Synthesis,molecular, crystal and electronic structure of [RuCl<Subscript>2</Subscript>(PPh<Subscript>3</Subscript>)<Subscript>2</Subscript>(3,5-Me<Subscript>2</Subscript>HPz)<Subscript>2</Subscript>]

The reaction of [RuCl₂(PPh₃)₃] complex with dimethylpyrazole has been examined. A new ruthenium complex—[RuCl₂(PPh₃)₂(3,5-Me₂HPz)₂] has been obtained and characterized by IR, ¹H NMR and UV-VIS measurements. Crystal and molecular structure of the complex has been determined. The electronic structure of the complex has been calculated by TDDFT method.     

The reaction between [RuCl<Subscript>2</Subscript>(PPh<Subscript>3</Subscript>)<Subscript>3</Subscript>] and hydroxyquinoline carboxylic acid

The reactions of [RuCl₂(PPh₃)₃] with 8-hydroxy-2-methyl-quinoline-7-carboxylic acid was examined, and a novel ruthenium(II) complex—[Ru(PPh₃)₂(C₅H₈NO)₂]—was obtained. The compound was studied by IR, UV–vis spectroscopy, and X-ray crystallography. The molecular orbital diagram of the complex was calculated with the density functional theory (DFT) method. The spin-allowed singlet–singlet electronic transitions of the compound were calculated using the time-dependent DFT method, and the UV–vis spectrum of the compound was discussed, on this basis. The luminescence property of the [Ru(PPh₃)₂(C₅H₈NO)₂]was examined.     

Steric distortion of planar NiP<Subscript>2</Subscript>N<Subscript>2</Subscript> chromophores: a spectral,cyclic voltammetric and single crystal X-ray structural study

The complexes trans-[Ni(4-MP)₂(NCS)₂]·MeCN (1) and trans-[Ni(3-MP)₂(NCS)₂] (2) (4-MP = tri(4-methylphenyl)phosphine, 3-MP = tri(3-methylphenyl)phosphine) were prepared and characterized by IR, UV–visible, NMR spectra, CV, TGA and single crystal X-ray crystallography. Both the complexes have planar geometry and are diamagnetic. The Ni–P distances in both complexes are relatively short as a result of strong back donation from nickel to phosphorus. The phenyl rings in the 3-MP analogue (2) show increased pitching with reference to the plane formed by the ipso carbons due to increased steric effects. For complex (2), the N–Ni–N and P–Ni–P angles are significantly lower than the almost linear N–Ni–N and N–Ni–P angles observed for both complex (1) and trans-[Ni(PPh₃)₂(NCS)₂]. This observation indicates that the 3-methylphosphine ligand forces complex (2) to distort towards a tetrahedral geometry. IR spectra of both complexes show strong bands around 2,090 cm⁻¹ due to N-coordinated thiocyanate, while the electronic spectra contain d–d transitions around 452 nm. Cyclic voltammograms show that the irreversible one-electron reduction potentials increase in the following order: trans- [Ni(PPh₃)₂(NCS)₂] < trans- [Ni(3-MP)₂(NCS)₂] < trans-[Ni(4-MP)₂(NCS)₂], revealing the electron releasing effect of the methyl groups. The planar complexes exhibit interallogony in coordinating solvents.     

Synthesis and characterization of η<Superscript>3</Superscript>-allyl palladium(II) complexes with Ph<Subscript>2</Subscript>P(S)CHP(S)Ph<Subscript>2</Subscript> and OC(CF<Subscript>3</Subscript>)CHCO(C<Subscript>4</Subscript>H<Subscript>3</Subscript>S) co-ligands

The new complexes [(η³-Me₂CCMeCH₂)Pd{η²-Ph₂P(S)CHP(S)Ph₂] (1), [(η³-Me₂CCMeCH₂)Pd{η²-OC(CF₃) CHCO(C₄H₃S)}] (2) and [(η³-CH₂CMeCH₂)Pd{η²-OC(CF₃)CHCO(C₄H₃S)}] (3) have been synthesized by reacting [(η³-allyl)Pd(μ-Cl)]₂ with Ph₂P(S)CH₂P(S)Ph₂ and OC(CF₃)CH₂CO(C₄H₃S) in the presence of base. All have been characterized by elemental analysis, FT-IR, ¹H-n.m.r and FAB-mass spectroscopy. Spectroscopic studies suggest that both ligands are bidentate, forming six-membered Pd-S-P-C-P-S and Pd-O-C-C-C-O palladacycles, the η³-allyl group completing the coordination sphere.     

