Novel Antimony Complexes: [Ph4Sb]4 +[Sb4I16]4− · 2Me2C=O and [Ph4Sb]3 +[Sb5I18]3−

The [Ph₄Sb]₄ ⁺[Sb₄I₁₆]^4– · 2Me₂C=O and [Ph₄Sb]₃ ⁺[Sb₅I₁₈]^3– complexes were synthesized by reacting tetraphenylstibonium salts Ph₄SbX (X = I, OSO₂C₆H₄Me-4) with antimony triiodide in acetone. According to X-ray diffraction data, their tetra- and pentanuclear anions [Sb₄I₁₆]^4– and [Sb₅I₁₈]^3– have cyclic and linear structure, respectively.     

Synthesis and structure of [Ph3MeP]3[Sb3I12]·Me2C=O, [Ph3MeP]3[Sb2I9], [Ph3MeP]2[SbI5], and [Ph3MeP]3[Sb3I12] antimony complexes

Complexes [Ph₃MeP]₃[Sb₃I₁₂]Me₂C=O (I), [Ph₃MeP]₃[Sb₂I₉] (II), and [Ph₃MeP]₂[SbI₅] (III) were obtained via the reaction of triphenylphosphonium iodide with antimony triiodide in acetone in 1:1, 3:2 and 2:1 molar ratios. Reaction of the complex III with antimony triiodide (1:1) affords [Ph₃MeP]₃[Sb₃I₁₂] (IV). The structure of the obtained complexes was confirmed by X-ray analysis.     

[μ‐(Me3SiCH2Sb)5–Sb1,Sb3–{W(CO)5}2] und [{(Me3Si)2CHSb}3Fe(CO)4] – zwei cyclische Komplexe mit Antimon‐Liganden

Syntheses and Crystal Structures of [μ‐(Me₃SiCH₂Sb)₅–Sb¹,Sb³–{W(CO)₅}₂] and [{(Me₃Si)₂CHSb}₃Fe(CO)₄] – Two Cyclic Complexes with Antimony Ligands cyclo‐(Me₃SiCH₂Sb)₅ reacts with [(THF)W(CO)₅] (THF = tetrahydrofuran) to form cyclo‐[μ‐(Me₃SiCH₂Sb)₅–Sb¹,Sb³–{W(CO)₅}₂] ( 1 ). The heterocycle cyclo‐ [{(Me₃Si)₂CHSb}₃Fe(CO)₄] ( 2 ) is formed by an insertion reaction of cyclo‐[(Me₃Si)₂CHSb]₃ and [Fe₂(CO)₉]. The crystal structures of 1 and 2 are reported.     

Synthese,Struktur und Eigenschaften der Komplexe [(H2O)Cl4Os≡N‐IrCl(C5Me5)(AsPh3)], [(Ph3Sb)Cl4Os≡N‐IrCl(C5Me5)(SbPh3)], [(Ph3Sb)2Cl3Os≡N‐IrCl(COD)] und [{(Me2PhP)2(CO)Cl2Re≡N}2ReNCl2(PMe2Ph)]

