Anionic Diversity in Iodobismuthate Chemistry

Three salts containing different iodobismuthate anions have been synthesized. [(CH₃)₂NH₂]₃[BiI₆] was prepared by oxidation of bismuth by iodine in N,N‐dimethylformamide. [(CH₃)₂NH₂]₃[BiI₆] crystallizes in the space group with a = 30.760(3) Å and c = 8.8039(5) Å and contains monomeric [BiI₆]^3? anions. The hydrate Na₄[Bi₂I₁₀] · 14H₂O was prepared by the oxidation of bismuth using iodine in acetonitrile in the presence of NaI. Na₄[Bi₂I₁₀] · 14H₂O crystallizes in the space group C2/m with a = 12.875(2) Å, b = 16.177(2) Å, c = 9.904(2) Å and β = 106.57(6)°. The structure contains dimeric [Bi₂I₁₀]^4? anions and rows of sodium ions, with bridging water molecules. The hydrate [Na{(CH₃)₂NCHO}₂(H₂O)]₃[Bi₂I₉] was prepared by dissolution of Na₄[Bi₂I₁₀] · 14H₂O in N,N‐dimethylformamide and crystallizes in the space group with a = 13.2309(13) Å, b = 13.3791(14) Å, c = 18.722(2) Å, α = 70.338(9)°, β = 72.651(9)° and γ = 62.183(5). The structure contains dimeric [Bi₂I₉]^3? anions and cationic polymers, equation/tex2gif-stack-1.gif[Na{(CH₃)₂NCHO}₂(H₂O)]⁺.     

Cationic Allyl Complexes of the Rare‐Earth Metals: Synthesis,Structural Characterization,and 1,3‐Butadiene Polymerization Catalysis

Monocationic bis‐allyl complexes [Ln(η³‐C₃H₅)₂(thf)₃]⁺[B(C₆X₅)₄]^? (Ln=Y, La, Nd; X=H, F) and dicationic mono‐allyl complexes of yttrium and the early lanthanides [Ln(η³‐C₃H₅)(thf)₆]²⁺[BPh₄]₂^? (Ln=La, Nd) were prepared by protonolysis of the tris‐allyl complexes [Ln(η³‐C₃H₅)₃(diox)] (Ln=Y, La, Ce, Pr, Nd, Sm; diox=1,4‐dioxane) isolated as a 1,4‐dioxane‐bridged dimer (Ln=Ce) or THF adducts [Ln(η³‐C₃H₅)₃(thf)₂] (Ln=Ce, Pr). Allyl abstraction from the neutral tris‐allyl complex by a Lewis acid, ER₃ (Al(CH₂SiMe₃)₃, BPh₃) gave the ion pair [Ln(η³‐C₃H₅)₂(thf)₃]⁺[ER₃(η¹‐CH₂CH?CH₂)]^? (Ln=Y, La; ER₃=Al(CH₂SiMe₃)₃, BPh₃). Benzophenone inserts into the La? C_allyl bond of [La(η³‐C₃H₅)₂(thf)₃]⁺[BPh₄]^? to form the alkoxy complex [La{OCPh₂(CH₂CH?CH₂)}₂(thf)₃]⁺[BPh₄]^?. The monocationic half‐sandwich complexes [Ln(η⁵‐C₅Me₄SiMe₃)(η³‐C₃H₅)(thf)₂]⁺[B(C₆X₅)₄]^? (Ln=Y, La; X=H, F) were synthesized from the neutral precursors [Ln(η⁵‐C₅Me₄SiMe₃)(η³‐C₃H₅)₂(thf)] by protonolysis. For 1,3‐butadiene polymerization catalysis, the yttrium‐based systems were more active than the corresponding lanthanum or neodymium homologues, giving polybutadiene with approximately 90 % 1,4‐cis stereoselectivity.     

