Syntheses and Structures of New Rare‐Earth Metal Tetracyanidoborates

Six new rare‐earth metal tetracyanidoborates were prepared and characterized by single‐crystal X‐ray diffraction. Crystals of these salts contain co‐crystallized solvent molecules, such as water, acetone, ethanol, or diethyl ether. In [La(EtOH)₃(H₂O)₂{B(CN)₄}₃] ( 1 ), [La(EtOH)(H₂O)₄{B(CN)₄}₃] · Et₂O ( 2 ), and [Y(EtOH)(H₂O)₄{B(CN)₄}₃] · EtOH ( 6 ) the tetracyanidoborate anions are all or in part bonded to the RE³⁺ ions, whereas in [Pr(H₂O)₉][B(CN)₄]₃ · (CH₃)₂CO ( 3 ), [Er(H₂O)₈][B(CN)₄]₃ · (CH₃)₂CO ( 4 ), and [Lu(EtOH)(H₂O)₇][B(CN)₄]₃ · EtOH · 0.5H₂O ( 5 ) the [B(CN)₄]^– anions are not coordinated to the central metal atoms. Only in 1 , one of the three crystallographically independent [B(CN)₄]^– anions acts as a bridging ligand.     

Scandium complexes with the tetraphenylethylene and anthracene dianions

The structural study of Sc complexes containing dianions of anthracene and tetraphenylethylene should shed some light on the nature of rare‐earth metal–carbon bonding. The crystal structures of (18‐crown‐6)bis(tetrahydrofuran‐κO)sodium bis(η⁶‐1,1,2,2‐tetraphenylethenediyl)scandium(III) tetrahydrofuran disolvate, [Na(C₄H₈O)₂(C₁₂H₂₄O₆)][Sc(C₂₆H₂₀)₂]·2C₄H₈O or [Na(18‐crown‐6)(THF)₂][Sc(η⁶‐C₂Ph₄)₂]·2(THF), ( 1b ), (η⁵‐1,3‐diphenylcyclopentadienyl)(tetrahydrofuran‐κO)(η⁶‐1,1,2,2‐tetraphenylethenediyl)scandium(III) toluene hemisolvate, [Sc(C₁₇H₁₃)(C₂₆H₂₀)(C₄H₈O)]·0.5C₇H₈ or [(η⁵‐1,3‐Ph₂C₅H₃)Sc(η⁶‐C₂Ph₄)(THF)]·0.5(toluene), ( 5b ), poly[[(μ₂‐η³:η³‐anthracenediyl)bis(η⁶‐anthracenediyl)bis(η⁵‐1,3‐diphenylcyclopentadienyl)tetrakis(tetrahydrofuran)dipotassiumdiscandium(III)] tetrahydrofuran monosolvate], {[K₂Sc₂(C₁₄H₁₀)₃(C₁₇H₁₃)₂(C₄H₈O)₄]·C₄H₈O}_n or [K(THF)₂]₂[(1,3‐Ph₂C₅H₃)₂Sc₂(C₁₄H₁₀)₃]·THF, ( 6 ), and 1,4‐diphenylcyclopenta‐1,3‐diene, C₁₇H₁₄, ( 3a ), have been established. The [Sc(η⁶‐C₂Ph₄)₂]⁻ complex anion in ( 1b ) contains the tetraphenylethylene dianion in a symmetrical bis‐η³‐allyl coordination mode. The complex homoleptic [Sc(η⁶‐C₂Ph₄)₂]⁻ anion retains its structure in THF solution, displaying hindered rotation of the coordinated phenyl rings. The 1D ¹H and ¹³C{¹H}, and 2D COSY ¹H–¹H and ¹³C–¹H NMR data are presented for M[Sc(Ph₄C₂)₂]·xTHF [M = Na and x = 4 for ( 1a ); M = K and x = 3.5 for ( 2a )] in THF‐d₈ media. Complex ( 5b ) exhibits an unsymmetrical bis‐η³‐allyl coordination mode of the dianion, but this changes to a η⁴ coordination mode for (1,3‐Ph₂C₅H₃)Sc(Ph₄C₂)(THF)₂, ( 5a ), in THF‐d₈ solution. A ⁴⁵Sc NMR study of ( 2a ) and UV–Vis studies of ( 1a ), ( 2a ) and ( 5a ) indicate a significant covalent contribution to the Sc—Ph₄C₂ bond character. The unique Sc ate complex, ( 6 ), contains three anthracenide dianions demonstrating both a η⁶‐coordination mode for two bent ligands and a μ₂‐η³:η³‐bridging mode of a flat ligand. Each [(1,3‐Ph₂C₅H₃)₂Sc₂(C₁₄H₁₀)₃]²⁻ dianionic unit is connected to four neighbouring units via short contacts with [K(THF)₂]⁺ cations, forming a two‐dimensional coordination polymer framework parallel to (001).     