Synthesis, Crystal Structure, and Properties of the Complexes [(H₂O)Cl₄Os≡N‐IrCl(C₅Me₅)(AsPh₃)], [(Ph₃Sb)Cl₄Os≡N‐IrCl(C₅Me₅)(SbPh₃)], [(Ph₃Sb)₂Cl₃Os≡N‐IrCl(COD)] and [{(Me₂PhP)₂(CO)Cl₂Re≡N}₂ReNCl₂(PMe₂Ph)] The dinuclear complexes [(H₂O)Cl₄Os≡N‐IrCl(C₅Me₅)(AsPh₃)]·H₂O ( 1 ·H₂O), [(Ph₃Sb)Cl₄Os≡N‐IrCl(C₅Me₅)(SbPh₃)] ( 2 ), and [(Ph₃Sb)₂Cl₃Os≡N‐IrCl(COD)] ( 3 ) result from the reaction of the nitrido complexes [(Ph₃As)₂OsNCl₃] and [(Ph₃Sb)₂OsNCl₃] with the iridium compounds [IrCl₂(C₅Me₅)]₂ and [IrCl(COD)]₂ in dichloromethane. 1 crystallizes as 1 ·H₂O in form of green platelets in the monoclinic space group Cm and a = 1105.53(6); b = 1486.76(9); c = 2024.88(10) pm, β = 97.191(4)°, Z = 4. The formation of 1 in air involves a ligand exchange, and the coordination of a water molecule in trans position to the Os‐N triple bond. The resulting complex fragments [(H₂O)Cl₄Os≡N] and [IrCl(C₅Me₅)(AsPh₃)] are connected by an asymmetric nitrido bridge Os≡N‐Ir. The nitrido bridge is characterised by an Os‐N‐Ir bond angle of 173.7(7)°, and distances Os‐N = 168(1) pm and Ir‐N = 191(1) pm. 2 crystallizes in clumped together brown platelets with the space group and a = 1023.3(3), b = 1476.2(3), c = 1872.5(6) pm, α = 74.60(2), β = 73.84(2), γ = 76.19(2)°, Z = 2. In 2 the asymmetric nitrido bridge Os≡N‐Ir joins the two complex fragments [(Ph₃Sb)Cl₄Os≡N] and [IrCl(C₅Me₅)(SbPh₃)], which are formed by a ligand exchange reaction. 3 forms dark green crystals with the triclinic space group and a = 1079.4(1), b = 1172.3(1), c = 1696.7(2) pm, α = 101.192(9),β = 92.70(1), γ = 92.61(1)°, Z = 2. The distances in the almost linear nitrido bridge (Os≡N‐Ir = 175.3(7)°) are Os‐N = 171(1) pm and Ir‐N = 183(1) pm. The reaction of [ReNCl₂(PMe₂Ph)₃] with [Mo(CO)₃(NCMe)₃] unexpectedly affords the trinuclear complex [{(Me₂PhP)₂(OC)Cl₂Re≡N}₂ReNCl₂(PMe₂Ph)] ( 4 ) as the main product. It forms triclinic brown crystals with the composition 4 ·2THF and the space group (a = 1382.70(7), b = 1498.58(7), c = 1760.4(1) pm, α = 99.780(7), β = 99.920(7), γ = 114.064(6)°, Z = 2). In the trinuclear complex, the central fragment, [ReNCl₂(PMe₂Ph)] is joined in trans position to two nitrido complexes [(Me₂PhP)₂(CO)Cl₂Re≡N], giving an almost linear Re≡N‐Re‐N≡Re arrangement. The bond angles and distances in the nitrido bridges are Re‐N‐Re = 167.8(3)°, Re‐N = 171.1(8) pm and 204.2(8) pm; and Re‐N‐Re = 168.1(4)°, Re‐N = 170.9(9) and 203.5(9) pm respectively. As expected, the Re‐N bond length to the terminal nitrido ligand on the central Re atom is much shorter at 161.2(9) pm than the triple bonds of the asymmetric bridges.     

Nitrosyltechnetium(I) Complexes with 2‐(Diphenylphosphanyl)aniline

[Tc^I(NO)Cl(H₂L1)₂]⁺ cations (H₂L1 = 2‐(diphenylphosphanyl)aniline) are formed during reactions of H₂L1 with (NBu₄)[Tc(NO)Cl₄(MeOH)] or (NH₄)TcO₄/HCl/NH₂OH mixtures. Different isomers were isolated depending on the counterions and solvents used. The technetium(I) complexes cis‐NO,Cl,trans‐P,P‐[Tc^I(NO)Cl(H₂L1)₂]Cl, trans‐NO,Cl,cis‐P,P‐[Tc^I(NO)Cl(H₂L1)₂]₂(TcCl₆), and trans‐NO,Cl,trans‐P,P‐[Tc^I(NO)Cl(H₂L1)₂](PF₆) were isolated in crystalline form and studied by spectroscopic methods and X‐ray crystallography. DFT calculations show that there are only minor energy differences between the three isomers and the formation of the individual compounds is most probably strongly influenced by interactions with solvents and counterions.     

