Synthesis,structure and physical properties of nickel bis(dithiolene) complexes with different cations

A series of new complexes of multi-sulfur 1,2-dithiolene ligands, [Ru(bipy)₃][Ni(L)₂]₂ (bipy?=?2,2′-bipyridine; L?=?pddt (6,7-dihydro-5H-1,4-dithiepin-2,3-dithiolate), dddt (5,6-dihydro-1,4-dithiin-2,3-dithiolate)), have been synthesized and characterized. One typical complex, [Ru(bipy)₃][Ni(pddt)₂]₂·2H₂O (1), crystallized in an acentric space group of P2₁2₁2₁, with the cell dimensions of a?=?8.634(1), b?=?14.560(1), c?=?49.889(5)?Å, α?=?β?=?γ?=?90°, and Z?=?4. It consists of alternating columns of cations and anions along the a direction. The structure was refined by full matrix least squares methods to R ₁?=?0.0340, wR ₂?=?0.0670. Magnetic studies on [Ph₂Cr][Ni(dddt)₂] are also reported.     

[Ni(NN)(SS)]混配配合物的合成与性质

Four new complexes of the general formula [Ni(SS)(NN)], Where SSis dddt (5,6-dihydro-1,4-dithiin-2,3-dithiolate) or pddt(6,7-dihydro-5H-1,4-dithiepin-2,3-dithiolate) and NNis bpy or phen were prepared. The UV/Vis.Spectra exhibit intense intramolecular ligand-to-ligand charge transfer bands ca.600 nm.Cyclic voltammetry shows a reversible oxidation step assigned to [Ni(SS)(NN)]⁰=[Ni(SS)(NN)]⁺. When the complex [Ni(dddt)(bpy)] was partially oxidized by I₂, a broad ESRsignal at g=2.003 appeared.     

Comparison of density functionals for the study of the high spin low spin gap in Fe(III) spin crossover complexes

A detailed investigation of the accuracy of different quantum mechanical methods for the study of iron(III) spin crossover complexes is presented. The energy spin state gap between the high and low spin states; ΔE (HS‐LS) of nine iron(III) quinolylsalicylaldiminate complexes were calculated with nine different DFT functionals, then compared. DFT functionals: B3LYP, B3LYP‐D3, B3LYP*, BH&HLYP, BP86, OLYP, OPBE, M06L, and TPSSh were tested with six basis sets: 3‐21G*, dgdzvp, 6‐31G**, cc‐pVDZ, Def2TZVP, and cc‐pVTZ. The cations from the X‐ray crystal structures of [Fe(qsal‐OMe)₂]Cl·MeCN·H₂O, [Fe(qsal‐OMe)₂]Cl·2MeOH·0.5H₂O, [Fe(qsal‐OMe)₂]BF₄·MeOH, [Fe(qsal‐OMe)₂]NCS·CH₂Cl₂, [Fe(qsal‐F)₂]NCS, [Fe(qsal‐Cl)₂]NCS·MeOH, [Fe(qsal‐Br)₂]NCS·MeOH, [Fe(qsal‐I)₂]OTf·MeOH, and [Fe(qsal)₂]NCS?CH₂Cl₂ were used as starting structures. The results show that B3LYP, B3LYP‐D3, OLYP, and OPBE with a 6‐31G**, Def2TZVP, and cc‐pVTZ basis set give reasonable results of ΔE (HS‐LS) compared with the experimental data. The enthalpy of [Fe(qsal‐I)₂]⁺ calculated with an OLYP functional and cc‐pVTZ basis set (1.48 kcal/mol) most closely matches the experimental data (1.34 kcal/mol). B3LYP* yields an enthalpy of 5.92 kcal/mol suggesting it may be unsuitable for these Fe(III) complexes, mirroring recent results by Kepp (Inorg . Chem ., 2016, 55 , 2717–2727).     

