(average)°}. Similar features have been observed for other [M(S 2 C 6 H 3 R) 2 ] n - complexes. The distortion from ideal T d symmetry can be described as an elongation of the molecule.…”

Section: Resultssupporting

confidence: 59%

Synthesis, Properties, and Crystal Structures of Benzene-1,2-dithiolato Complexes of Thallium(I) and -(III)

et al. 1996

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The syntheses, molecular structures and properties of homoleptic 1,2-S(2)C(6)H(4) complexes of thallium(I) and thallium(III) with four-coordinated metal centers are described. Anaerobic treatment of TlCl, TlNO(3), or Tl(2)CO(3) with solutions of sodium methanolate and 1,2-(HS)(2)C(6)H(4) in methanol gave after metathesis with [NEt(4)]Br yellow solutions of [NEt(4)](2)[{Tl(1,2-(&mgr;-S)(2)C(6)H(4))}(2)] ([NEt(4)](2)1). Yellow single crystals were obtained from saturated acetone solutions at -10 degrees C and the crystal data for [NEt(4)](2)1 are monoclinic, P2(1)/c, with Z = 2, a = 7.440(1) Å, b = 16.373(3) Å, c = 13.201(2) Å, and beta = 97.08(1) degrees. Complex 1(2)(-)(), the first structurally characterized homoleptic ionic thiolate complex of thallium(I), contains rectangular bipyramidal [TlS(4)Tl] cages with the four sulfur atoms defining the equatorial plane and the two thallium atoms in axial positions. The S(2)C(6)H(4) fragments are almost coplanar with the S(4) plane. In the crystal lattice, nearly linear Tl.Tl chains align along the a-axis (offset ca. 3.0 degrees ) with the ligand planes parallel to the bc-plane. Within and between dimers short Tl.Tl distances are observed (Tl.Tl' within a dimeric unit, 3.5116(4) Å; Tl.Tl between dimeric units, 3.9371(3) Å) with the distance between dimeric units being the shortest contact between anions-Tl.S distances between dimeric units are longer than 5.8 Å. Aerobic treatment of TlCl, TlNO(3), or Tl(2)CO(3) with solutions of sodium methanolate and 1,2-(HS)(2)C(6)H(4) in methanol and metathesis with [NEt(4)]Br led to [NEt(4)][Tl(1,2-S(2)C(6)H(4))(2)] ([NEt(4)]2). Yellow single crystals were obtained from saturated acetone solutions at 0 degrees C and the crystal data for [NEt(4)]2 are orthorhombic, Pnn2, with Z = 2, a = 11.449(2) Å, b = 10.060(2) Å, c = 9.950(2) Å. Complex 2(-) is the first homoleptic four-coordinate thiolate of thallium(III) and contains the unusually short Tl-S distance of 2.469(4) Å. In solution, ion pairing results in chemical and magnetic inequivalence of the S(2)C(6)H(4) ligands. Although both preparations employ the reaction of thallium(I) salts with 1,2-(NaS)(2)C(6)H(4) in a 1:2 stoichiometry, complex 1(2)(-) is probably not an intermediate to the formation of 2(-). Exposing anaerobically prepared solutions of 1(2)(-) to air results in a series of color changes in the solution over a 20 min period; however, 2(-) could not be observed by NMR spectroscopy.

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Section: Resultssupporting

confidence: 59%

Synthesis, Properties, and Crystal Structures of Benzene-1,2-dithiolato Complexes of Thallium(I) and -(III)

et al. 1996

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“…With the new phenomenon identified, a search for new examples of such molecules is in progress, both in Mn III chemistry and elsewhere. Several years ago, we and others briefly reported the synthesis of the first examples of stable Mn III thiolate complexes. − More recently, we have returned to magnetochemically characterize these molecules in detail with a particular emphasis on the ground state S and D values to be encountered in this area. We herein describe the syntheses, full structural details, and magnetochemical properties of several of these species spanning nuclearities 1 to 3 and at the oxidation level Mn III or mixed-valent Mn II , Mn III .…”

Section: Introductionmentioning

confidence: 99%

Structural and Magnetochemical Properties of Mono-, Di-, and Trinuclear Manganese(III) Dithiolate Complexes