Structural Studies on some Iodoantimonate and Iodobismuthate Anions

The reaction between BiI₃ and two equivalents of dmpu (dmpu = N,N′-dimethylpropylene urea) in thf (tetrahydrofuran) or toluene affords dark red crystals of the complex [Bi(dmpu)₆][Bi₃I₁₂] which was characterised by X-ray crystallography and consists of octahedral [Bi(dmpu)₆]³⁺ cations and [Bi₃I₁₂]^3? anions both with 3 symmetry. An analogous reaction between SbI₃ and dmpu afforded orange crystals of what is probably a hydrolysis product, [C₅NH₆]₂[H(dmpu)₂][Sb₂I₉], which was also characterised by X-ray crystallography and contains a face-shared bioctahedral [Sb₂I₉]^3? anion with two pyridinium cations and a hydrogen bonded [H(dmpu)₂]⁺ cation. [CH₂?C(C₆H₄-4-NO₂)CH₂NMe₃]I and one equivalent of SbI₃ afforded the orange crystalline complex [CH₂?C(C₆H₄-4-NO₂)CH₂NMe₃]₃[Sb₂I₉] an X-ray crystallographic study of which revealed a face-shared bioctahedral [Sb₂I₉]^3? anion similar to that present in [C₅NH₆]₂[H(dmpu)₂][Sb₂I₉]. Four equivalents of BiI₃ and [CH₂?C(C₆H₄-4-NO₂)CH₂NMe₃]I afforded the complex [CH₂?C(C₆H₄-4-NO₂)CH₂NMe₃]₃[Bi₃I₁₂], the [Bi₃I₁₂]^3? anion being essentially identical to that encountered in [Bi(dmpu)₆][Bi₃I₁₂]. [CH₃(CH₂)₂COS(CH₂)₂NMe₃]I and four equivalents of SbI₃ yielded orange crystals of the complex [CH₃(CH₂)₂COS(CH₂)₂NMe₃]₄[Sb₈I₂₈] which was also characterised by X-ray crystallography and shown to contain a new structural type of [E₈X₂₈]^4? anion (E = As, Sb, Bi; X = halide).     

Synthesis and single crystal X‐ray determination of the Schiff base 1‐[(2‐isopropyl‐5‐methylphenoxy)hydrazono] ethyl ferrocene

The reaction of acetylferrocene [Fe(η‐C₅H₅)(η‐C₅H₄COCH₃)] (1) with (2‐isopropyl‐5‐methylphenoxy) acetic acid hydrazide [CH₃C₆H₃CH(CH₃)₂OCH₂CONHNH₂] (2) in refluxing ethanol gives the stable light‐orange–brown Schiff base 1‐[(2‐isopropyl‐5‐methylphenoxy)hydrazono] ethyl ferrocene, [CH₃C₆H₃CH(CH₃)₂OCH₂CONHN?C(CH₃)Fe(η‐C₅H₅)(η‐C₅H₄)] (3). Complex 3 has been characterized by elemental analysis, IR, ¹H NMR and single crystal X‐ray diffraction study. It crystallizes in the monoclinic space group P2₁/n, with a = 9.6965(15), b = 7.4991(12), c = 29.698(7) Å, β = 99.010(13) °, V = 2132.8(7) ų, D_calc = 1.346 Mg m^?3; absorption coefficient, 0.729 mm^?1. The crystal structure clearly shows the characteristic [N? H···O] hydrogen bonding between the two adjacent molecules of 3. This acts as a bidentale ligand, which, on treatment with [Ru(CO)₂Cl₂] _n, gives a stable bimetallic yellow–orange complex (4). Copyright © 2002 John Wiley & Sons, Ltd.     

Reactivity Studies of η5‐ Indenyl and η5‐Cp* Ruthenium(II) Complexes towards some Polypyridyl Ligands

The reaction of [(η⁵‐L³)Ru(PPh₃)₂Cl], where; L³ = C₉H₇ ( 1 ), C₅Me₅ (Cp*) ( 2 ) with acetonitrile in the presence of [NH₄][PF₆] yielded cationic complexes [(η⁵‐L³)Ru(PPh₃)₂(CH₃CN)][PF₆]; L³= C₉H₇ ([3]PF₆) and L³ = C₅Me₅ ([4]PF₆), respectively. Complexes [3]PF₆ and [4]PF₆ reacts with some polypyridyl ligands viz, 2,3‐bis (α‐pyridyl) pyrazine (bpp), 2,3‐bis (α‐pyridyl) quinoxaline (bpq) yielding the complexes of the formulation [(η⁵‐L³)Ru(PPh₃)(L²)]PF₆ where; L³ = C₉H₇, L² = bpp, ([5]PF₆), L³ = C₉H₇, L² = bpq, ([6]PF₆); L³ = C₅Me₅, L² = bpp, ([7]PF₆) and bpq, ([8]PF₆), respectively. However reaction of [(η⁵‐C₉H₇)Ru(PPh₃)₂(CH₃CN)][PF₆] ([3]PF₆) with the sterically demanding polypyridyl ligands, viz. 2,4,6‐tris(2‐pyridyl)‐1,3,5‐triazine (tptz) or tetra‐2‐pyridyl‐1,4‐pyrazine (tppz) leads to the formation of unexpected complexes [Ru(PPh₃)₂(L²)(CH₃CN)][PF₆]₂; L² = tppz ([9](PF₆)₂), tptz ([11](PF₆)₂) and [Ru(PPh₃)₂(L²)Cl][PF₆]; L² = tppz ([10]PF₆), tptz ([12]PF₆). The complexes were isolated as their hexafluorophosphate salts. They have been characterized on the basis of micro analytical and spectroscopic data. The crystal structures of the representative complexes were established by X‐ray crystallography.     