Synthesis,structure, and NO-donor activity of the paramagnetic complex [Fe<Subscript>2</Subscript>(SC<Subscript>3</Subscript>H<Subscript>5</Subscript>N<Subscript>2</Subscript>)<Subscript>2</Subscript>(NO)<Subscript>4</Subscript>] as a model of nitrosyl [2FE-2S] proteins

The neutral dinuclear iron nitrosyl complex [Fe₂(SC₃H₅N₂)₂(NO)₄] (1) of the “g = 2.03” family with a ligand analogous to natural mercaptohistidine was synthesized by the metathesis reaction of the thiosulfate ligands in the [Fe₂(S₂O₃)₂(NO)₄]²⁻ anion with imidazolidine-2-thiolate ligands. The electrochemical determination of nitrogen oxide in solution showed that compound 1 has a lower NO-donor ability compared to the iron complexes with 1-methylimidazole-2-thiol and imidazole-2-thiol synthesized earlier. Study of the magnetic properties of polycrystals of 1 demonstrated that the effective magnetic moment at room temperature is ca. 2.45 μ_B and corresponds to a molecule containing a pair of the noninteracting spins S = 1/2. This is evidence that each iron coordination unit in complex 1 contains one unpaired electron, and the iron atom is in the low-spin state. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 28–34, January, 2007.     

Synthesis and catalytic epoxidation potential of oxodiperoxo molybdenum(VI) complexes with 2-hydroxybenzohydroxamate and 2-hydroxybenzoate: the crystal structure of PPh<Subscript>4</Subscript>[MoO(O<Subscript>2</Subscript>)<Subscript>2</Subscript>(HBA)]

(PPh₄)₂[MoO(O₂)₂(SHAH)]·H₂O and PPh₄[MoO(O₂)₂(HBA)] (SHAH₃ = 2-hydroxybenzohydroxamic acid and HBAH = 2-hydroxybenzoic acid) have been synthesized and characterized by physico-chemical and spectroscopic methods. In addition, the second complex has been structurally characterized by single-crystal X-ray diffraction analysis. We have compared the catalytic activities of these two new complexes, together with the previously reported PPh₄[MoO(O₂)₂(BZ)] (BZH = benzoic acid), with respect to the epoxidation of alkenes. The hydroxamate complex is the most efficient catalyst among the three complexes, showing excellent catalytic activity for the substrates cyclohexene, cyclooctene, cinnamyl alcohol, pent-4-en-1-ol and hex-1-ene.     

Cyclotrimerization and linear oligomerization of phenylacetylene on the nickel(I) monocyclopentadienyl complex CpNi(PPh<Subscript>3</Subscript>)<Subscript>2</Subscript>

The reactions of the CpNi(PPh₃)₂ monocyclopentadienyl complex with phenylacetylene and diphenylacetylene in toluene have been studied by ESR. When an alkyne is in twofold molar excess over nickel, it substitutes rapidly for PPh₃ ligands to form the bisalkyne π complex CpNi(η²-C₂PhR)₂, where R = H or Ph. In the case of phenylacetylene, two structural isomers of the Ni(I) π complex have been identified. Irreversible clustering occurs in the system as time passes. When phenylacetylene is in excess, it oligomerizes actively at ambient temperature. The composition of the oligomerization products depends substantially on the reaction temperature: at T = 20°C, the main product is 1,2,4-triphenylbenzene (97% of the conversion products); at T = 40°C, the main products are linear oligomers with an average molecular weight of 1050. The formation and stabilization of active complexes in the system take place when the substrate is in excess. Phenylacetylene trimerization and linear oligomerization schemes in which the Ni(I) monocyclopentadienyl complex stabilized by substrate molecules is the active species are suggested.     

