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.     

Synthesis and structure of antimony complexes [Ph3AmP] 2 + [Sb2I8 · 2DMSO]2−, [Ph3PrP] 2 + [Sb2I8 · C4H8O2]2−, and [(HOCH2CH2)3NH] 4 + [Sb4I16]4−

The reaction of equimolar amounts of triphenylamyl- and triphenylpropylphosphonium iodides and triethanolammonium iodide with antimony iodide in dimethyl sulfoxide, dioxane, or acetone gave complexes [Ph₃AmP] ₂ ⁺ [Sb₂I₈ · 2DMSO]^2?, [Ph₃PrP] ₂ ⁺ [Sb₂I₈ · C₄H₈O₂]^2?, and [(HOCH₂CH₂)₃NH] ₄ ⁺ [Sb₄I₁₆]^4?, the structure of which was established by X-ray diffraction analysis. The cations of all complexes have slightly distorted tetrahedral structure, and the antimony atoms in the anions are hexacoordinated. The crystals of the complexes have intra- and intermolecular contacts, which form the structure.     

Synthesis and structure of tetra-p-tolylantimony complexes [(4-MeC6H4)4Sb] 2 + [Hg2I6]2−, [(4-MeC6H4)4Sb] 2 + [HgI4]2−, [(4-MeC6H4)4Sb] 3 + [Sb3I12]2−, and [(4-MeC6H4)4Sb]+[ReO4]−

Complexes [(4-MeC₆H₄)₄Sb] ₂ ⁺ [Hg₂I₆]^2? (I), [(4-MeC₆H₄)₄Sb] ₂ ⁺ [HgI₄]^2? (II), [(4-MeC₆H₄)₄Sb] ₃ ⁺ [Sb₃I₁₂]^2? (III), were synthesized by reactions of tetra-p-tolylantimony iodide with mercury iodide and antimony iodide, respectively. Tetra-p-tolylantimony perrhenate [(4-MeC₆H₄)₄Sb]⁺[ReO₄]^? (IV) was prepared from tetra-p-tolylantimony chloride and sodium perrhenate in acetone. Crystal structures of complexes I, II, and IV were determined by X-ray crystallography. Mercury and rhenium atoms have tetrahedral coordinations in these complexes. The Hg-I and Re-O distances in the structures of I, II, and IV vary within 2.7719(13)–2.7908(12)Å, 2.7028(3)–2.9163(3) Å, and 1.693(3)–1.744(3) Å, respectively. Antimony atoms in two crystallographically independent trinuclear centrosymmetric [Sb₃I₁₂]^2? anions of complex III have an octahedral environment. Each terminal SbI₃ fragment (Sb-I_t, 2.8265(9)–2.8333(10)Å) is bound to the central atom through tree bridging iodine atoms (Sb(2)-I_br, 3.2275(9)–3.3620(10)Å). The distances between the central Sb atom and bridging iodine atoms are much shorter (Sb(1)-I_br, 3.0153(6)–3.0316(6) Å; Sb(3)-I_br, 2.9926(6)–3.0074(6) Å).     

Synthesis and structure of bismuth-containing complexes [(Ph4BiO)2{2,5-(CH3)2C6H3S(O)}] 2 + [Ph2Bi2I6]2−,[(Ph4Bi]+[PhBi(C5H5N)I3]−, [Ph4Sb] 4 + [Bi4I16]4−⋅2(CH3)2 C=O, and [Ph4Sb] 3 + [Bi5I18]3−

The reactions of tetraphenylbismuthonium and -stibonium salts Ph₄EX (E = Bi, Sb; X = I, OSO₂ (C₆H₃(CH₃)₂-2,5), OSO₂C₆H₃(OH-4)(COOH-3)) with bismuth triiodide in acetone afford complexes [Ph₄Bi]⁺[PhBi(C₅H₅N)I₃]^-, [(Ph₄BiO)₂S(O){2,5-(CH₃)₂C₆H₃S(O)} [Ph₂Bi₂I₆]^2–, [Ph₄Sb [Bi₄I₁₆]^4-·2(CH₃)²C=O, and [Ph₄Sb] ₃₊ ⁺ [Bi₅I₁₈]^3-, whose structural units, according to the X-ray diffraction data, are tetraphenylbismuthonium (-stibonium) cations and mono-, di-, tetra-, and pentanuclear anions, respectively.     