et al. 1998

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Aerial oxidation of Mn(II)/ptt(3)(-) (ptt(3)(-) = propane-1,2,3-trithiolate) mixtures gives [Mn(2)(pttd)(2)](2)(-), where pttd(4)(-) is the mono(disulfide) of ptt(3)(-). (NEt(3)Bz)(2)[Mn(2)(pttd)(2)] (2) crystallizes in space group P2(1)/c with (at -158 degrees C) a = 11.540(2) Å, b = 12.115(2) Å, c = 17.478(4) Å, beta = 101.78(1) degrees, and Z = 2. The anion contains a doubly-bridged [Mn(2)S(8)] core (Mn.Mn = 3.598(2) Å) with five-coordinate Mn(III) ions, very similar to previously reported [Mn(2)(edt)(4)](2)(-) (anion of 1; edt(2)(-) = ethane-1,2-dithiolate). Aerial oxidation of Mn(II)/pdt(2)(-) (pdt(2)(-) = propane-1,3-dithiolate) mixtures gives [Mn(3)(pdt)(5)](2)(-), which is mixed valent (Mn(II), 2Mn(III)). (PPh(4))(2)[Mn(3)(pdt)(5)] (3) crystallizes in space group P&onemacr; with (at -161 degrees C) a = 14.385(6) Å, b = 23.734(11) Å, and Z = 2. The anion contains a near-linear Mn(III)Mn(II)Mn(III) unit with five-coordinate Mn(III), six-coordinate Mn(II), and three thiolate bridges between each Mn(2) pair; Mn.Mn separations are 3.123(3) and 3.101(3) Å. Aerial oxidation of Mn(II)/edt(2)(-)/ImH (ImH = imidazole) mixtures gives [Mn(edt)(2)(ImH)](-). (NEt(4))[Mn(edt)(2)(ImH)] (4) crystallizes in space group P2(1)/n with (at -72 degrees C) a = 13.974(5) Å, b = 14.317(5) Å, c = 10.564(3) Å, beta = 90.13(2) degrees, and Z = 4. The anion is five-coordinate and square-pyramidal. Aerial oxidation of Mn(II)/edt(2)(-)/Im(-) mixtures gave [Mn(2)(Im)(edt)(4)](3)(-), which contains two Mn(III) ions. (NMe(4))(3)[Mn(2)(Im)(edt)(4)] (5) crystallizes in space group Pna2(1) with (at -160 degrees C) a = 17.965(5) Å, b = 16.094(4) Å, c = 14.789(3) Å, and Z = 4. The five-coordinate Mn(III) ions are bridged by the Im(-) group across a Mn.Mn separation of 6.487(2) Å. The anion of 4 contains high-spin Mn(III) (S = 2) and exhibits inter-anion antiferromagnetic exchange interactions (J = -0.15 cm(-)(1), g = 1.91) propagated by interanion NH.S hydrogen bonds. Complexes 1-3 and 5 all possess intraanion antiferromagnetic exchange interactions; the fitting parameters are as follows: 1, J = -19.0 cm(-)(1), g = 1.96, D = -0.22 cm(-)(1); 2, J = -16.4 cm(-)(1), g = 1.96, D = -0.22 cm(-)(1); 3, J = -18.8 cm(-)(1), g = 2.00; 5, J = -1.75 cm(-)(1), g = 1.84, D = -0.028 cm(-)(1) (H = -2JS(i)()S(j)() convention). Complexes 1, 2, and 5 have S = 0 ground states, while that of 3 is S = (3)/(2).

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“…The first evidence for manganese binding to sulfur donor group in metalloprotein is tryptophan-modified Mn(III) containing acid phosphatise [4]. As compared to the other transition metals, manganese forms complexes with 1,1-dithio and 1,2-dithiolene ligands such as [Mn(SPh) 4 ] 2− , [MnCl(SPh) 3 ] 2− , [Mn 4 (SPh) 10 ] 2− , [Mn(edt) 2 ] 2− , [Mn 2 (edt) 4 ] 2− (edt = ethane-1,2-dithiolate), and [Mn 2 (S 2 -O-xyl) 2 X 2 ] 2− (X = PhS − , Et 2 NCS 2 − ; X 2 = S 2 -O-xyl 2− ) [5]. …”

Section: Introductionmentioning

confidence: 99%

Spectroscopic, Thermal, Electrochemical, and Antimicrobial Studies of Mononuclear Manganese(II) Ditolyldithiophosphates

Khajuria

Syed

Kumar

et al. 2013

Bioinorganic Chemistry and Applications

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New complexes of manganese(II) corresponding to [{(ArO)2PS2}2Mn] and [{(ArO)2PS2}2Mn.nL] (Ar = o-, m-, p-CH3C6H4 and p-Cl-m-CH3C6H3; n = 1, L = N2C12H8, N2C10H8; n = 2, L = NC5H5, P(C6H5)3) have been synthesized and characterized by microelemental analyses (C, H, and N), magnetic susceptibility, molar conductance, thermogravimetric, cyclic voltammetry, and spectral analyses including ESI mass spectrometry, IR, and UV-visible. The presence of a four-and-six coordinated Mn atoms has been established in the complexes and adducts, respectively. Antimicrobial screening of the complexes against gram negative bacteria E. coli, K. pneumonia, and P. aeruginosa and fungus S. rolfsii has shown potential bioactivity.

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Preparation, structure, and properties of manganese toluene-3,4-dithiolate complexes in different oxidation states

Cited by 19 publications

References 0 publications

Synthesis, Properties, and Crystal Structures of Benzene-1,2-dithiolato Complexes of Thallium(I) and -(III)

Synthesis, Properties, and Crystal Structures of Benzene-1,2-dithiolato Complexes of Thallium(I) and -(III)

Structural and Magnetochemical Properties of Mono-, Di-, and Trinuclear Manganese(III) Dithiolate Complexes

Spectroscopic, Thermal, Electrochemical, and Antimicrobial Studies of Mononuclear Manganese(II) Ditolyldithiophosphates

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