Metal complexes of dithiolate ligands: 5,6-dihydro-l,4-dithiin-2,3-dithiolato (dddt), 5,7-dihydro-l,4,6-trithiin-2,3-dithiolato (dtdt), and 2-thioxo-1,3-dithiole-4,5-dithiolato (dmit). Synthesis, electrochemical studies, crystal and electronic structures, and conducting properties
Inorganic Chemistry, ISSN: 0020-1669, Vol: 35, Issue: 13, Page: 3856-3873
1996
- 56Citations
- 19Captures
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Article Description
New precursors to potentially conductive noninteger oxidation state (NIOS) compounds based on metal complexes [ML] [M = Ni, Pd, Pt; L = 5,6-dihydro-1,4-dithiin-2,3-dithiolato (dddt), 5,7-dihydro-1,4,6-trithiin-2,3-dithiolato (dtdt), and 2-thioxo-1,3-dithiole-4,5-dithiolato (dmit); n = 2, 1,0] have been investigated. Complexes of the series (NR)[ML] (R = Me, Et, Bu; L = dddt, dtdt) have been isolated and characterized, and the crystal structure of (NBu)[Pt(dtdt)] (1) has been determined (1 = CHNPtS, a -12.064(2) Å, b = 17.201(3) Å, c = 16.878(2) Å, β= 102.22(2)̊, V= 3423(1) Å, monoclinic, P2/n, Z = 4}. Oxidation of these complexes affords the corresponding neutral species [ML]. Another series of general formula (cation)[M(dmit)] [cation = PPN, BTP, and (SMeEt) with y = 0, 1, 2, and 3, n = 2, 1, M = Ni, Pd] has also been studied. All of these (cation)[M(dmit)] complexes have been isolated and characterized [with the exception of (cation)[Pd-(dmit)] for cation = (SMeEt)]. The crystal structures of (PPN)LNi(dmit)]·(CH)CO (2) and (SMeEt)[Ni(dmit)] (3) have been determined {2 = CHNNiSPO, a = 12.310(2) Å, b = 13.328(3) Å, c = 15.850(3) Å, α = 108.19(3)°, β= 96.64(2)°, γ = 99.67(2)°, V = 2373(1) Å, triclinic, PĪ, Z = 2; 3 = CMNiS, a = 7.171(9) Å, b = 17.802(3) Å, c = 16.251(3) Å, β = 94.39(4)°, V = 2068(2) Å, monoclinic, P2/n, Z = 4} NIOS salts derived from the preceding precursors were obtained by electrochemical oxidation. Electrochemical studies of the [M(dddt)] complexes show that they may be used for the preparation of NIOS radical cation salts and [M(dddt)][M'(dmit)] compounds, but not for the preparation of (cation)[M(dddt)] NIOS radical anion salts. The electrochemical oxidation of the [M(dtdt)] complexes always yields the neutral [M(dtdt)] species. The crystal structure of [Pt(dddt)][Ni(dmit)] (4) has been determined and is consistent with the low compaction powder conductivity (5 × 10 S cm at room temperature) {4 = CHNiPtS, a = 20.336(4) Å, b = 7.189(2) Å, c = 14.181(2) Å, β = 97.16(2)°, V = 2057(1) Å, monoclinic, C2/m, Z = 2}. The crystal structures of the semiconducting NIOS compounds (BTP)[Ni(dmit)] (5) and (SMe)[Ni(dmit)] (6) have been determined {5 = CHPNiS, a = 11.927(2) Å, b = 24.919(2) Å, c = 11.829(3) Å, α = 93.11(1)°, β= 110.22(1)°, γ = 83.94(1)°, V = 3284(1) Å3, triclinic, PĪ, Z = 2; 6 = CHNiS, a = 7.882(1) Å, b = 11.603(2) Å, c = 17.731(2) Å, α = 77.44(1)°, β= 94.39(1)°, γ = 81.27(1)°, V = 1563(1) Å, triclinic, PĪ, Z = 2}. The parent compound (SEt)[Ni(dmit)] (unknown stoichiometry) is also a semiconductor with a single-crystal conductivity at room temperature of 10 S cm. By contrast, the single-crystal conductivity at room temperature of (SMeEt)[Pd(dmit)] (7) is rather high (100 S cm). 7 behaves as a pseudometal down to 150 K and undergoes an irreversible metal-insulator transition below this temperature. The crystal structure of 7 has been determined {7 = CHNPdS, a = 7.804(4) Å, b = 36.171(18) Å, c = 6.284(2) Å, α = 91.68(4)°, β= 112.08(4)°, γ = 88.79(5)°, V = 1643(1) Å3, triclinic, P1̄. Z = 2}. The electronic structure of (SMeEt)[Pd(dmit)] (7) and the possible origin of the metal-insulator transition at 150 K are discussed on the basis of tight-binding band structure calculations.
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