Hydrated hexacyanometallate(III) salts of triaqua(18‐crown‐6)lanthanoid(III) and tetraaqua(18‐crown‐6)lanthanoid(III) cations containing nine‐ and ten‐coordinate lanthanoids

Tetraaqua(18‐crown‐6)cerium(III) hexacyanoferrate(III) dihydrate, [Ce(C₁₂H₂₄O₆)(H₂O)₄][Fe(CN)₆]·2H₂O, and tetraaqua(18‐crown‐6)neodymium(III) hexacyanoferrate(III) dihydrate, [Nd(C₁₂H₂₄O₆)(H₂O)₄][Fe(CN)₆]·2H₂O, are isomorphous and isostructural in the C2/c space group, where the cations, which contain ten‐coordinate lanthanoid centres, lie across twofold rotation axes and the anions lie across inversion centres. In these compounds, an extensive series of O—H...O and O—H...N hydrogen bonds links the components into a continuous three‐dimensional framework. Triaqua(18‐crown‐6)lanthanoid(III) hexacyanoferrate(III) dihydrate, [Ln(C₁₂H₂₄O₆)(H₂O)₃][Fe(CN)₆]·2H₂O, where Ln = Sm, Eu, Gd or Tb, are all isomorphous and isostructural in the P space group, as are triaqua(18‐crown‐6)gadolinium(III) hexacyanochromate(III) dihydrate, [Gd(C₁₂H₂₄O₆)(H₂O)₃][Cr(CN)₆]·2H₂O, and triaqua(18‐crown‐6)gadolinium(III) hexacyanocobaltate(III) dihydrate, [Gd(C₁₂H₂₄O₆)(H₂O)₃][Co(CN)₆]·2H₂O. In these compounds, there are two independent anions, both lying across inversion centres, and the lanthanoid centres exhibit nine‐coordination; in the crystal structures, an extensive series of hydrogen bonds links the components into a three‐dimensional framework.     

Synthesis,Structure and Characterization of Dinuclear Pentacoordinate Molybdenum(V) Complexes with Thiosemicarbazone Ligands

New dinuclear pentacoordinate molybdenum(V) complexes, [Mo₂^VO₃L₂] [L = thiosemicarbazonato ligand: C₆H₄(O)CH:NN:C(S)NHR′ and C₁₀H₆(O)CH:NN:C(S)NHR′; R′ = H, CH₃, C₆H₅) were obtained either by oxygen atom abstraction from Mo^VIO₂L with triphenylphosphine or by using [Mo₂O₃(acac)₄] in the reaction with the corresponding ligands H₂L. Crystal and molecular structure of [Mo₂O₃{C₆H₄(O)CH:NN:C(S)NHC₆H₅}₂] · CH₃CN has been determined by the single‐crystal X‐ray diffraction method.     

Reductive nitrosylation of tetraoxometallates—XI. Molybdate hydroxylamine reaction in the presence of cyanide: Synthesis of mono- and dinitrosyl cyan

The new molybdenum cyanonitrosyl complexes, R₂[Mo(NO)(CN)₅]·2H₂O (R = Ph₄P and Bu₄N) and [Mo(NO)(CN)₃(L-L)]·H₂O [L-L =     

P−P Condensation and P−N/P−P Bond Metathesis: Facile Synthesis of Cationic Tri‐ and Tetraphosphanes