Synthesen und NMR‐Untersuchungen von Salzen mit den neuen Anionen [PtXn(CF3)6‐n]2— (n = 0 ‐ 5, X = F,OH, Cl,CN) und die Kristallstrukturanalyse von K2[(CF3)2F2Pt(μ‐OH)2PtF2(CF3)2]·2H2O

Syntheses and NMR Spectroscopic Ivestigations of Salts containing the Novel Anions [PtX_n(CF₃)_6‐n]^2— (n = 0 ‐ 5, X = F, OH, Cl, CN) and Crystal Structure of K₂[(CF₃)₂F₂Pt(μ‐OH)₂PtF₂(CF₃)₂]·2H₂O The first syntheses of trifluoromethyl‐complexes of platinum through fluorination of cyanoplatinates are reported. The fluorination of tetracyanoplatinates(II), K₂[Pt(CN)₄], and hexacyanoplatinates(IV), K₂[Pt(CN)₆], with ClF in anhydrous HF leads after working up of the products to K₂[(CF₃)₂F₂Pt(μ‐OH)₂PtF₂(CF₃)₂]·2H₂O. The structure of the salt is determined by a X‐ray structure analysis, P2₁/c (Nr. 14), a = 11.391(2), b = 11.565(2), c = 13.391(3)Å, β = 90.32(3)°, Z = 4, R₁ = 0.0326 (I > 2σ(I)). The reaction of [Bu₄N]₂[Pt(CN)₄] with ClF in CH₂Cl₂ generates mainly cis‐[Bu₄N]₂[PtCl₂(CF₃)₄] and fac‐[Bu₄N]₂[PtCl₃(CF₃)₃], but in contrast that of [Bu₄N]₂[Pt(CN)₆] with ClF in CH₂Cl₂ results cis‐[Bu₄N]₂[PtX₂(CF₃)₄], [Bu₄N]₂[PtX(CF₃)₅] (X = F, Cl) and [Bu₄N]₂[Pt(CF₃)₆]. In the products [Bu₄N]₂[PtX_n(CF₃)_6‐n] (X = F, Cl, n = 0—3) it is possibel to exchange the fluoro‐ligands into chloro‐ and cyano‐ligands by treatment with (CH₃)₃SiCl und (CH₃)₃SiCN at 50 °C. With continuing warming the trifluoromethyl‐ligands are exchanged by chloro‐ and cyano‐ligands, while as intermediates CF₂Cl and CF₂CN ligands are formed. The identity of the new trifluoromethyl‐platinates is proved by ¹⁹⁵Pt‐ and ¹⁹F‐NMR‐spectroscopy.     

η5‐(3)‐1‐Methyl‐1,2‐dicarbollyl‐η5‐2′,5′‐dimethylpyrrolylcobalt(III)

In the title compound, (η⁵‐2,5‐di­methyl­pyrrolyl)[(7,8,9,10,11‐η)‐7‐methyl‐7,8‐dicarba‐nido‐undecaborato]­cobalt(III), [3‐Co{η⁵‐[2,5‐(CH₃)₂‐NC₄H₂]}‐1‐CH₃‐1,2‐C₂B₉H₁₀] or [Co(C₃H₁₃B₉)(C₆H₈N)], the Co^III atom is sandwiched between the pentagonal faces of the pyrrolyl and dicarbollide ligands, resulting in a neutral mol­ecule. The C—C distance in the dicarbollide cage is 1.649 (3) Å.     