Über die Kronenetherkomplexe [K(15-Krone-5)2]3[Sb3I12], [TeCl3(15-Krone-5)][TeCl5] und [TeCl3(15-Krone-5)]2[TeCl6]

On the Crown Ether Complexes [K(15-Crown-5)₂]₃[Sb₃I₁₂], [TeCl₃(15-Crown-5)][TeCl₅], and [TeCl₃(15-Crown-5)]₂[TeCl₆] Orange-coloured crystals of [K(15-crown-5)₂]₃[Sb₃I₁₂] are formed in the reaction of potassium iodide with antimony triiodide and 15-crown-5 in acetonitrile solution. An X-ray structure determination reveals severe disorder of the crown ether molecules, which coordinate to the potassium atoms in a sandwich array; so only the [Sb₃I₁₂]^3? ion and the potassium positions were ascertained. The anion is a centrosymmetric trimer (symmetry C_2h), which can be understood as central SbI₆^3? ion, coordinated by two SbI₃ molecules. (Space group C2/m), Z = 2, 3263 observed, independent reflections, R = 0.06, lattice dimensions at 20°C: a = 2541.1 pm, b = 1441.7 pm, c = 1588.4 pm, β = 113.33°. The tellurium complexes [TeCl₃(15-crown-5)] [TeCl₅] and [TeCl₃(15-crown-5)]₂[TeCl₆] are prepared by reaction of TeCl₄ with 15-crown-5 in acetonitrile solution, forming yellow-green crystals sensitive to moisture. They are characterized by their i.r. spectra.     

Tripyridine‐Derivative‐Derived Semiconducting Iodo‐Argentate/Cuprate Hybrids with Excellent Visible‐Light‐Induced Photocatalytic Performance

Through regulating the pH values, a series of iodo‐argentate/cuprate hybrids, [Me₃(4‐TPT)]₄[Ag₆I₁₈] ( 1 , Me₃(4‐TPT)=N,N′,N′′‐trimethyl‐2,4,6‐tris(4‐pyridyl)‐1,3,5‐triazine), [Me₃(4‐TPT)][M₅I₈] (M=Ag/ 2 , Cu/ 2 a ), [Me₃(3‐TPT)][M₅I₈] (Me₃(3‐TPT)=N,N′,N′′‐trimethyl‐2,4,6‐tris(3‐pyridyl)‐1,3,5‐triazine, M=Ag/ 3 , Cu/ 4 ), which exhibit adjustable structural variations with different dimensional structures, have been obtained under solvothermal conditions. They are directed by two types of in situ N‐alkylation TPT‐derivatives (Me₃(4‐TPT) for 1 / 2 / 2 a and Me₃(3‐TPT) for 3 / 4 ) and represent the isolated units ( 1 ), 1D polymeric chain ( 4 ), 2D layered structures ( 2 / 2 a , 3 ) based on diverse metal iodide clusters. These compounds possess reducing band gaps as compared with the bulk β‐AgI and CuI and belong to potential semiconductor materials. Iodocuprates feature highly efficient photocatalytic activity in the sunlight‐induced degradation of organic dyes. The detailed study on the possible photocatalytic mechanism, including radical trapping tests and theoretical calculations, reveals that the N‐alkylation TPT moieties contribute to the narrow semiconducting behavior and effectively inhibit the recombination of photogenerated electron‐hole pairs, which result in an excellent visible‐light‐induced photocatalytic performance.     

Distibanes and Distibenes from Reduction of Sb(NONR)Cl by using MgI Reagents

The bis(amidodimethyl)disiloxane antimony chlorides Sb(NON^R)Cl (NON^R=[O(SiMe₂NR)₂]²⁻; R=tBu, Ph, 2,6-Me₂C₆H₃=Dmp, 2,6-iPr₂C₆H₃=Dipp, 2,6-(CHPh₂)₂-4-tBuC₆H₂=tBu-Bhp) are reduced to Sb^II and Sb^I species by using Mg^I reagents, [Mg(BDI^R′)]₂ (BDI=[HC{C(Me)NR′}₂]⁻; R′=2,4,6-Me₃C₆H₂=Mes, Dipp). Stoichiometric reactions with Sb(NON^R)Cl (R=tBu, Ph) form dimeric Sb^II stibanes [Sb(NON^R)]₂, shown crystallographically to contain Sb−Sb single bonds. The analogous distibane with R=Dmp substituents has an exceptionally long Sb−Sb interaction and exhibits spectroscopic and reactivity properties consistent with radical character in solution. When R=Dipp, reductions with Mg^I reagents directly give distibenes [Sb(μ-NON^Dipp)Mg(BDI^R′)(THF)_n]₂ (R′=Mes, n=1; R′=Dipp, n=0). Crystallographic analysis shows a trans-substitution of the Sb=Sb double bond, with bridging NON^Dipp-ligands between the Sb^I and Mg^II centres. An attempt to access the NON^Ph-analogue using the same protocol afforded the polystibide cluster Sb₈[μ₄,η^2:2:2:2-Mg(BDI^Mes)]₄, which co-crystallized with the ligand transfer product, [Mg(BDI^Mes)]₂(μ-NON^Ph).     