[L_C^RP((PhP)₂C₂H₄)][OTf] ( 4 a,b [OTf]) and [L_C^iPrP(PPh₂)₂][OTf] ( 5 b [OTf]) were prepared from the reaction of imidazoliumyl‐substituted dipyrazolylphosphane triflate salts [L_C^RP(pyr)₂][OTf] ( 3 a,b [OTf]; a : R=Me, b =iPr; L_C^R=1,3‐dialkyl‐4,5‐dimethylimidazol‐2‐yl; pyr=3,5‐dimethylpyrazol‐1‐yl) with the secondary phosphanes PhP(H)C₂H₄P(H)Ph) and Ph₂PH. A stepwise double P?N/P?P bond metathesis to catena‐tetraphosphane‐2,3‐diium triflate salt [(Ph₂P)₂(L_C^MeP)₂][OTf]₂ ( 7 a [OTf]₂) is observed when reacting 3 a [OTf] with diphosphane P₂Ph₄. The coordination ability of 5 b [OTf] was probed with selected coinage metal salts [Cu(CH₃CN)₄]OTf, AgOTf and AuCl(tht) (tht=tetrahydrothiophene). For AuCl(tht), the helical complex [{(Ph₂PPL_C^iPr)Au}₄][OTf]₄ ( 9 [OTf]₄) was unexpectedly formed as a result of a chloride‐induced P?P bond cleavage. The weakly coordinating triflate anion enables the formation of the expected copper(I) and silver(I) complexes [( 5 b )M(CH₃CN)₃][OTf]₂ (M=Cu, Ag) ( 10 [OTf]₂, 11 [OTf]₂).     

Synthesis and Chloride Affinity of Sterically Demanding Ditopic Lithium Bis(pyrazol‐1‐yl)borates

The synthesis and full characterization of the sterically demanding ditopic lithium bis(pyrazol‐1‐yl)borates Li₂[p‐C₆H₄(B(Ph)pz^R₂)₂] is reported (pz^R = 3‐phenylpyrazol‐1‐yl ( 3 ^Ph), 3‐t‐butylpyrazol‐1‐yl ( 3 ^tBu)). Compound 3 ^Ph crystallizes from THF as THF‐adduct 3 ^Ph(THF)₄ which features a straight conformation with a long Li···Li distance of 12.68(1) Å. Compound 3 ^tBu was found to function as efficient and selective scavenger of chloride ions. In the presence of LiCl it forms anionic complexes [ 3 ^tBuCl]⁻ with a central Li‐Cl‐Li core (Li···Li = 3.75(1) Å).     

(Ph4P)2[Be3(μ‐OH)3(H2O)6]Cl5: Kristallstruktur und DFT‐Rechnungen

Bis(tetraphenylphosphonium)‐tris(μ‐hydroxo)hexaaquatriberylliumpentachloride, (Ph₄P)₂[Be₃(μ‐OH)₃(H₂O)₆]Cl₅ ( 1 ), was surprisingly obtained by reaction of (Ph₄P)N₃ · n H₂O with BeCl₂ in dichloromethane suspension and subsequent crystallization from acetonitrile to give single crystals of composition 1· 5.25CH₃CN. According to the crystal structure determination space group P , Z = 2, lattice dimensions at 100 K: a = 1354.8(2), b = 1708.7(2), c = 1753.2(2) pm, α = 114.28(1)°, β = 94.80(1)°, γ = 104.51(1)°, R₁ = 0.0586] the [Be₃(μ‐OH)₃(H₂O)₆]³⁺ cations form six‐mem‐bered Be₃O₃ rings with boat conformation and distorted tetrahedrally coordinated beryllium atoms with the terminally coordinated H₂O molecules. The structure ist characterized by a complicated three dimensional hydrogen‐bridging network including O–H ··· O, O–H ··· Cl, and O–H ··· NCCH₃ contacts. DFT calculations result in nearly planar [Be₃(OH)₃] six‐membered ring conformations.     