Synthesis and structure of bismuth complexes [Ph3MeP] 2 + [BiI3.5Br1.5(C5H5N)]2− · C5H5N, [Ph4Bi] 4 + [Bi4I16]4− · 2Me2C=O, and [Ph3(iso-Am)P] 4 + [Bi8I28]4− · 2Me2C=O

Complexes [Ph₃MeP] ₂ ⁺ [BiI_3.5Br_1.5(C₅H₅N)]^2? · C₅H₅N(I), [Ph₄Bi] ₄ ⁺ [Bi₄I₁₆]^4? · 2Me₂C=O (II), and [Ph₃(iso-Am)P] ₄ ⁺ [Bi₈I₂₈]^4? · 2Me₂C=O (III) were synthesized by reactions of bismuth iodide with triphenylmethylphosphonium bromide, triphenylbismuthonium sulfosalicylate, and triphenylisoamylphosphonium iodide, respectively. The crystal structures of complexes I–III were determined by X-ray crystallography. The complexes contain, in addition to cations and solvent molecules, mono-, tetra-, and octanuclear anions, in which bismuth atoms are in octahedral coordination.     

Synthesis and structures of zirconium complexes [Et2H2N]+2[ZrCl6]2–, [Me3NCH2Ph]+2[ZrCl6]2–•MeCN, [Ph3PC6H4(CHPh2-4)]+2[ZrCl6]2–•2 MeCN,and [Ph4Sb]+2[ZrCl6]2–

Russian Chemical Bulletin - The complexes [Et2H2N]+2[ZrCl6]2– (1), [Me3NCH2Ph]+2[ZrCl6]2–?MeCN (2), [Ph3PC6H4(CHPh2-4)]+2[ZrCl6]2–?2 MeCN (3), and...     

Synthesis and structure of bismuth-containing complexes [Ph3PMe] 2 + [BiI5]2− and [Ph3PMe] 2 + [BiI5 · C5H5N]2− · C5H5N

The complexes [Ph₃PMe] ₂ ⁺ [BiI₅]^2? (I) and [Ph₃PMe] ₂ ⁺ [BiI₅ · C ₅H₅N]^2? · C ₅H₅N (II) were synthesized by the reaction of bismuth triiodide with triphenylmethylphosphonium iodide, and their structures were determined by X-ray diffraction analysis. The P atom in cation I has slightly distorted tetragonal coordination polyhedron (the CPC angles 109.42(4)° and 109.52(4)°, the bond lengths P-C_Ph 1.779(2), P-C_Me 1.793(1) Å. The Bi atom in the anion of complex I has an ideal trigonal-bipyramidal coordination polyhedron (Bi-I_eq 3.0031(4), Bi-I_eq 3.0485(5) Å). The crystal of complex II consists of the anions [BiI₅ · C ₅H₅N]^2?, solvated pyridine molecules, and two types of crystallographically independent tetrahedral triphenylmethylphosphonium cations (the angles CPC 106.9(1)°–111.7(1)°, the distances P-C_Ph 1.785(3)–1.792(3), P-C_Me 1.793(3), 1.786(3) Å). The Bi atoms in the anion of complex II have a distorted octahedral coordination polyhedron (Bi-I 3.0878(4)–3.1240(3), Bi-N(1) 2.628(3) Å).     