Ansa‐Complexes of [Mn(η5‐C5H5)(η6‐C6H6)]: Preparation,Characterization, and Reactivity of [n]Manganoarenophanes (n=1, 2, 3)

We report the synthesis of [n]manganoarenophanes (n=1, 2) featuring boron, silicon, germanium, and tin as ansa‐bridging elements. Their preparation was achieved by salt‐elimination reactions of the dilithiated precursor [Mn(η⁵‐C₅H₄Li)(η⁶‐C₆H₅Li)]?pmdta (pmdta=N,N,N′,N′,N′′‐pentamethyldiethylenetriamine) with corresponding element dichlorides. Besides characterization by multinuclear NMR spectroscopy and elemental analysis, the identity of two single‐atom‐bridged derivatives, [Mn(η⁵‐C₅H₄)(η⁶‐C₆H₅)SntBu₂] and [Mn(η⁵‐C₅H₄)(η⁶‐C₆H₅)SiPh₂], could also be determined by X‐ray structural analysis. We investigated for the first time the reactivity of these ansa‐cyclopentadienyl–benzene manganese compounds. The reaction of the distannyl‐bridged complex [Mn(η⁵‐C₅H₄)(η⁶‐C₆H₅)Sn₂tBu₄] with elemental sulfur was shown to proceed through the expected oxidative addition of the Sn?Sn bond to give a triatomic ansa‐bridge. The investigation of the ring‐opening polymerization (ROP) capability of [Mn(η⁵‐C₅H₄)(η⁶‐C₆H₅)SntBu₂] with [Pt(PEt₃)₃] showed that an unexpected, unselective insertion into the C_ipso?Sn bonds of [Mn(η⁵‐C₅H₄)(η⁶‐C₆H₅)SntBu₂] had occurred.     

Halobismuth(III) salts with substituted aminopyridinium cations

The crystal structures of six halobismuth(III) salts of variously substituted aminopyridinium cations display discrete mononuclear [BiCl₆]^3? and dinuclear [Bi₂X₁₀]^4? anions (X = Cl or Br), and polymeric cis‐double‐halo‐bridged [Bi_nX_4n]^n? anionic chains (X = Br or I). Bis(2‐amino‐3‐ammoniopyridinium) hexachloridobismuth(III) chloride monohydrate, (C₅H₉N₃)₂[BiCl₆]Cl·H₂O, (1), contains discrete mononuclear [BiCl₆]^3? and chloride anions. Tetrakis(2‐amino‐3‐methylpyridinium) di‐μ‐chlorido‐bis[tetrachloridobismuth(III)], (C₆H₉N₂)₄[Bi₂Cl₁₀], (2), tetrakis(2‐amino‐3‐methylpyridinium) di‐μ‐bromido‐bis[tetrabromidobismuth(III)], (C₆H₉N₂)₄[Bi₂Br₁₀], (3), and bis(4‐amino‐3‐ammoniopyridinium) di‐μ‐chlorido‐bis[tetrachloridobismuth(III)] dihydrate, (C₅H₉N₃)₂[Bi₂Cl₁₀]·2H₂O, (4), incorporate discrete [Bi₂X₁₀]^4? anions (X = Cl or Br), while catena‐poly[2,6‐diaminopyridinium [[cis‐diiodidobismuth(III)]‐di‐μ‐iodido]], {(C₅H₈N₃)[BiI₄]}_n, (5), and catena‐poly[2,6‐diaminopyridinium [[cis‐dibromidobismuth(III)]‐di‐μ‐bromido]], {(C₅H₇N₂)[BiBr₄]}_n, (6), include [Bi_nX_4n]^n? anionic chains (X = Br or I). Structures (2) and (3) are isostructural, while that of (5) is a pseudomerohedral twin. There is no discernible correlation between the type of anionic species obtained and the cation or halide ligand used. The Bi^III centres always have a slightly distorted octahedral geometry and there is a correlation between the Bi—X bond lengths and the number of classic N—H…X hydrogen bonds that the X ligand accepts, with a greater number of interactions corresponding with slightly longer Bi—X distances. The supramolecular networks formed by classic N—H…X hydrogen bonds include ladders, bilayers and three‐dimensional frameworks.     