Oxorhenium(V) Complexes with 1,3,4‐Triphenyl‐1,2,4‐triazol‐5‐ylidene

Reactions of the oxorhenium(V) complexes [ReOX₃(PPh₃)₂] (X = Cl, Br) with the N‐heterocyclic carbene (NHC) 1,3,4‐triphenyl‐1,2,4‐triazol‐5‐ylidene (L^Ph) under mild conditions and in the presence of MeOH or water give [ReOX₂(Y)(PPh₃)(L^Ph)] complexes (X = Cl, Br; Y = OMe, OH). Attempted reactions of the carbene precursor 5‐methoxy‐1,3,4‐triphenyl‐4,5‐dihydro‐1H‐1,2,4‐triazole ( 1 ) with [ReOCl₃(PPh₃)₂] or [NBu₄][ReOCl₄] in boiling xylene resulted in protonation of the intermediately formed carbene and decomposition products such as [HL^Ph][ReOCl₄(OPPh₃)], [HL^Ph][ReOCl₄(OH₂)] or [HL^Ph][ReO₄] were isolated. The neutral [ReOX₂(Y)(PPh₃)(HL^Ph)] complexes are purple, airstable solids. The bulky NHC ligands coordinate monodentate and in cis‐position to PPh₃. The relatively long Re–C bond lengths of approximate 2.1Å indicate metal‐carbon single bonds.     

Triphenylphosphane Oxide Complexes of Lanthanide Nitrates: Polymorphs and Photophysics

A series of mer‐[Ln(NO₃)₃(Ph₃PO)₃] complexes were prepared from Ln(NO₃)₃ · xH₂O and Ph₃PO in chloroform (Ln = La, Nd, Sm, Eu, Gd, Tb, Dy, and Er). The La and Nd complexes were 0.25 CHCl₃ solvates, whereas the others were solvent‐free. The identical reaction using Yb(NO₃)₃ · xH₂O produced the unique salt trans‐[Yb(NO₃)₂(Ph₃PO)₄][Yb(NO₃)₄(Ph₃PO)] · Et₂O. All nitrate ions in all complexes are η²‐chelating. A comparison of the various [Ln(NO₃)₃(Ph₃PO)₃] structures, including those in the literature, reveals at least four common polymorphs, each of which is represented by isomorphic structures of multiple Ln ions. Luminescence of mer‐[Ln(NO₃)₃(Ph₃PO)₃] (Ln = Y, La, Nd, Sm, Eu, Gd, Tb, and Dy), trans‐[Yb(NO₃)₂(Ph₃PO)₄][Yb(NO₃)₄(Ph₃PO)] and Ph₃PO assignments are reported. Latva's empirical rule allows for the antenna effect, in which energy is transferred from the triplet state of the Ph₃PO ligand, to occur only for Tb³⁺. Excitation via Ph₃PO results in strong green luminescence for Tb³⁺ having twice the intensity as that which results from direct excitation of the f‐f transitions.     

4‐Iodo­anilinium 3‐nitro­phthalate(1–): tripartite sheets built from O—H...O and N—H...O hydrogen bonds

In the title compound, 4‐iodoanilinium 2‐carboxy‐6‐nitrobenzoate, C₆H₇IN⁺·C₈H₄NO₆⁻, the anions are linked by an O—H...O hydrogen bond [H...O = 1.78 Å, O...O = 2.614 (3) Å and O—H...O = 171°] into C(7) chains, and these chains are linked by two two‐centre N—H...O hydrogen bonds [H...O = 1.86 and 1.92 Å, N...O = 2.700 (3) and 2.786 (3) Å, and N—H...O = 153 and 158°] and one three‐centre N—H...(O)₂ hydrogen bond [H...O = 2.02 and 2.41 Å, N...O = 2.896 (3) and 2.789 (3) Å, N—H...O = 162 and 105°, and O...H...O = 92°], thus forming sheets con­taining R(6), R(8), R(13) and R(18) rings.     