The unusual stability of [NpO2Cl4]2−: Synthesis and characterisation of [NpO2(DPPMO2)2Cl]2[NpO2Cl4] and [Ph3PNH2]2[NpO2Cl4]

The [NpO₂(DPPMO₂)₂Cl][NpO₂Cl₄] complex (where DPPMO₂ = bis(diphenylphosphino)methanedioxide) contains the linear neptunyl group, {NpO₂}²⁺, with two bidentate P=O donor ligands. Coordinating anion Cl^? fills the fifth equatorial coordination site yielding a complex of general formula [NpO₂(DPPMO₂)₂X]₂[Y] (1) (where X = Cl^? and Y = [NpO₂Cl₄]^2?. Reaction between our newly prepared neptunium starting material [NpO₂Cl₂(thf)]_n and phosphinimine ligand produced crystals of [Ph₃PNH₂]₂[NpO₂Cl₄] (2). Compounds 1 and 2 have been structurally characterised.     

Synthesis and structure of [(μ4-succinato)hexadecaphenyltetraantimony] triiodide solvate with benzene [(Ph4Sb)2O2CCH2CH2CO2(Ph4Sb)2][I3]2 · 4PhH

Russian Journal of Coordination Chemistry - The reaction of bis(tetraphenylantimony) succinate with iodine in benzene affords [(μ4-succinato) hexadecaphenyltetraantimony] triiodide solvate...     

Synthesis,structure, and luminescence of the octahedral molybdenum cluster [Mo6I8(SC6F4H)6]2−

A new thiolate cluster complex (Bu₄N)₂[Mo₆I₈(SC₆F₄H)₆] was synthesized by the metathesis reaction of (Bu₄N)₂[Mo₆I₁₄] and HC₆F₄SAg in methylene chloride. According to the X-ray structure determination, the cluster core {Mo₆I₈}⁴⁺ coordinates six thiolate ligands 2,3,5,6-HC₆F₄S^?. The Mo-Mo and Mo-I distances have their usual values. The average Mo-S distance is 2.538(4) Å, and the Mo-S-C angles range from 107 to 109°. Compound (Bu₄N)₂[Mo₆I₈(SC₆F₄H)₆] both in solid and in solution displays a bright red microsecond luminescence, which is typical of octahedral molybdenum halide complexes.     

σ-Aromaticity-Induced Stabilization of Heterometallic Supertetrahedral Clusters [Zn6Ge16]4− and [Cd6Ge16]4−

In this work, the largest heterometallic supertetrahedral clusters, [Zn₆Ge₁₆]⁴⁻ and [Cd₆Ge₁₆]⁴⁻, were directly self-assembled through highly-charged [Ge₄]⁴⁻ units and transition metal cations, in which 3-center–2-electron σ bonding in Ge₂Zn or Ge₂Cd triangles plays a vital role in the stabilization of the whole structure. The cluster structures have an open framework with a large central cavity of diameter 4.6 Å for Zn and 5.0 Å for Cd, respectively. Time-dependent HRESI-MS spectra show that the larger clusters grow from smaller components with a single [Ge₄]⁴⁻ and ZnMes₂ units. Calculations performed at the DFT level indicate a very large HOMO–LUMO energy gap in [M₆Ge₁₆]⁴⁻ (2.22 eV), suggesting high kinetic stability that may offer opportunities in materials science. These observations offer a new strategy for the assembly of heterometallic clusters with high symmetry.     

Synthesis,structure, and electrochemical properties of [M(N-MeIm)6]2+ (M = Ni,Co, Cu) associated with [HgCl4]2−

Reaction of Hg(NO₃)₂ with 4 equivalent KI in water afford K₂[HgI₄]. By using K₂[HgI₄] as the precursor, three new heterobimetallic compounds [Ni(N-MeIm)₆][HgI₄] (I), [Co(N-MeIm)₆][HgI₄] (II), and [Cu(N-MeIm)₆][HgI₄] (III) have been characterized by elemental analysis, IR spectra, and the singlecrystal X-ray crystallorgraphy analysis. Three complexes are isomorphous and crystallized in monoclinic symmetry space group P2₁/c. The coordination around each center metal(II) atom is octahedral with six nitrogen atoms of N-MeIm ligand. Each structure contains one tetrahedral [HgI₄]^2? as an anion to balance the charge of the molecular. Thermogravimetry analysis indicates these complexes have the similar departure process and cyclic voltammogram exhibits a significant pair of redox peaks.     