Tetrakis­[phthalocyaninato(2–)­antimony(III)] hexadecaiodotetraantimony(III)

Crystals of a new antimony(III) phthalocyanine complex with the formula [Sb(C₃₂H₁₆N₈)]₄(Sb₄I₁₆), or (SbPc)·[Sb₄I₁₆]^4?, where Pc is phthalocyaninate, have been obtained by the reaction of pure powdered antimony with phthalo­nitrile under a stream of iodine vapour. The crystals are built up from separate but interacting (SbPc)⁺ cations and centrosymmetric [Sb₄I₁₆]^4? anions. Each Sb atom of two independent (SbPc)⁺ units is bonded to the four iso­indole N atoms of the phthalocyaninate(2?) macrocycle and lies 1.0 Å out of the plane defined by four iso­indole N atoms. The anionic part of the complex consists of four SbI₆ distorted octahedra joined together into a centrosymmetric [Sb₄I₁₆]^4? anion. The arrangement of oppositely charged moieties in the crystal is mainly determined by ionic attraction and by a set of distinct donor–acceptor interactions between (SbPc)⁺ and [Sb₄I₁₆]^4? ions.     

Synthesen und Kristallstrukturanalysen von [SbI3(SbMe3)(THF)]2 und [Li(THF)4]2[Bi2Cl8(THF)2]

Syntheses and Crystal Structure Analyses of [SbI₃(SbMe₃)(THF)]₂ and [Li(THF)₄]₂[Bi₂Cl₈(THF)₂] The reaction of Me₃Sb with SbI₃ in tetrahydrofuran (THF) gives [SbI₃(SbMe₃)(THF)]₂ ( 1 ). [Li(THF)₄]₂[Bi₂Cl₈(THF)₂] ( 2 ) is formed by reaction of LiCl and BiCl₃ in tetrahydrofuran. The structures of ( 1 ) and ( 2 ) have been determined by X-ray diffractometry. Both structures contain centrosymmetric dimers with the geometry of edge sharing octahedra.     

Reactions of Distibanes with [Fe2(CO)9]: Synthesis,Structure and DFT Calculations of [(Et2Sb)4Fe4(CO)14], [(nPr2Sb)4Fe3(CO)10], [{(Me3SiCH2)2Sb}4Fe2(CO)6], and [2‐(Me2NCH2)C6H4SbFe2(CO)8]

The iron complexes [(Et₂Sb)₄Fe₄(CO)₁₄] ( 1 ), [(nPr₂Sb)₄Fe₃(CO)₁₀] ( 2 ), [{(Me₃SiCH₂)₂Sb}₄Fe₂(CO)₆] ( 3 ), and [2‐(Me₂NCH₂)C₆H₄SbFe₂(CO)₈] ( 4 ) were prepared by reactions of distibanes with Fe₂(CO)₉. Compounds 1 – 4 were characterized by X‐ray diffraction, ¹H NMR and IR spectroscopy as well as mass spectrometry; complex 1 was additionally characterized by density functional calculations.     