The in vitro antifungal activity of some dithiocarbamate organotin(IV) compounds on Candida albicans— a model for biological interaction of organotin complexes

The in vitro antifungal activity of the dithiocarbamate organotin complexes [Sn{S₂CN(CH₂)₄}₂Cl₂] ( 1 ), [Sn{S₂CN(CH₂)₄}₂Ph₂] ( 2 ), [Sn{S₂CN(CH₂)₄}Ph₃] ( 3 ), [Sn{S₂CN(CH₂)₄}₂n‐Bu₂] ( 4 ), [Sn{S₂CN(CH₂)₄}Cy₃] {Cy = cyclohexyl} ( 5 ), [Sn{S₂CN(C₂H₅)₂}₂Cl₂] ( 6 ), [Sn{S₂CN(C₂H₅)₂}₂Ph₂] ( 7 ), [Sn{S₂CN(C₂H₅)₂}Ph₃] ( 8 ), [Sn{S₂CN(C₂H₅)₂}₃Ph] ( 9 ) and [Sn{S₂CN(C₂H₅)₂}Cy₃] ( 10 ) has been screened against Candida albicans (ATCC 18804), Candida tropicalis (ATCC 750) and resistant Candida albicans collected from HIV‐positive Brazilian patients with oral candidiasis. All compounds exhibited antifungal activities and complexes 3 and 8 displayed the best results. We have investigated the effect of compounds 1–10 on the cellular activity of the yeast cultures. Changes in mitochondrial function have not been detected. However, all drugs reduced ergosterol biosynthesis. Preliminary studies on DNA integrity indicated that the compounds do not cause gross damage to yeast DNA. The data suggest that these compounds share some mechanisms of action on cell membranes similar to that of polyene but not with azole drugs, normally used in Candida infections. Copyright © 2008 John Wiley & Sons, Ltd.     

Synthesis,Crystal Structures and Magnetic Properties of Ion-Pair Complexes with Hydrogen Bonding Network: Ln(DMA)n(H2O)m Cr(CN)6· xH2O(Ln = Sm,Gd: n = 4, m = 3, x = 2; Ln = Er: N = 3, m = 4, x = 0)

Three ion-pair Ln-Cr complexes [Sm(DMA)₄(H₂O)₃][Cr(CN)₆] · 2H₂O, [Gd(DMA)₃(H₂O)₄][Cr(CN)₆] · 2H₂O and [Er(DMA)₃(H₂O)₄][Cr(CN)₆] (DMA = dimethylacetamide) have been synthesized. X-ray structure analyses of the title complexes revealed that there is a hydrogen-bonding network through CN groups and H₂O molecules. Variable temperature magnetic susceptibilities indicate weak antiferromagnetic interactions between cation and anion pairs moderated through the hydrogen bonding network.     

Ligand Substitution Reactions on Aquapentachloro‐ and Hexachloroplatinic Acid — Synthesis and Characterization of Tetrachloroplatinum(IV) Complexes with Heterocyclic N,N Donors

Reactions of aquapentachloroplatinic acid, (H₃O)[PtCl₅(H₂O)]·2(18C6)·6H₂O ( 1 ) (18C6 = 18‐crown‐6), and H₂[PtCl₆]·6H₂O ( 2 ) with heterocyclic N, N donors (2, 2′‐bipyridine, bpy; 4, 4′‐di‐tert‐butyl‐2, 2′‐bipyridine, tBu₂bpy; 1, 10‐phenanthroline, phen; 4, 7‐diphenyl‐1, 10‐phenanthroline, Ph₂phen; 2, 2′‐bipyrimidine, bpym) afforded with ligand substitution platinum(IV) complexes [PtCl₄(N∩N)] (N∩N = bpy, 3a ; tBu₂bpy, 3b ; Ph₂phen, 5 ; bpym, 7 ) and/or with protonation of N, N donor yielding (R₂phenH)₂[PtCl₆] (R = H, 4a ; Ph, 4b ) and (bpymH)⁺ ( 8 ). With UV irradiation Ph₂phen and bpym reacted with reduction yielding platinum(II) complexes [PtCl₂(N∩N)] (N∩N = Ph₂phen, 6 ; bpym, 9 ). Identities of all complexes were established by microanalysis as well as by NMR (¹H, ¹³C, ¹⁹⁵Pt) and IR spectroscopic investigations. Molecular structures of [PtCl₄(bpym)]·MeOH ( 7 ) and [PtCl₂(Ph₂phen)] ( 6 ) were determined by X‐ray diffraction analyses. Differences in reactivity of bpy/bpym and phen ligands are discussed in terms of calculated structures of complexes [PtCl₅(N∩N)]^— with monodentately bound N, N ligands (N∩N = bpy, 10a ; phen, 10b ; bpym, 10c ).     