Synthesis and structure of [Hg2(L)2(NO3)2] (L = (4-nitrophenyl)pyridin-2-ylmethyleneamine); a theoretical study on Hg–Hg bond in this and in linear Hg2X2 (X = F, Cl, Br, I, Ph) complexes

A new binuclear mercury(I) complex, [Hg₂(L)₂(NO₃)₂] (L = (4-nitrophenyl)pyridin-2-ylmethyleneamine), 1, has been synthesized and characterized by CHN analyses, IR, UV–vis spectroscopy and X-ray crystal structure analysis. The complex contains a metal–metal bonded core, [Hg–Hg]²⁺, in which a single bidentate imine ligand is coordinated to each mercury atom. The Hg atoms have an additional interaction with the oxygen atom of the NO₃ ^? ion. Theoretical studies show that the interaction energy between the two {Hg(L)NO₃} fragments is about 45–59 kcal/mol depending on the level of calculation. The Mayer-Mulliken and Wiberg bond indices (WBI) for Hg–Hg bond at different levels of theory are about 0.75–0.88 and 0.60–0.70, respectively, and are significantly larger than that for Hg–N and Hg–O bonds. The NBO calculations by using different methods and basis sets also show that the S character in Hg–Hg bond is very large (94.65–97.81 %). All above data for this complex are compared with those for linear Hg₂X₂ (X = F,Cl, Br, I, Ph) complexes. Interestingly, the bond order for Hg–Hg bond in complex 1 is comparable with that for Hg₂F₂ and larger than those in above linear complexes. This is consistent with the experimental data indicating that the Hg–Hg bond in 1 is shorter than that in all above complexes, except Hg₂F₂.     

121Sb and57Fe Mössbauer spectra of antimony-containing iron carbonyl complexes: [HSb{Fe(CO)4}3]2− and [Sb{Fe(CO)4}4]3−

¹²¹Sb Mössbauer spectra of the title complexes, whose isomer shifts are intermediate between the organoantimony(III) and organoantimony(V) compounds, suggest that considerable electrons are donated from hydrido ligand and Fe(CO)₄ fragments to the antimony atom.     

Synthesis, Electrochemistry and Crystal Structure of the [Ni36Pt4(CO)45]6− and [Ni37Pt4(CO)46]6− Hexaanions

The [Ni₃₆Pt₄(CO)₄₅]^6- and [Ni₃₇Pt₄(CO)₄₆]^6- clusters have been obtained in mixture upon reaction in acetonitrile of [Ni₆(CO)₁₂]^2- salts with K₂PtCl₄ in a 2.5:1 molar ratio. The two hexaanions were indistinguishable by spectroscopic techniques. Crystallization of their trimethylbenzylammonium salts led to crystals of composition 0.5[NMe₃CH₂Ph]₆[Ni₃₆Pt₄(CO)₄₅]-0.5[NMe₃CH₂Ph]₆[Ni₃₇Pt₄(CO)₄₆]·C₃H₈O, hexagonal,space group P6₃ (No. 173), a=17.853(9), c=27.127(13) Å, Z=2; final R=0.057. The metal core of the [Ni₃₆Pt₄(CO)₄₅]^6- anion consists of a Pt₄ tetrahedron fully encapsulated in a shell of 36 Ni atoms belonging to a very distorted and incomplete ₅ tetrahedron. The [Ni₃₇Pt₄(CO)₄₆]^6- hexaanion derives from the former by capping the unique triangular face of the metal polyhedron with an additional Ni(CO) fragment. The [Ni₃₆Pt₄(CO)₄₅]^6--[Ni₃₇Pt₄(CO)₄₆]^6- mixture is rapidly degraded to the known [Ni₉Pt₃(CO)₂₁]^4- cluster by exposure to carbon monoxide. Its reaction with protic acids initially affords the corresponding [H_6-nNi₃₆Pt₄(CO)₄₅]^n--[H_6-nNi₃₇Pt₄(CO)₄₆]^n- (n=5, 4) derivatives, and eventually leads to rearrangement to the known [H_6-n Ni₃₈Pt₆(CO)₄₈]^n- species. Both [Ni₃₆Pt₄(CO)₄₅]^6--[Ni₃₇Pt₄(CO)₄₆]^6- and [HNi₃₆Pt₄(CO)₄₅]^5--[HNi₃₇Pt₄(CO)₄₆]^5- mixtures have been chemically and electrochemically reduced to their corresponding [Ni₃₆Pt₄(CO)₄₅]^n--[Ni₃₇Pt₄(CO)₄₆]^n- (n=7–9) and [HNi₃₆Pt₄(CO)₄₅]^n--[HNi₃₇Pt₄(CO)₄₆]^n- (n=6–8) mixtures.     