Synthesis, structure, and electroconductivity of new radical cation salt [Pd(dddt)2]2GaBr4

A new radical cation salt based on the dithiolate complex Pd(dddt)₂ (dddt=5,6-dihydro-1,4-dithiine-2,3-dithiolate) with the tetrahedral anion [GaBr₄]^? was synthesized. The crystal and molecular structure was determined by XRD analysis. The crystal structure of the salt contains Pd(dddt)₂ cation layers alternating with layers of [GaBr₄]^? anions along thec axis of the unit cell. The cation layers contain stacks of Pd(dddt)₂, with a Pd...Pd distance of 3.011 Å. The electroconductivity of [Pd(dddt)₂]₂GaBr₄, single crystals at room temperature is 0.25 Ohm^?1 cm^?1 and decreases with temperature decrease, the activation energy beingE _a=0.66 eV.     

A chromium(III) bis-acetylide complex containing a trans-diethyl-ethylenedithio-substituted tetrathiafulvalene (TTF) derivative: synthesis,crystal structures,and magnetic properties

A new Cr(III) bis-acetylide complex containing redox-active ethynyl-substituted 4-methyl-4′,5′-trans-diethyl-ethylenedithio-tetrathiafulvalene, [Cr(III)cyclam(C≡C-MeEt₂EDT-TTF)₂]ⁿ⁺ ([1]ⁿ⁺) was synthesized. The crystal structures of two salts, [1][Ni(dmit)₂] (dmit?=?2-thioxo-1,3-dithiole-4,5-dithiolate) and [1][Ni(mnt)₂]₃ (mnt?=?maleonitriledithiolate), were determined by single-crystal X-ray diffraction. In the crystal of [1][Ni(dmit)₂], the trans-diethyl group of [1]⁺ is in the axial position and prevents π-stacking of the TTF units, resulting in a negligibly weak spin–spin interaction between Cr³⁺ and [Ni(dmit)₂]^?. In contrast, in [1][Ni(mnt)₂]_3, the trans-diethyl group is in the equatorial position in [1][Ni(mnt)₂]₃ owing to the strong attractive force between the π-stacked TTF⁺ units and the [Ni(mnt)₂]^? anions. This π-stacking has a significant effect on the magnetic property of [1] [Ni(mnt)₂]₃. The π-stacked TTF⁺ units and [Ni(mnt)₂]^? anions behave approximately as a one-dimensional S?=?1/2 antiferromagnetic chain connecting the spins of Cr³⁺ antiferromagnetically.

     

Crystal Structures and Magnetic Properties of Charge-Transfer Salts: Cobaltocenium Bis(cis 1,2-diphenylethene-1,2-dithiolato)metalates (Metal = Ni,Pd, Pt)

Charge-transfer salts [Co(C₅H₅)₂][M(dpt)₂] (M = Ni and Pt; dpt = cis-1,2-diphenylethene-1,2-dithiolate) were synthesized and crystallographically characterized. [Co(C₅H₅)₂][Ni(dpt)2] crystallizes in the monoclinic space group C2/c with a = 25, 607(3) Å, b = 9.4151(11) Å, c = 14.407(4) Å, β = 101.373(22)°, V = 3405.3(10) Å₃ and Z = 4. [Co(C₅H₅)₂][Pt(dpt)₂] belongs to the triclinic space group $ {\rm P}\bar 1 $ with a = 9.4666(11) Å, b = 13.9869(12) Å, c = 14.2652(9) Å, α = 99.983(6)°, β = 90.034(7)°, γ = 109.751(7)°, V = 1747.2(3) ų and Z = 2. Both structures consist of ··· D⁺A^?D⁺A^?D⁺A^? ··· linear chains with the local C₅ axis of the eclipsed [Co(C₅H₅)₂]⁺ cation parallel to the best MS₄ plane of the [M(dpt)₂]^? anion. Magnetic susceptibility measurements show that χ_M T values of the complexes [Co(C₅H₅)₂][M(dpt)₂] (M = Ni, Pd, and Pt) remain nearly constant in the temperature range 15–300 K, but decrease rapidly with further decreasing of temperature, indicating weak antiferromagnetic interactions at low temperatures.     