New Rh(III) complexes of 5‐methyl‐5‐(pyridyl)‐2,4‐imidazolidenedione: Synthesis,X‐ray structure,electrochemical study and catalytic behaviour for hydrogenation of ketones

We describe the reaction of anion [RhCl₆]³⁻ with a series of hydantoin ligands (HL1, HL2 and HL3 = 5‐methyl‐5‐(2‐, 3‐ and 4‐pyridyl)‐2,4‐imidazolidenedione, respectively). Based on spectroscopic, cyclic voltammetric, elemental and MS analyses, the complexes have the general formula K[RhCl₂(L1)₂] ( 1 ), cis ‐ and trans ‐K[RhCl₄(HL2)₂] ( 2a and 2b ) and cis ‐ and trans ‐K[RhCl₄(HL3)₂] ( 3a and 3b ). Complexes 2a , 2b , 3a and 3b were characterized successfully using infrared, ¹H NMR and ¹³C NMR spectral analyses. Dissolution of complex 1 in dimethylsulfoxide (DMSO) led to elimination of one KL1 ligand and coordination of two DMSO molecules as ligands and transformation of this complex to cis ‐ and trans ‐[RhCl₂L1(DMSO)₂] ( 1a and 1b ). Recrystallization led to separation and isolation of crystals of 1a from the initial mixture. X‐ray analysis results showed that this complex was crystallized as solvated complex cis ‐[RhCl₂L1(DMSO)₂]DMSO. The catalytic activity of these complexes was then evaluated for the hydrogenation of various ketones.     

Synthesis and Structural Characterization of Magnesium‐Substituted Polystibides [(LMg)4Sb8]

Redox reactions of [(L^1,2Mg)₂] and Sb₂R₄ (R=Me, Et) yielded the first Mg‐substituted realgar‐type Sb₈ polystibides [(L^1,2Mg)₄(μ₄,η^2:2:2:2‐Sb₈)] (L¹=HC[C(Me)N(2,4,6‐Me₃C₆H₂)]₂, L²=HC[C(Me)N(2,6‐i‐Pr₂C₆H₃)]₂). Compounds [(L^1,2Mg)₂] serve both as reducing agents, initiating the cleavage of the Sb?C bonds, and as stabilizers for the resulting Sb₈ polyanion. The polystibides were characterized by NMR and IR spectroscopies, elemental analysis, and X‐ray structure analysis. In addition, results from quantum chemical calculations are presented.     

Synthese und Kristallstrukturen der Thiochloroantimonate(III) PPh4[Sb2SCl5] und (PPh4)2[Sb2SCl6] · CH3CN

Syntheses and Crystal Structures of the Thiochloroantimonates(III) PPh₄[Sb₂SCl₅] and (PPh₄)₂[Sb₂SCl₆]. CH₃CN (PPh₄)₂Sb₃Cl₁₁, obtained from Sb₂S₃, PPh₄Cl and HCl, reacts with Na₂S₄ in acetonitrile forming PPh₄[Sb₂SCl₅]. From this and Na₂S₄ or from (PPh₄)₂[Sb₂Cl₈] and Na₂S₄ or K₂S₅ in acetonitrile (PPh₄)₂[Sb₂SCl₆] · CH₃CN is obtained. Data obtained from the X-ray crystal structure determinations are: PPh₄[Sb₂SCl₅], monoclinic, space group P2₁/c, a = 1002.9(3), b = 1705.6(5), c = 1653.7(5) pm, β = 99.12(2)°, Z = 4, R = 0.068 for 1283 reflextions; (PPh₄)₂[Sb₂SCl₆] · CH₃CN, triclinic, space group P1 , a = 1287.8(7), b = 1343.6(9), c = 1696.5(9) pm, α = 69.82(5), β = 85.08(4), γ = 71.54(6)°, Z = 2, R = 0.059 for 6409 reflexions. In every anion two Sb atoms are linked via one sulfur and one ore two chloro atoms, respectively. Paris of [SbSCl₅]^? ions are associated via Sb …? S and Sb …? Cl contacts forming dimer units. In both compounds every Sb atom has a distorted octahedral coordination when the lone electron pair is included in the counting.     