Double-tandem [4π+2π]·[2π+2π]·[4π+2π]·[2π+2π] synthetic sequence with photoprotolytic oxametathesis and photoepoxidation in the chromone series

Chromones are introduced into a double-tandem [4(π)+2(π)]·[2(π)+2(π)]·[4(π)+2(π)]·[2(π)+2(π)] synthetic sequence, culminating in photoprotolytic oxametathesis, which leads to an expeditious growth of molecular complexity over a few experimentally simple steps. The overall reaction can potentially be utilized in diversity-oriented synthesis, as it allows for three or more diversity inputs furnishing novel unique polycyclic scaffolds decorated with a variety of functionalities and aromatic/heterocyclic pendants. The polycyclic alkenes, resulting from the oxametathesis step, were found to undergo efficient and clean photoinduced epoxidation when irradiated in the presence of molecular oxygen.     

Fixation and reduction of molecular nitrogen by [WH4(PC2H5Ph2)4] and [WH4(PCH3Ph2)4] in a γ-radiation field

Hydride complexes of W(IV) with dpep (diphenylethylphosphine) and dpmp (diphenylmethylphosphine) were irradiated in thf+C₆H₁₂(11) solutions, saturated with N₂+H₂(13). Radiation yields of hydrazine, ammonia and amines were evaluated. The mechanism of reduction of molecular nitrogen is discussed.     

Crystal structure and magnetic properties of a three-dimensional complex constructed from [CuL]2+ and [Fe(CN)6]3− precursors

Self-assembly of the precursor [Cu(L)]²⁺ (L = 3,10-dipropyl-1,3,5,8,10,12-hexaazacyclotetradecane) with hexacyanometalate [Fe(CN)₆]³⁻ produces a 3-D cyano-bridged Cu(II)–Fe(III) bimetallic assembly, [CuL]₂[Fe(CN)₆]ClO₄ · H₂O (1), characterized by single-crystal X-ray diffraction studies, and magnetic measurements. The crystallographic determination reveals that each hexacyanoferromate(III) ion connects four copper(II) ions using four co-planar CN⁻ groups which axially coordinate to the copper ion in a trans fashion forming trans-CuL(N≡C)₂ moieties in (1). Magnetic studies reveal that (1) displays a ferromagnetic interaction between Cu(II) and Fe(III) through the CN linkage.     

从固相反应产物[NEt4]4[Mo2O2S6Cu6I4Br2]合成原子簇[MoOS3Cu3I(3,5-diMePy)4]·CH3CN和(EtN)4[Mo4Cu8O4S12{(Ph2PS)2}4](英文)

Treatment of iodide-bridged dimer [NEt4] 4[Mo2O2S6Cu6I4Br2] 1 with 3, 5-bimethylpyridine or with K[(Ph2PS) 2N] in CH3CN afforded the tetranuclear cluster [MoOS3Cu3I(3,5-diMePy)4]·CH3CN 2 and dodecanuclear cluster (Et4N)4[Mo4Cu8O4S12{(Ph2PS)2N}4] 3. Monomeric 2 possess a nest-shaped skeleton.The structure of oligomeric 3 can be regarded as a tetramer of nest-shaped MoCu3OS3[(Ph2PS)aN]groups co-polymerized by sharing the limbic Cu atoms.