Electron interactions in the (η<Superscript>2</Superscript>-C<Subscript>60</Subscript>)Pd[P(Ph<Subscript>2</Subscript>)C<Subscript>5</Subscript>H<Subscript>4</Subscript>]<Subscript>2</Subscript>Fe complex

The electronic structure of the (η²-C₆₀)Pd[P(Ph₂)C₅H₄]₂Fe complex was calculated by the “hybrid” B3LYP method. Comparison of the experimental X-ray emission C-Kα spectrum and theoretical spectrum of the compound demonstrated that the electron interactions between the C₆₀ core, palladium atom, and organometallic fragment are described correctly in the framework of the quantum chemical method used. The electronic structure of the organometallic fullerene complex can be presented as a set of blocks of orbitals corresponding to different types of chemical bond. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2640–2644, December, 2005.     

Kinetics and mechanisms of homogeneous catalytic reactions: Part 13. Regioselective reduction of quinoline catalysed by Rh(acac)(CO)[P(<Superscript>t</Superscript>Bu)(CH<Subscript>2</Subscript>CH=CH<Subscript>2</Subscript>)<Subscript>2</Subscript>]

The complex Rh(acac)(CO)[P(^tBu)(CH₂CH=CH₂)₂] (1) proved to be an efficient precatalyst for the regioselective hydrogenation of quinoline (Q) to 1,2,3,4-tetrahydroquinoline (THQ) under mild reaction conditions (125 °C and 4 atm H₂). A kinetic study of this reaction led to the rate law:

$$ r \, = \{ K_{1} k_{2} /(1 \, + \, K_{1} {\text{H}}_{ 2} )\} [{\text{Rh}}][{\text{H}}_{ 2} ]^{2} $$

which becomes

$$ r \, = \, K_{1} k_{2} [{\text{Rh}}][{\text{H}}_{ 2} ]^{2} $$

at hydrogen pressures below 4 atm. The active catalytic species is the cationic complex {Rh(Q)₂(CO)[P(^tBu)(CH₂CH=CH₂)₂]}⁺ (2). The mechanism involves the partial hydrogenation of one coordinated Q of (2) to yield a complex containing a 1,2-dihydroquinoline (DHQ) ligand, {Rh(DHQ)(Q)(CO)[P(^tBu)(CH₂CH=CH₂)₂]}⁺ (3), followed by hydrogenation of the DHQ ligand to give THQ and a coordinatively unsaturated species {Rh(Q)(CO)[P(^tBu)(CH₂CH=CH₂)₂]}⁺ (4); this reaction is considered to be the rate-determining step. Coordination of a new Q molecule to (4) regenerates the active species (2) and restarts the catalytic cycle.

     

Sulfur‐assisted Chloride and Triphenylphosphine Dissociation of Palladium(II) Complex with Phenyloxythiocarbonyl,PhOC(S), Containing Ligand: X‐Ray Structure of [Pd(PPh3)2{η1‐C(S)OPh}(Cl)]

Treatment of Pd(PPh₃)₄ with phenylchlorothionoformate, PhOC(S)Cl, in dichloromethane at ?20 °C produces the phenyloxythiocarbonyl complex [Pd(PPh₃)₂{η¹‐C(S)OPh}(Cl)], 1 . The ³¹P{¹H} NMR spectrum of 1 shows the dissociation of either the chloride or the triphenylphosphine ligand to form complex [Pd(PPh₃)₂(η²‐SCOPh)][Cl], 2 or the dipalladium complex [Pd(PPh₃)Cl]₂(μ,η²‐SCOPh)₂, 3 . Continuous stirring of the dichloromethane solution of 1 at room temperature for 4 h forms the dipalladinum complex [Pd(PPh₃)Cl]₂(μ,η²‐SCOPh)₂, 3 as the final product. Respective reactions of 1 and Et₂NCS₂Na or dppa {bis(diphenylphosphino)amine} gives complex [Pd(PPh₃){η¹‐C(S)OPh}(η²‐S₂CNEt₂)], 4 or [Pd(PPh₃){η¹‐C(S)OPh}(η²‐dppa)][Cl], 5 . Complex 1 is determined by single‐crystal X‐ray diffraction and crystallized in the monoclinic space group P2₁ with Z = 4. The cell dimensions of 1 are as follows: a = 9.5613(1) Å, b = 33.6732(3) Å, c = 12.2979(1) Å.     