A Mixed‐Valence {Fe13} Cluster Exhibiting Metal‐to‐Metal Charge‐Transfer‐Switched Spin Crossover

It is promising and challenging to manipulate the electronic structures and functions of materials utilizing both metal‐to‐metal charge transfer (MMCT) and spin‐crossover (SCO) to tune the valence and spin states of metal ions. Herein, a metallocyanate building block is used to link with a Fe^II‐triazole moiety and generates a mixed‐valence complex {[(Tp^4‐Me)Fe^III(CN)₃]₉[Fe^II₄(trz‐ph)₆]}?[Ph₃PMe]₂?[(Tp^4‐Me)Fe^III(CN)₃] ( 1 ; trz‐ph=4‐phenyl‐4H‐1,2,4‐triazole). Moreover, MMCT occurs between Fe^III and one of the Fe^II sites after heat treatment, resulting in the generation of a new phase, {[(Tp^4‐Me)Fe^II(CN)₃][(Tp^4‐Me)Fe^III(CN)₃]₈ [Fe^IIIFe^II₃(trz‐ph)₆]}? [Ph₃PMe]₂?[(Tp^4‐Me)Fe^III(CN)₃] ( 1 a ). Structural and magnetic studies reveal that MMCT can tune the two‐step SCO behavior of 1 into one‐step SCO behavior of 1 a . Our work demonstrates that the integration of MMCT and SCO can provide a new alternative for manipulating functional spin‐transition materials with accessible multi‐electronic states.     

Trans Influence of Triphenylstibine: Crystal Structures of cis‐[PtBr2(SbPh3)2], trans‐[PtBr(Ph)(SbPh3)2], [NMe4][PtBr3(SbPh3)], and cis‐[PtBr2(SbPh3)(PPh3)]

The work reports the unexpected reaction of diphenyldibromo antimonates (III) with PtCl₂ and cis‐[PtCl₂(PPh₃)₂]. The reaction gives triphenylstibine containing Pt^II complexes viz. cis‐[PtBr₂(SbPh₃)₂] ( 1 ), trans‐[[PtBr(Ph)(SbPh₃)₂] ( 2 ), [NMe₄][PtBr₃(SbPh₃)] ( 3 ), and cis‐[PtBr₂(PPh₃)(SbPh₃)] ( 4 ). All the complexes were characterised by elemental analyses, IR, Raman, ¹⁹⁵Pt NMR, FAB mass spectroscopy and X‐ray crystallography. A plausible mechanism via the phenyl migration is proposed for the formation of these complexes. The average Pt–Br distance in 1 is 2.456(2) Å, in 2 2.496 Å(trans to Ph) while in 3 it is 2.476 Å (trans to Sb) implying a comparable trans influence of Ph₃Sb and Ph₃P.     

N‐Methylimidazolkomplexe des Berylliums: [Be(Me‐Im)4]I2 und [Be3(μ‐OH)3(Me‐Im)6]Cl3

Tetra(N‐methylimidazole)‐beryllium‐di‐iodide, [Be(Me‐Im)₄]I₂ ( 1 ), was prepared from beryllium powder and iodine in N‐methylimidazole suspension to give yellow single crystal plates, which were characterized by X‐ray diffraction and IR spectroscopy. Compound 1 crystallizes tetragonally in the space group I 2d with four formula units per unit cell. Lattice dimensions at 100(2) K: a = b = 1784.9(1), c = 696.2(1) pm, R₁ = 0.0238. The structure consists of homoleptic dications [Be(Me‐Im)₄]²⁺ with short Be–N distances of 170.3(3) pm and iodide ions with weak interionic C–H ··· I contacts. Experiments to yield crystalline products from reactions of N‐methylimidazole with BeCl₂ and (Ph₄P)₂[Be₂Cl₆], respectively, in dichloromethane solutions were unsuccessful. However, single crystals of [Be₃(μ‐OH)₃(Me‐Im)₆]Cl₃ ( 2 ) were obtained from these solutions in the presence of moisture air. According to X‐ray diffraction studies, two different crystal individuals ( 2a and 2b ) result, depending on the starting materials BeCl₂ and (Ph₄P)₂[Be₂Cl₆], respectively [ 2a : Space group P2₁/n, Z = 4; 2b : Space group P , Z = 2]. As a side‐product from the reaction of N‐methylimidazole with (Ph₄P)₂[Be₂Cl₆] single crystals of (Ph₄P)Cl·CH₂Cl₂ ( 3 ) were identified crystallographically (P2₁/n, Z = 4) which are isotypical with the corresponding known bromide (Ph₄P)Br·CH₂Cl₂.     

