Eisen- und Cobaltkomplexe mit Schwefelliganden: Darstellung und Kristallstrukturen von [Me4N][FeCl{S2P(OMe)2}2], [Me4N][CoCl{S2P(OMe)2}2], [Et4N][FeCl{S2P(p-C6H4Me)2}2], [Et4N]2[FeCl{ S2PS(OMe) } 2] und [Fe { S2P(OMe)2 }3] / Iron and Cobalt Complexes with Sulfur-Containing Ligands: Preparation and Crystal Structures of [Me4N][FeCl{S2P(OMe)2}2],[Me4N][CoCl{S2P(OMe)2}2], [Et4N][FeCl{S2P(p-C6H4Me)2}2], [Et4N]2[FeCl{S2PS(OMe)}2] and [Fe{S2P(OMe)2}3]

Autor: Kristin Kirschbaum, Uta Bönnighausen, Ewald Gesing, Klaus Greiwe, Ulrich Kuhlmann, Henry Strasdeit, Bernt Krebs, Gerald Henkel
Rok vydání: 1990
Předmět:
Zdroj: Zeitschrift für Naturforschung B. 45:245-257
ISSN: 1865-7117
0932-0776
DOI: 10.1515/znb-1990-0219
Popis: The reaction systems MCl2/K{S2P(OMe)2} (M = Fe(II), Co(II)), FeCl2/Na{S2S2P(p-C6H4Me)2}, and FeCl3/K2{S2PS(OMe)} in methanol afford the mononuclear complexes [FeCl{S2P(OMe)2}2]-, [CoCl{S2P(OMe)2}2]-, [FeCl{S2P(p-C6H4Me)2}2]-, and [FeCl{S2PS(OMe)}2]2-, which were isolated as salts [Me4N][FeCl{S2P(OMe)2}2] (1), [Me4N][CoCl{S2P(OMe)2}2] (2), [Et4N][FeCl{S2P(p-C6H4Me)2}2] (3) and [Et4N]2[FeCl{S2PS(OMe)}2] (4), respectively. Crystals of [Me4N][MCl{S2P(OMe)2}2] are triclinic, space group P 1 (Z = 2): Fe(II), a = 7.165(3), b = 8.628(3), c = 16.526(6)Å, α = 83.98(3), β = 85.32(3), γ = 89.80(3)°; Co(II), a = 7.164(2), b = 8.612(2), c = 16.504(4)Å, α = 84.59(2), β = 84.63(2), γ = 89.41(2)°. The structures of 1 and 2 were refined to R (Rw) = 0.034 (0.043) and 0.028 (0.032), respectively. Compound 3 is monoclinic, space group C2/c, Z = 4 with a = 23.831(5), b = 10.536(3), c = 17.133(4)Å, β = 114.43(3)°. Its structure was refined to R (Rw) = 0.046 (0.052). 4 crystallizes in the orthorhombic space group Pccn with a = 13.310(2), b = 12.982(2), c = 18.968(3) Å, and Z = 4. The refinement converged to R (Rw) = 0.042 (0.039). The anions of the compounds 1—4 contain five-coordinated metal centers which reside in distorted trigonal-bipyramidal (1, 2, and 3) or square pyramidal (4) S4Cl-environments. The neutral complex [Fe{S2P(OMe)2}3] (5) with six-coordinated metal sites was isolated from the reaction system FeCl3/K{S2P(OMe)2} in CH2Cl2. 5 is monoclinic, space group C 2/c (Z = 4) with a = 14.211(2), b = 11.115(2), c = 12.823(2) Å, β = 97.23(1)°. The refinement converged to R (Rw) = 0.022 (0.031). The anions of 1, 2, and 3 represent the first examples of structurally defined mononuclear Fe(II) and Co(II) complexes containing 1,1-dithiolate groups and halide ions simultaneously.
Databáze: OpenAIRE
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