Synthesis, structures, and magnetic properties of carboxylate-bridged trinuclear complexes based on low-spin manganese(III)/iron(III) building blocks

Four linear trinuclear transition metal complexes have been prepared and characterized. The complexes [M^II(MeOH)₄][Fe^III(L)₂]₂·2MeOH (M = Fe (1) or Ni (2)), [Co^II(EtOH)₂(H₂O)₂][Fe^III(L)₂]₂·2EtOH (3), and [Mn^II(phen)₂][Mn^III(L)₂]₂·4MeOH (4) (H₂L = ((2-carboxyphenyl)azo)-benzaldoxime, phen = 1,10-phenanthroline) possesses a similar syn–anti carboxylate-bridged structure. The terminal Fe(III) or Mn(III) ions are low spin, and the central M(II) ions are high spin. Magnetic measurements show that antiferromagnetic interactions were present between the adjacent metal ions via the syn–anti carboxylate bridges. The antiferromagnetic coupling between low-spin Fe(III) and Ni(II) is unusual, which has been tentatively assigned to the structural distortion of Fe(III).     

Preparation and properties of [PtII(SS)(NN)]-type complexes and their iodine-doped analogues

Summary Complexes of the general formula [Pt(SS) (NN)], where SS is dddt (5,6-dihydro-1,4-dithiin-2,3-dithiolate) or pddt (6,7-dihydro-5H-1,4-dithiepin-2,3-dithiolate) and NN is bipy (2,2-bipyridine) or phen (1,10-phenanthroline), were prepared by the reaction of [PtCl₂(NN)] with dithiolate ligands. The¹H-n.m.r. spectra shows upfield shifts in the bipy or phen signals upon substitution of the chlorides in [PtCl₂(bipy)] or [PtCl₂(phen)] by dddt or pddt. The u.v.-vis. spectra exhibits intense intramolecular ligand-to-ligand charge transfer bands ca. 600 nm. Cyclic voltammograms show a reversible oxidation step, assigned to [Pt(SS) (NN)]⁰/[Pt(SS)(NN)]⁺. When the complexes were partially oxidized by I₂, two broad e.s.r. signals atg = 1.91,g = 2.02 appeared. Raman spectra show the presence of I ₃ ^– and I^5/– in the iodine-doped complexes. The electrical conductivities of the neutral mixed ligand complexes (10^–9-10^–10S cm^–1) are raised to 10^–7–10^–8S cm^–1 by I₂ doping.     

Synthesis,crystal structures and magnetic properties of two iron (II) tris(pyridyl)phosphine selenides complexes

We reported the synthesis of tris(pyridyl)phosphine selenide (TppSe) and tris(4-methylpyridin-2-yl)phosphine selenide (MeTppSe), which were prepared by a simple and straightforward one-pot method with red phosphorus in a KOH/DMSO suspension, and treatment of resulted phosphines with selenium in hot toluene. These compounds were characterized by mass spectroscopy, ¹H, ¹³C and ³¹P NMR spectroscopies and the structure of MeTppSe was characterised by a single-crystal X-ray diffraction. Furthermore, The reactions of selenides with Fe(ClO₄)₂·6H₂O afforded two new iron(II) mononuclear metal complexes [Fe(TppSe)₂][ClO₄]₂·3DMF (1) and [Fe(MeTppSe)₂][ClO₄]₂·2DMF (2). Detailed structural analyses and magnetic susceptibility measurements confirm no spin transition from low-spin to the high-spin state between 2 and 300 K in two iron(II) complexes.     

Über die Kristallstrukturen der Cyanokomplexe [Co(NH3)6][Fe(CN)6], [Co(NH3)6]2[Ni(CN)4]3 · 2 H2O und [Cu(en)2][Ni(CN)4]