Synthesis and structure of antimony iodide complexes: [Ph3MeP] + 2 [SbI5]2−, [Ph3MeP] + 3 [Sb3I12]3−·Me2C=O, [Ph3MeP] + 3 [Sb3I12]3−, and [Ph3MeP] + 3 [Sb2I9]3−

Complexes with antimony-containing anions, [Ph₃MeP] ₊ ² [SbI₅]^2? (I), [Ph₃MeP] ₊ ² [Sb₃I₁₂]^3? (II), [Ph₃MeP] ₊ ³ [Sb₃I₁₂]^3? · Me₂C=O (III), and [Ph₃MeP] ₊ ³ [Sb₂I₉]^3? (IV), were synthesized by reacting triphenylmethylphosphonium iodide with antimony iodide. The central atom in the cations of the complexes has a distorted tetrahedral coordination. In the trinuclear anions of complexes II and III, each of the terminal SbI₃ groups is bound to the central Sb atom through two μ₂- and one μ₃ iodine bridges (SbSbSb angles are 103.0° and 102.2°, respectively). In the binuclear anion of complex IV, antimony atoms are linked with each other via three bridging iodine atoms.     

(Bzl4P)2[Bi2I8] – ein Iodobismutat mit fünffach koordiniertem Bi3+‐Ion

(Bzl₄P)₂[Bi₂I₈] – an Iodobismuthate with Penta‐coordinated Bi³⁺ Ions (Bzl₄P)₂[Bi₂I₈] ( 1 , Bzl = –CH₂–C₆H₅) is the first iodobismuthate showing square pyramidal coordination of the Bi³⁺ ion. The anion structure of 1 is compared with that of (Ph₄P)₂[Bi₂I₈(thf)₂] ( 2 ), in which the vacant coordination sites in 1 are occupied by THF ligands. (Bzl₄P)₂[Bi₂I₈] ( 1 ): Space group P1 (No. 2), a = 1300.6(6), b = 1316.8(6), c = 2157.0(9) pm, α = 78.66(3), β = 87.17(3), γ = 60.62(3)°, V = 3151(2)_.10⁶ pm³; (Ph₄P)₂[Bi₂I₈(thf)₂] ( 2 ): Space group P1 (No. 2), a = 1146.5(1), b = 1181.2(1), c = 1249.2(1) pm, α = 92.28(1), β = 105.71(1), γ = 95.67(1)°, V = 1616.6(2)_.10⁶ pm³.     

Iodoplumbate mit polymeren Anionen – Synthese und Kristallstrukturen von [Na3(OCMe2)12][Pb4I11(OCMe2)], (Ph4P)2[Pb5I12] und (Ph4P)4[Pb15I34(dmf)6]

Iodoplumbates with Polymeric Anions – Synthesis and Crystal Structures of [Na₃(OCMe₂)₁₂][Pb₄I₁₁(OCMe₂)], (Ph₄P)₂[Pb₅I₁₂], and (Ph₄P)₄[Pb₁₅I₃₄(dmf)₆] Reactions of PbI₂ with NaI in polar organic solvents followed by crystallization with large cations yield iodoplumbate complexes with various compositions and structures. [Na₃(OCMe₂)₁₂][Pb₄I₁₁(OCMe₂)] 3 , (Ph₄P)₂[Pb₅I₁₂] 4 and (Ph₄P)₄[Pb₁₅I₃₄(dmf)₆] 7 contain one-dimensional infinite anionic chains of face- or edge-sharing PbI₆ or PbI₅L (L = acetone, DMF) octahedra. [Na₃(OCMe₂)₁₂][Pb₄I₁₁(OCMe₂)] 3 : Space group P1 (No. 1), a = 1120.3(5), b = 1265.3(6), c = 1608.3(8) pm, α = 74.64(4), β = 70.40(4), γ = 85.24(4)°, V = 2071(2) · 10⁶ pm³; (Ph₄P)₂[Pb₅I₁₂] 4 : Space group C2/c (No. 15), a = 787.00(10), b = 2812.0(5), c = 3115.9(5) pm, β = 96.240(13)°, V = 6885(2) · 10⁶ pm³; (Ph₄P)₄[Pb₁₅I₃₄(dmf)₆] 7 : Space group P2₁/n (No. 14), a = 2278.8(4), b = 1782.6(3), c = 2616.8(4) pm, β = 114.432(13)°, V = 9678(3) · 10⁶ pm³.