Co(en)3[B4O5(OH)4]Cl·3H2O和[Ni(en)3][B5O6(OH)4]2·2H2O的合成、结构以及热力学性质

利用水热法合成了两种过渡金属配合物为模板剂的含水硼酸盐晶体Co(en)3[B4O5(OH)4]Cl·3H2O(1) 和 [Ni(en)3][B5O6(OH)4]2·2H2O (2),并通过元素分析、X射线单晶衍射、红外光谱及热重分析对其进行了表征。化合物1晶体结构的主要特点是在所有组成Co(en)33+, [B4O5(OH)4]2–, Cl– 和 H2O之间通过O–H…O、O–H…Cl、N–H…Cl和N–H…O四种氢键连接形成网状超分子结构。化合物2晶体结构的特点是[B5O6(OH)4]–阴离子通过O–H…O氢键连接形成沿a方向有较大通道的三维超分子骨架,模板剂[Ni(en)3]2+阳离子和结晶水分子填充在通道中。     

Synthesis and structural characterization of diorganotin(IV) complexes with 2,6‐pyridinedicarboxylic acid

Two new diorganotin(IV) derivatives of 2,6‐pyridinedicarboxylic acid, {[Ph₂Sn(2,6‐C₅H₃N)(COO)₂][Na(2,6‐C₅H₃N)(COOH) (COO)(CH₃OH)₂]} ( 1 ) and [Me₂Sn(2,6‐C₅H₃N)(COO)₂(H₂O)]^•H₂O ( 2 ) were synthesized by the reaction of Ph₃SnCl and PhMe₂SnI with 2,6‐pyridinedicarboxylic acid, respectively in the presence of sodium methoxide or potassium iso‐propoxide. The prepared compounds were characterized by mass spectrometry, IR, ¹H, ¹³C and ¹¹⁹Sn NMR spectroscopies. The molecular structures of both complexes were determined by a single‐crystal X‐ray analysis. The X‐ray structure revealed pentagonal bipyramidal geometry around the tin atom for compound 1, which is incorporated with a hexacoordinated monosodium derivative of 2,6‐pyridinedicarboxylic acid. Complex 2 adopts a monomeric structure with two carboxylate oxygen atoms coordinated to tin in monodenate form from equatorial positions, and the coordination number is raised to six as the oxygen of water and pyridine nitrogen occupies the other equatorial positions of octahedron. Copyright © 2007 John Wiley & Sons, Ltd.     

P−P Condensation and P−N/P−P Bond Metathesis: Facile Synthesis of Cationic Tri- and Tetraphosphanes

[L_C^RP((PhP)₂C₂H₄)][OTf] ( 4 a,b [OTf]) and [L_C^iPrP(PPh₂)₂][OTf] ( 5 b [OTf]) were prepared from the reaction of imidazoliumyl-substituted dipyrazolylphosphane triflate salts [L_C^RP(pyr)₂][OTf] ( 3 a,b [OTf]; a : R=Me, b =iPr; L_C^R=1,3-dialkyl-4,5-dimethylimidazol-2-yl; pyr=3,5-dimethylpyrazol-1-yl) with the secondary phosphanes PhP(H)C₂H₄P(H)Ph) and Ph₂PH. A stepwise double P−N/P−P bond metathesis to catena-tetraphosphane-2,3-diium triflate salt [(Ph₂P)₂(L_C^MeP)₂][OTf]₂ ( 7 a [OTf]₂) is observed when reacting 3 a [OTf] with diphosphane P₂Ph₄. The coordination ability of 5 b [OTf] was probed with selected coinage metal salts [Cu(CH₃CN)₄]OTf, AgOTf and AuCl(tht) (tht=tetrahydrothiophene). For AuCl(tht), the helical complex [{(Ph₂PPL_C^iPr)Au}₄][OTf]₄ ( 9 [OTf]₄) was unexpectedly formed as a result of a chloride-induced P−P bond cleavage. The weakly coordinating triflate anion enables the formation of the expected copper(I) and silver(I) complexes [( 5 b )M(CH₃CN)₃][OTf]₂ (M=Cu, Ag) ( 10 [OTf]₂, 11 [OTf]₂).     