Single Crystals of the Dodecaiodo‐closo‐dodecaborate Cs2[B12I12] · 2 CH3CN (≡ {Cs(NCCH3)}2[B12I12]) from Acetonitrile

Colourless, lath‐shaped single crystals of Cs₂[B₁₂I₁₂] · 2 CH₃CN (monoclinic, C2/m; a = 1550.3(2), b = 1273.2(1), c = 1051.5(1) pm, β = 120.97(1)°; Z = 2) are obtained by the reaction of Cs₂[B₁₂H₁₂] with an excess of I₂ and ICl (molar ratio: 1 : 2) in methylene iodide (CH₂I₂) at 180 °C (8 h) and recrystallization of the crude product from acetonitrile (CH₃CN). The crystal structure contains quasi‐icosahedral [B₁₂I₁₂]^2– anions (d(B–B) = 176–182 pm, d(B–I) = 211–218 pm) which arrange in a cubic closest‐packed fashion. All octahedral interstices are filled with centrosymmetric dimer‐cations {[Cs(N≡C–CH₃)]₂}²⁺ containing a diamond‐shaped four‐membered (Cs–N–Cs–N) ring of Cs⁺ cations and nitrogen atoms of the solvating acetonitrile molecules (d(Cs–N) = 321 pm, 2 ×). The cesium cations themselves actually reside in the distorted tetrahedral voids of the cubic [B₁₂I₁₂]^2– packing (d(Cs–I) = 402–461 pm, 10 ×) if one ignores the solvent particles.     

Crystalline Diuranium Phosphinidiide and μ‐Phosphido Complexes with Symmetric and Asymmetric UPU Cores

Reaction of [U(Tren^TIPS)(PH₂)] ( 1 , Tren^TIPS=N(CH₂CH₂NSiPrⁱ₃)₃) with C₆H₅CH₂K and [U(Tren^TIPS)(THF)][BPh₄] ( 2 ) afforded a rare diuranium parent phosphinidiide complex [{U(Tren^TIPS)}₂(μ‐PH)] ( 3 ). Treatment of 3 with C₆H₅CH₂K and two equivalents of benzo‐15‐crown‐5 ether (B15C5) gave the diuranium μ‐phosphido complex [{U(Tren^TIPS)}₂(μ‐P)][K(B15C5)₂] ( 4 ). Alternatively, reaction of [U(Tren^TIPS)(PH)][Na(12C4)₂] ( 5 , 12C4=12‐crown‐4 ether) with [U{N(CH₂CH₂NSiMe₂Bu^t)₂CH₂CH₂NSi(Me)(CH₂)(Bu^t)}] ( 6 ) produced the diuranium μ‐phosphido complex [{U(Tren^TIPS)}(μ‐P){U(Tren^DMBS)}][Na(12C4)₂] [ 7 , Tren^DMBS=N(CH₂CH₂NSiMe₂Bu^t)₃]. Compounds 4 and 7 are unprecedented examples of uranium phosphido complexes outside of matrix isolation studies, and they rapidly decompose in solution underscoring the paucity of uranium phosphido complexes. Interestingly, 4 and 7 feature symmetric and asymmetric UPU cores, respectively, reflecting their differing steric profiles.     

Heterobimetallische Komplexe von Lithium,Aluminium und Gold mit dem N‐[2‐N′,N′‐(Dimethylaminoethyl)‐N‐methyl‐aminoethyl]‐ferrocenyl‐Liganden (η5‐C5H5)Fe{η5‐C5H3[CH(CH3)N(CH3)CH2CH2NMe2]‐2}

Heterobimetallic Complexes of Lithium, Aluminum, and Gold with the N ‐[2‐ N ′, N ′‐(dimethylaminoethyl)‐ N ‐methyl‐aminoethyl]‐ferrocenyl Ligand (η⁵‐C₅H₅)Fe{η⁵‐C₅H₃[CH(CH₃)N(CH₃)CH₂CH₂NMe₂]‐2} N‐[2‐N′,N′‐(dimethylaminoethyl)‐N‐methyl‐aminoethyl]ferrocene FcN,NH ( 1 ) reacts with ⁿBuLi under formation of the lithium organyl (FcN,N)Li ( 2 ). At reactions of 2 with AlBr₃ and AuCl · PPh₃ the heterobimetallic organo derivatives (FcN,N)AlBr₂ ( 3 ), (FcN,N)Au · PPh₃ ( 4 ) are formed. A detailed characterization of 2 – 4 was carried out by single crystal x‐ray analyses as well as by NMR and Mößbauer spectroscopy.     