On the Crystal Structures of the Cyano Complexes [Co(NH₃)₆][Fe(CN)₆], [Co(NH₃)₆]₂[Ni(CN)₄]₃ · 2 H₂O, and [Cu(en)₂][Ni(CN)₄] Of the three title compounds X‐ray structure determinations were performed with single crystals. [Co(NH₃)₆][Fe(CN)₆] (a = 1098.6(6), c = 1084.6(6) pm, R3, Z = 3) crystallizes with the CsCl‐like [Co(NH₃)₆][Co(CN)₆] type structure. [Co(NH₃)₆]₂[Ni(CN)₄]₃ · 2 H₂O (a = 805.7(5), b = 855.7(5), c = 1205.3(7) pm, α = 86.32(3), β = 100.13(3), γ = 90.54(3)°, P1, Z = 1) exhibits a related cation lattice, the one cavity of which is occupied by one anion and 2 H₂O, whereas the other contains two anions parallel to each other with distance Ni…Ni: 423,3 pm. For [Cu(en)₂][Ni(CN)₄] (a = 650.5(3), b = 729.0(3), c = 796.5(4) pm, α = 106.67(2), β = 91.46(3), γ = 106.96(2)°, P1, Z = 1) the results of a structure determination published earlier have been confirmed. The compound is weakly paramagnetic and obeys the Curie‐Weiss law in the range T < 100 K. The distances within the complex ions of the compounds investigated (Co–N: 195.7 and 196.4 pm, Ni–C: 186.4 and 186.9 pm, resp.) and their hydrogen bridge relations are discussed.     

CpNi(dithiolene)] (and diselenolene) neutral radical complexes

Various preparations of the neutral radical [CpNi(dddt)] complex (dddt = 5,6-dihydro-1,4-dithiin-2,3-dithiolate) were investigated with CpNi sources, [Cp2Ni], [Cp2Ni](BF4), [CpNi(CO)]2, and [CpNi(cod)](BF4), and dithiolene transfer sources, O=C(dddt), the naked dithiolate (dddt(2-)), the monoanion of square-planar Ni dithiolene complex (NBu4)[Ni(dddt)2], and the neutral complex [Ni(dddt)2]. The reaction of [CpNi(cod)](BF4) with (NBu4)[Ni(dddt)2] gave the highest yield for the preparation of [CpNi(dddt)] (86%). [CpNi(ddds)] (ddds = 5,6-dihydro-1,4-dithiin-2,3-diselenolate), [CpNi(dsdt)] (dsdt = 5,6-dihydro-1,4-diselenin-2,3-dithiolate), [CpNi(bdt)] (bdt = 1,2-benzenedithiolate), and [CpNi(bds)] (bds = 1,2-benzenediselenolate) were synthesized by the reactions of [Cp2Ni] with the corresponding neutral Ni dithiolene complexes [Ni(ddds)2]2, [Ni(dsdt)2], [Ni(bdt)2], and [Ni(bds)2], respectively. The five, formally Ni(III), radical complexes oxidize and reduce reversibly. They exhibit, in the neutral state, a strong absorption in the NIR region, from 1000 nm in the dddt/ddds/dsdt series to 720 nm in the bdt/bds series with epsilon values between 2500 and 5000 M(-1) cm(-1). The molecular and solid state structures of the five complexes were determined by X-ray structure analyses. [CpNi(dddt)] and [CpNi(ddds)] are isostructural, while [CpNi(dsdt)] exhibits a closely related structure. Similarly, [CpNi(bdt)] and [CpNi(bds)] are also isostructural. Correlations between structural data and magnetic measurements show the presence of alternated spin chains in [CpNi(dddt)], [CpNi(ddds)], and [CpNi(dsdt)], while a remarkably strong antiferromagnetic interaction in [CpNi(bdt)] and [CpNi(bds)] is attributed to a Cp...Cp face-to-face sigma overlap, an original feature in organometallic radical complexes.     

Two spin systems based on [Ni(dmit)2]− building blocks exhibiting 1-D chain and 2-D sheet structures: crystal structures and magnetic properties