Mononuclear and heterobimetallic palladium(II) and platinum(II) complexes containing the mixed ligands <Emphasis Type="Italic">N</Emphasis>-(2-pyridyl or 2-pyrimidyl) acetamide and tertiary diphosphine

Palladium(II) and platinum(II) complexes containing mixed ligands N-(2-pyridyl)acetamide (AH) or N-(2-pyrimidyl)acetamide (BH) and the diphosphines Ph₂P(CH₂) _n PPh₂, (n = 1, 2 or 3) have been prepared. The prepared complexes [Pd(A)₂(diphos)] or [Pd(B)₂(diphos)] have been used effectively to prepare bimetallic complexes of the type [(diphos)Pd(μ-L)₂M′Cl₂] where M′ = Co, Cu, Mn, Ni, Pd, Pt or SnCl₂; L = A or B. The prepared complexes were characterized by elemental analysis magnetic susceptibility, i.r. and UV–Vis spectral data. ³¹P–{¹H}-n.m.r. data have been applied to characterize the produced linkage isomers.     

First heteroleptic Mo<Subscript>3</Subscript>S<Subscript>7</Subscript> clusters containing non-innocent phenanthroline ligands

Reaction of the thiobromide [Mo₃S₇Br₆]²⁻ cluster anion with 5,6-dimethyl-1,10-phenanthroline (Me₂Phen) in solution leads to the substitution of two bromide ligands and the subsequent formation of a new mixed-ligand neutral complex [Mo₃S₇Br₄(Me₂Phen)] (I). Reaction of [Mo₃S₇Br₆]²⁻ with 5,6-dimethyl-1,10-phenanthroline in CH₂Cl₂ followed by treatment of I with Na(Dtc) · 3H₂O (Dtc = diethyldithiocarbamate) results in the new mixed-ligand cluster complex [Mo₃S₇(Dtc)₂(Me₂Phen)]²⁺ (IIa). Slow evaporation of the CHCl₃ solution of the complex in the presence of PF₆⁻ gives crystals of {[Mo₃S₇(Dtc)₂(Me₂Phen)]Br}PF₆ · 3CHCl₃ (II) characterized by X-ray structural analysis. Close contacts S...S result in the formation of cationic dimers {[Mo₃S₇(Dtc)₂(Me₂Phen)]₂}⁴⁺ which form infinite chains through additional S_ax...Br contacts. All compounds were characterized by IR, elemental analysis and ESI-MS. Synthesized complexes represent the first examples of heteroleptic Mo₃S₇ clusters containing phenanthroline ligands.     

XAFS investigation of [Pd(NH<Subscript>3</Subscript>)<Subscript>4</Subscript>][AuCl<Subscript>4</Subscript>]<Subscript>2</Subscript> and its thermolysis products

Thermolysis of double complex salt [Pd(NH₃)₄][AuCl₄]₂ has been studied in helium atmosphere from ambient to 350 °C. The XAFS of Pd K and Au L₃ edges and thermogravimetry measurements have been carried out to characterize the intermediates and the final product. In the temperature range 115–160 °C the complex is decomposed to form Pd(NH₃)₂Cl₂ and AuCl_4−x N _x species with x ranging from 2 to 3. Subsequent heating of the intermediate up to 300 °C leads to the total loss of NH₃. The Au–Cl and Au–Au bonds form the local environment of Au at the stage of decomposition while only four chlorine atoms are around Pd. At the temperature of 330 °C the Au and Pd nanoparticles as well as residues of palladium chloride are detected. The final product consists of separated Au and Pd nanoparticles.     