(6‐Oxido‐2‐oxo‐1,2‐dihydropyrimidine‐5‐carboxylato‐κ2O5,O6)bis[2‐(2‐pyridyl)‐1H‐benzimidazole‐κ2N2,N3]manganese(II) monohydrate

In the title compound, [Mn(C₅H₂N₂O₄)(C₁₂H₉N₃)₂]·H₂O, the Mn^II centre is surrounded by three bidentate chelating ligands, namely, one 6‐oxido‐2‐oxo‐1,2‐dihydropyrimidine‐5‐carboxylate (or uracil‐5‐carboxylate, Huca²⁻) ligand [Mn—O = 2.136 (2) and 2.156 (3) Å] and two 2‐(2‐pyridyl)‐1H‐benzimidazole (Hpybim) ligands [Mn—N = 2.213 (3)–2.331 (3) Å], and it displays a severely distorted octahedral geometry, with cis angles ranging from 73.05 (10) to 105.77 (10)°. Intermolecular N—H...O hydrogen bonds both between the Hpybim and the Huca²⁻ ligands and between the Huca²⁻ ligands link the molecules into infinite chains. The lattice water molecule acts as a hydrogen‐bond donor to form double O...H—O—H...O hydrogen bonds with the Huca²⁻ O atoms, crosslinking the chains to afford an infinite two‐dimensional sheet; a third hydrogen bond (N—H...O) formed by the water molecule as a hydrogen‐bond acceptor and a Hpybim N atom further links these sheets to yield a three‐dimensional supramolecular framework. Possible partial π–π stacking interactions involving the Hpybim rings are also observed in the crystal structure.     

catena‐Poly­[[(di‐2‐pyridyl­amine)­silver(I)]‐μ‐nicotinato] and catena‐poly­[[(di‐2‐pyridyl­amine)silver(I)]‐μ‐2,6‐di­hydroxy­benzoato]

In catena‐poly­[[(di‐2‐pyridyl­amine‐κ²N,N′)silver(I)]‐μ‐nico­tinato‐κ²N:O], [Ag(C₆H₄NO₂)(C₁₀H₉N₃)]_n, the Ag^I atom is tetracoordinated by two N atoms from the di‐2‐pyridyl­amine (BPA) ligand [Ag—N = 2.3785 (18) and 2.3298 (18) Å] and by one N atom and one carboxyl­ate O atom from nicotinate ligands [Ag—N = 2.2827 (15) Å and Ag—O = 2.3636 (14) Å]. Bridging by nicotinate N and O atoms generates a polymeric chain structure, which extends along [100]. The carboxyl O atom not bonded to the Ag atom takes part in an intrachain C—H⋯O hydrogen bond, further stabilizing the chain. Pairs of chains are linked by N—H⋯O hydrogen bonds to generate ribbons. There are no π–π interactions in this complex. In catena‐poly­[[(di‐2‐pyridyl­amine‐κ²N,N′)silver(I)]‐μ‐2,6‐di­hydroxy­benzoato‐κ²O¹:O²], [Ag(C₇H₅O₄)(C₁₀H₉N₃)]_n, the Ag^I atom has a distorted tetrahedral coordination, with three strong bonds to two pyridine N atoms from the BPA ligand [Ag—N = 2.286 (5) and 2.320 (5) Å] and to one carboxyl­ate O atom from the 2,6‐di­hydroxy­benzoate ligand [Ag—O = 2.222 (4) Å]; the fourth, weaker, Ag‐atom coordination is to one of the phenol O atoms [Ag⋯O = 2.703 (4) Å] of an adjacent moiety, and this interaction generates a polymeric chain along [100]. Pairs of chains are linked about inversion centers by N—H⋯O hydrogen bonds to form ribbons, within which there are π–π interactions. The ribbons are linked about inversion centers by pairs of C—H⋯O hydrogen bonds and additional π–π interactions between inversion‐related pairs of 2,6‐di­hydroxy­benzoate ligands to generate a three‐dimensional network.     

catena‐Poly­[fac‐tri­chloro­methyl­tin(IV)‐μ‐[meso‐1,2‐bis­(phenyl­sulfinyl)­ethane‐O:O′]]

In the title compound, [SnCl₃(CH₃)(C₆H₅SOCH₂)₂]_n, the octahedral Sn^IV centres are bridged by meso‐1,2‐bis­(phenyl­sulfinyl)­ethane ligands forming infinite chains along the [100] direction.     