The crystal structures and magnetic properties for two ion-pair complexes, [MG][Ni(dmit)₂] (1) and [RhB][Ni(dmit)₂] (2) (MG⁺ = N-(4-((4-(dimethylamino)phenyl)(phenyl)methylene)cyclohexa-2,5-dienylidene)-N-methylmethanaminium, RhB⁺ = 9-(2-carboxyphenyl)-3,6-bis(diethylamino)xanthylium; dmit^2? = 1,3-dithiole-2-thione-4,5-dithiolate), have been investigated. Complex 1 crystallizes in the monoclinic space group P2₁/c, the stacking interactions between the GM⁺ and [Ni(dmit)₂]^? lead to the anion exhibiting a banana-shaped molecular geometry; the neighboring anions form a 1-D alternating chain along the crystallographic [1 1 0] direction via intermolecular lateral-to-lateral and head-to-head S ··· S contacts. The temperature dependence of magnetic susceptibility from 2–350 K does not display the magnetic character of a 1-D chain; the magnetic susceptibility data were fit to the Curie–Weiss equation to give C = 0.351(15) emu K mol^?1, θ = ?3.51(28) K, and χ ₀ = 8.00(3) × 10^?5 emu mol^?1. Complex 2 belongs to the triclinic space group P-1 with two crystallographic inequivalent [Ni(dmit)₂]^? anions, which exhibit perfect planar geometry. Two ethyl groups of RhB⁺ are disordered over two positions at 296 K, and one becomes ordered at 150 K. The [Ni(dmit)₂]^? anions form a 2-D molecular layer via intermolecular lateral-to-lateral and head-to-lateral S ··· S interactions with the anionic layer parallel to the crystallographic (0 1 ?1) plane. The temperature variation of magnetic susceptibility from 2 to 350 K shows that antiferromagnetic coupling dominates in the anionic layer, and the disorder–order changes of cationic structure are not coupled to magnetic property.     

[Au(Et2dtc)2][TcNCl4] – Darstellung und Struktur

[Au(Et₂dtc)₂][TcNCl₄] – Synthesis and Structure [Au(Et₂dtc)₂][TcNCl₄] (Et₂dtc^– = N,N‐diethyldithiocarbamate) is formed by the reaction of [Au(CO)Cl] with [TcN(Et₂dtc)₂] in dichloromethane. The solid state structure of the compound is characterized by a large triclinic unit cell (space group, P1, a = 9.422(2), b = 22.594(5), c = 32.153(7) Å, α = 72.64(1), β = 85.19(1), γ = 86.15(1)°, Z = 12) and shows an unusual arrangement due to long‐range contacts between the technetium atoms and sulfur atoms of the [Au(Et₂dtc)₂]⁺ units (3.45–3.56 Å) which assemble two anions and one cation to {[TcNCl₄][Au(Et₂dtc)₂] · [TcNCl₄]}^– moieties.     

First heterobimetallic MnII/MII(M = Cu,Ni) complexes with open-chain aliphatic schiff-base ligands obtained by direct template synthesis

Four new heterobimetallic complexes [CuL¹][MnCl₄] (1), [CuL²][MnCl₄] (2), [NiL¹][MnCl₄] (3), [NiL²][MnCl₄] (4) (L¹?=?4,6,6-trimethyl-1,9-diamino-3,7-di-aza-nona-3-ene; L²?=?1,15-dihydroxy-7,9,9-trimethyl-3,6,10,13-tetra-aza-pentadeca-6-ene) have been prepared from elemental metals, ethylenediamine dihydrochloride or its N-(2-hydroxyethyl) derivative and acetone by the template condensation reaction. All complexes have been characterized by elemental analysis, IR and UV-Visible spectroscopy. The structures of 2 and 3 have been determined by X-ray crystallography (2: Orthorhombic, Pna2 _1, a?=?20.136(4), b?=?11.185(2), c?=?10.251(2)Å, Z?=?4; 3: Orthorhombic, Pca2 _1, a?=?14.335(2), b?=?11.405(2), c?=?11.154(2)Å, Z?=?4 ). Both crystals consist of alternating complex cations [ML]²⁺ and anions [MnCl₄]^2? linked together by N–H···Cl–Mn and O–H···Cl–Mn hydrogen bonds forming 2D corrugated sheets in (2) and 1D helical chains in (3). Complex 2 represents the first single crystal structure elucidation of the complex containing L².     