Crystal Structures,Magnetic Properties and Catecholase‐Like Activities of μ‐Alkoxo‐μ‐Carboxylato Double Bridged Dinuclear and Tetranuclear Copper(II) Complexes

One μ‐alkoxo‐μ‐carboxylato bridged dinuclear copper(II) complex, [Cu₂(L¹)(μ‐C₆H₅CO₂)] ( 1 )(H₃L¹ = 1,3‐bis(salicylideneamino)‐2‐propanol)), and two μ‐alkoxo‐μ‐dicarboxylato doubly‐bridged tetranuclear copper(II) complexes, [Cu₄(L¹)₂(μ‐C₈H₁₀O₄)(DMF)₂]·H₂O ( 2 ) and [Cu₄(L²)₂(μ‐C₅H₆O₄]·2H₂O·2CH₃CN ( 3 ) (H₃L² = 1,3‐bis(5‐bromo‐salicylideneamino)‐2‐propanol)) have been prepared and characterized. The single crystal X‐ray analysis shows that the structure of complex 1 is dimeric with two adjacent copper(II) atoms bridged by μ‐alkoxo‐μ‐carboxylato ligands where the Cu···Cu distances and Cu‐O(alkoxo)‐Cu angles are 3.5 11 Å and 132.8°, respectively. Complexes 2 and 3 consist of a μ‐alkoxo‐μ‐dicarboxylato doubly‐bridged tetranuclear Cu(II) complex with mean Cu‐Cu distances and Cu‐O‐Cu angles of 3.092 Å and 104.2° for 2 and 3.486 Å and 129.9° for 3 , respectively. Magnetic measurements reveal that 1 is strong antiferromagnetically coupled with 2J =‐210 cm^?1 while 2 and 3 exhibit ferromagnetic coupling with 2J = 126 cm^?1 and 82 cm^?1 (averaged), respectively. The 2J values of 1–3 are correlated to dihedral angles and the Cu‐O‐Cu angles. Dependence of the pH at 25 °C on the reaction rate of oxidation of 3,5‐di‐tert‐butylcatechol (3,5‐DTBC) to the corresponding quinone (3,5‐DTBQ) catalyzed by 1–3 was studied. Complexes 1–3 exhibit catecholase‐like active at above pH 8 and 25 °C for oxidation of 3,5‐di‐tert‐butylcatechol.     

Functionalization of Pentaphosphorus Cations by Complexation

The chemistry of polyphosphorus cations has rapidly developed in recent years, but their coordination behavior has remained mostly unexplored. Herein, we describe the reactivity of [P₅R₂]⁺ cations with cyclopentadienyl metal complexes. The reaction of [Cp^ArFe(μ‐Br)]₂ (Cp^Ar=C₅(C₆H₄‐4‐Et)₅) with [P₅R₂][GaCl₄] (R=iPr and 2,4,6‐Me₃C₆H₂ (Mes)) afforded bicyclo[1.1.0]pentaphosphanes ( 1‐R , R=iPr and Mes), showing an unsymmetric “butterfly” structure. The same products 1‐R were formed from K[Cp^Ar] and [P₅R₂][GaCl₄]. The cationic complexes [Cp^ArCo(η⁴‐P₅R₂)][GaCl₄] ( 2‐R [GaCl₄], R=iPr and Cy) and [(Cp^ArNi)₂(η^3:3‐P₅R₂)][GaCl₄] ( 3‐R [GaCl₄]) were obtained from [P₅R₂][GaCl₄] and [Cp^ArM(μ‐Br)]₂ (M=Co and Ni) as well as by using low‐valent “Cp^ArM^I” sources. Anion metathesis of 2‐R [GaCl₄] and 3‐R [GaCl₄] was achieved with Na[BArF₂₄]. The P₅ framework of the resulting salts 2‐R [BArF₂₄] can be further functionalized with nucleophiles. Thus reactions with [Et₄N]X (X=CN and Cl) give unprecedented cyano‐ and chloro‐functionalized complexes, while organo‐functionalization was achieved with CyMgCl.     

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.