Synthese und strukturelle Studien von Aluminiumdialkylaminen und ‐amiden: N‐Chiralität von (CH3)3AlNHRR′ und cis‐trans‐Isomerie an X2AlNRR′ (X = CH3, Cl,H)

Synthesis and Structural Studies of Aluminum Dialkylamines and Dialkylamides: N‐Chirality of (CH₃)₃AlNHRR′ and cis‐trans ‐Isomerism at X₂AlNRR′ (X = CH₃, Cl, H) Aluminum dialkylamines and dialkylamides were prepared from Al(CH₃)₃ and NH(CH₃)R′ (R′: –C₂H₅, –^tC₄H₉) and characterized by elemental analyses, ¹H‐, ¹³C‐, and ²⁷Al‐NMR spectroscopy. The crystal structures of [(CH₃)₂AlN(CH₃)(–^tC₄H₉)]₂ ( IV ), [Cl₂AlN(CH₃)(C₂H₅)]₂ ( V ), and [H₂AlN(CH₃)(C₂H₅)]_∞ ( VI‐trans and VI‐cis ) are discussed.     

Redetermination of bis[μ3‐1,3,5‐triamino‐1,3,5‐trideoxy‐cis‐inositolato(3–)]tribismuth(III) trichloride hexahydrate

The crystal structure of the title compound, [Bi₃(C₆H₁₂N₃O₃)₂]Cl₃·6H₂O, which was described in the space group R3 [Hegetschweiler, Ghisletta & Gramlich (1993). Inorg. Chem. 32 , 2699–2704], has been redetermined in the revised space group R32 as suggested by Marsh [Acta Cryst. (2002), B 58 , 893–899]. Accordingly, the significant difference in the Bi—N bond distances of 2.43 (2) and 2.71 (1) Å, as noted in the previous study, proved to be an artifact. As a consequence, the [Bi₃(H₋₃taci)₂]Cl_6/3 entity (taci is 1,3,5‐triamino‐1,3,5‐trideoxy‐cis‐inositol) adopts D₃ symmetry and the three Bi atoms lie on C₂ axes with equal Bi—N bond distances of 2.636 (3) Å.     

(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.     

Bis(1,10‐phenanthroline)(thio­sulfato)­manganese(II) methanol solvate and catena‐poly­[[di­aqua(2,9‐di­methyl‐1,10‐phenanthroline)­manganese(II)]‐μ‐thio­sulfato]

The structure of bis(1,10‐phenanthroline‐κ²N,N′)(thio­sulfato‐κ²O:S)­manganese(II) methanol solvate, [Mn(S₂O₃)(C₁₂H₈N₂)₂]·CH₃OH, is made up of Mn²⁺ centers coordinated to two bidentate phenanthroline (phen) groups and an S,O‐chelating thio­sulfate anion, forming monomeric entities. The structure of catena‐poly­[[di­aqua(2,9‐di­methyl‐1,10‐phen­anthro­line‐κ²N,N′)­manganese(II)]‐μ‐thio­sulfato‐κ²O:S], [Mn(S₂O₃)(C₁₄H₁₂N₂)(H₂O)₂]_n, is polymeric, consisting of Mn(dmph)(H₂O)₂ units (dmph is 2,9‐di­methyl‐1,10‐phenanthroline) linked by thio­sulfate anions acting in an S,O‐chelating manner.     

Reaktionen eines Dibismutans und von Cyclobismutanen mit Metallcarbonylen ‐ Synthesen von Komplexen mit R2Bi‐, RBi‐, Bi2‐ und Bin‐Liganden (R = Me3CCH2, Me3SiCH2)

Reactions of a Dibismuthane and of Cyclobismuthanes with Metal Carbonyls ‐ Syntheses of Complexes with R₂Bi‐, RBi‐, Bi₂‐ and Bi_n‐ligands (R = Me₃CCH₂, Me₃SiCH₂) Reactions of [Fe₂(CO)₉] with [(Me₃CCH₂)₄Bi]₂ or cyclo‐(Me₃SiCH₂Bi)_n (n = 3 ‐ 5) lead to the complexes [(R₂Bi)₂Fe(CO)₄], [RBiFe(CO)₄]₂[R = Me₃CCH₂, Me₃SiCH₂] and [Bi₂Fe₃(CO)₉]. [Bi₂{Mn(CO)₂C₅H₄CH₃}₃] forms in a photochemical reaction of [Mn(CO)₃C₅H₄CH₃] with cyclo‐(Me₃SiCH₂Bi)_n.