The Spin Gap Transition around 180 K Observed in a New Molecular Magnet based on the [Ni(mnt)2]– Monoanion and Substituted Benzylpyridinium

A new molecular magnet, [NO₂BrBzPyCH₃][Ni(mnt)₂] ( 1 ) ([NO₂BrBzPyCH₃]⁺ = 1‐(2′‐bromo‐4′‐nitrobenzyl)‐2‐methylpyridinium, and mnt^2– = maleonitriledithiolate), has been prepared and characterized by single crystal X‐ray diffraction and magnetic measurements. The Ni(III) ions of 1 form a quasi‐one‐dimensional alternating zig‐zag magnetic chain within a Ni(mnt)₂^– column by intermolecular Ni···S, Ni···Ni or π···π interactions, and the [NO₂BrBzPyCH₃]⁺ cations stack into a column via weak Br···O interaction, p···π stacking interactions and C‐H···O hydrogen bonds between the cations. Magnetic susceptibility measurements in the temperature range 1.8‐300 K show that 1 exhibits a spin‐gap transition around 180 K, and an antiferromagnetic interaction in the high‐temperature phase (HT) and spin gap behavior in the low‐temperature phase (LT). The transition for 1 is a second‐order phase transition as determined by DSC analyses.     

Cyano-bridged heterometallic complexes directed by binuclear copper units

A tridentate N,O-donor, 1,3-bis(3,5-dimethylpyrazol-1-yl)propan-2-ol (HL), has been employed to synthesize cyano-bridged complexes and six heterometallic complexes with [Cu₂L₂] or [Cu₂L₂(H₂O)] have been generated by using slow diffusion. With slightly different synthetic conditions, subtle variations in the crystal structures of the complexes occur. [Cu₂L₂][Fe(CN)₅NO]?2CH₃CN (1) and [Cu₂L₂][Fe(CN)₅NO]?H₂O (2), synthesized in different solvents with the same precursor, exhibit a very similar 1-D zig-zag chain motif in different space groups, P2₁ and P-1, respectively. Similarly, [Cu₂L₂(H₂O)][Ni(CN)₄]·H₂O (3) and [Cu₂L₂][Ni(CN)₄]?H₂O (4), synthesized with different diffusion methods, feature trinuclear and 1-D zig-zag chain structures, which indicates a solvent effect of water. [Cu₂L₂(H₂O)]₂[Cu₂L₂][W(CN)₈]₂·8H₂O (5) is composed of two [W(CN)₈]^3? and three [Cu₂L₂]²⁺ units. In the octanuclear structure, [W(CN)₈]^3? and one [Cu₂L₂]²⁺ bridge and the other two [Cu₂L₂]²⁺ are terminal to stop extending the 1-D structure. [CuL][Ag_2.24Cu_0.76(CN)₄] (6) exhibits a discrete structure, in which the complex anion forms a unique 2-D 6³ network and the complex cations are inserted in the space between two adjacent networks. Magnetic properties of 1 and 4 are discussed.     

A New Paramagnetic Pd(dmit)2 Salt: Tris(2,2′-Bipyridine)Nickel(II) Bis(1,3-Dithiole-2-Thione-4,5-Dithiolato)Palladate(II) Mono-Acetonitrile; [Ni(bpy)3][Pd(dmit)2]·CH3CN

Combination of the [Ni(bpy)₃]²⁺ cation complex and the [Pd(dmit)₂]⁻ anion (dmit=C₃S₅²⁻=1,3-dithiole-2thione-4,5-dithiolate) has resulted in the paramagnetic [Ni(bpy)₃][Pd(dmit)₂]·CH₃CN compound, a suitable precursor for a molecular magnetic conductor. Its crystal structure consists of a Pd(dmit)₂ anion arrangement that is quite different from segregated stack layers often found for M(dmit)₂−based compounds. The reduction of the [Pd(dmit)₂]^- to the 2− charged anion in the title compound most probably is the result of a charge disproportionation between Pd(dmit)₂ anions.     

[M(phen)3][Ni(mnt)2](M2+=Ni2+，Fe2+；phen=1，10-菲咯啉，mnt2-=马来二腈二硫烯)离子对配合物的合成、晶体结构、电子光谱和磁性质

本文制备了2种新的离子对配合物[M(phen)3][Ni(mnt)2](phen=1,10-菲咯啉,mnt2-=马来二腈二硫烯;M2+=Ni2+,1;Fe2+,2),并进行了结构表征。2种离子对配合物晶体的空间群都为P21/n,具有类似的晶胞参数和堆积结构。紫外可见-近红外光谱显示在近红外区域没有出现明显的吸收峰。在2到400 K的温度范围内,化合物1表现居里-外斯型的顺磁性行为,并在磁性[Ni(phen)3]2+离子之间存在弱的反铁磁作用,而且在八面体配位环境下Ni2+离子自旋基态S=1。化合物2在40 K向上显示抗磁性,意味[Fe(phen)3]2+离子处于低自旋态。低于40 K时,弱居里尾巴可能是由于小部分顺磁性[Ni(mnt)2]-杂质导致的。     

Molecular Conductors Based on M(dddt)2 Bisdithiolene Cation Complexes

The synthesis, structure and properties of molecular conductors based on M(dddt)₂ cation complexes (dddt = 5,6-dihydro-1,4-dithiin-2,3-dithiolate) which are metal complex analogs of bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF or ET) salts are considered. Formally, the central C=C bond of ET is substituted by a metal ion in the M(dddt)₂ complexes. The effect of metal (M=Ni, Pt, Pd) and counterion on crystal structure and conducting properties of M(dddt)₂ complexes is analyzed. The similarity and distinction in structures and properties of M(dddt)₂ and ET salts are discussed.     

Koordinationspolymere 1, 2‐Dithiooxalato‐ und 1, 2‐Dithioquadratato‐Komplexe. Synthese und Strukturen von [BaCr2(bipy)2(1, 2‐dtox)4(H2O)2], [Ni(cyclam)(1, 2‐dtsq)]·2DMF, [Ni(cyclam)Mn(1, 2‐dtsq)2(H2O)2]·2H2O und [H3O][H5O2][Cu(cyclam)]3[Cu2(1, 2‐dtsq)3]2

Coordination Polymeric 1, 2‐Dithiooxalato and 1, 2‐Dithiosquarato Complexes. Syntheses and Structures of [BaCr₂(bipy)₂(1, 2‐dtox)₄(H₂O)₂], [Ni(cyclam)(1, 2‐dtsq)]·2DMF, [Ni(cyclam)Mn(1, 2‐dtsq)₂(H₂O)₂]·2H2₂, and [H₃O][H₅O₂][Cu(cyclam)]₃[Cu₂(1, 2‐dtsq)₃]₂ 1, 2‐Dithioxalate and 1, 2‐dithiosquarate ions have a pair of soft and hard donor centers and thus are suited for the formation of coordination polymeric complexes containing soft and hard metal ions. The structures of four compounds with building blocks containing these ligands are reported: In [BaCr₂(bipy)₂(1, 2‐dtox)₄(H₂O)₂] Barium ions and pairs of Cr(bipy)(1, 2‐dtox)₂ complexes form linear chains by the bisbidentate coordination of the dithiooxalate ligands towards Ba²⁺ and Cr³⁺. In [Ni(cyclam)(1, 2‐dtsq)]·2DMF short NÖH···O hydrogen bonds link the NiS₂N₄‐octahedra with C_2v‐symmetry to an infinite chain. In [Ni(cyclam)Mn(1, 2‐dtsq)₂(H₂O)₂]·2H₂O the 1, 2‐dithiosquarato ligand shows a rare example of S‐coordination towards manganese(II). The sulfur atoms of cis‐MnO₂S₄‐polyedra are weakly coordinated towards the axial sites of square‐planar NiN₄‐centers, thus forming a zig‐zag‐chain of Mn···Ni···Mn···Ni polyhedra. [H₃O][H₅O₂][Cu (cyclam)]₃[Cu₂(1, 2‐dtsq)₃]₂ contains square planar [Cu^II(cyclam)]²⁺ ions and dinuclear [Cu^I₂(1, 2‐dtsq)₃]^4— ions. Here each copper atom is trigonally planar coordinated by S‐donor atoms of the ligands. The Cu…Cu distance is 2.861(4)Å.