Ruthenium Carbonyl Cluster Complexes with Phenylgermyl Ligands from the Reactions of Ph<Subscript>3</Subscript>GeH with Ru(CO)<Subscript>5</Subscript> and Ru<Subscript>3</Subscript>(CO)<Subscript>12</Subscript>

Four new triphenylgermylruthenium carbonyl compounds HRu(CO)₄GePh₃, 14; Ru(CO)₄(GePh₃)₂, 15; Ru₂(CO)₈(GePh₃)₂, 16; and Ru₃(CO)₉(GePh₃)₃(μ-H)₃, 17 were obtained from the reaction of Ru(CO)₅ with Ph₃GeH in hexane solvent at reflux, 68 °C. The major product 14 was formed by loss of CO from the Ru(CO)₅ and an oxidative addition of the GeH bond of the Ph₃GeH to the metal atom. This six coordinate complex contains one terminal hydrido ligand. Compound 15 is formed from 14 and contains two trans-positioned GePh₃ ligands in the six coordinate complex. Compound 16 contains two Ru(CO)₄(GePh₃) fragments joined by an Ru–Ru single bond. Compound 17 contains a triangular cluster of three ruthenium atoms with three bridging hydrido ligands and one terminal GePh₃ ligand on each metal atom. When heated to 125 °C, 14 was converted to the new triruthenium compound Ru₃(CO)₁₀(μ-GePh₂)₂, 18. Compound 18 consists of a triangular tri-ruthenium cluster with two GePh₂ ligands bridging two different edges of the cluster and one bridging CO ligand. Ru₃(CO)₁₂ was found to react with Ph₃GeH at 97 °C to yield three products: 15, and two new compounds Ru₃(CO)₉(μ-GePh₂)₃, 19 and Ru₂(CO)₆(μ-GePh₂)₂(GePh₃)₂, 20 were obtained. Compound 19 is similar to 18 having a triangular tri-ruthenium cluster but has three bridging GePh₂ ligands, one on each Ru–Ru bond. Compound 20 contains only two ruthenium atoms joined by a single Ru–Ru bond that has two bridging GePh₂ ligands and a terminal GePh₃ ligand on each metal atom. All compounds were characterized by a combination of IR, ¹H NMR, single-crystal X-ray diffraction analyses. This report is dedicated to Professor Dieter Fenske on the occasion of his 65th birthday for his many pioneering contributions to the chemistry of metal chalcogenide cluster complexes.     

Hydrothermal synthesis and crystal structure of [Ni(Bptc)<Subscript>2</Subscript>(Bimb)<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>]

In the compound [Ni(Bptc)₂(Bimb)₂(H₂O)₂] (I), where H₄Bptc is 3,3′,4,4′-biphenyltetracarboxylic acid; Bimb is 4,4′-bis(1-imidazolyl)biphenyl), Ni(II) has a distorted octahedral coordination geometry, which was bonded with two N atoms from two Bimb ligands, two O atoms from two H₂Bptc²⁻ ligands and two water O atoms. The crystal structure of compound I is stabilized by the π-π-stacking and hydrogen bonds interaction.     

Studies on the copolymerization of norbornene with CO catalyzed by a new catalytic system PdCl<Subscript>2</Subscript>/phen/M(CF<Subscript>3</Subscript>SO<Subscript>3</Subscript>)<Subscript>n</Subscript>

A new three-component catalytic system, PdCl₂/phen/M(CF₃SO₃)_n where M = La, Y, Yb, Zn, and Cu, was studied for the copolymerization of norbornene (NBE) with CO to prepare polyketone (PK). It was found that the CF₃SO₃H catalytic system gave a low catalytic activity for the copolymerization of norbornene with CO, but when M(CF₃SO₃)_n was introduced instead of CF₃SO₃H, the PdCl₂/phen/M(CF₃SO₃)_n catalytic system exhibited much higher activity. The effects of ligands, M(CF₃SO₃)_n, solvents, and temperatures on the copolymerization have been discussed in detail. The results showed that with 1,10-phenanthroline (phen) and Cu(CF₃SO₃)₂ used as cocatalysts, the corresponding reaction rate reached 82 000 g PK (mol Pd)⁻¹h⁻¹ when the reaction was carried out in methanol at 90°C and 3.0 MPa of CO, and the weight average molecular weight (M _w) of the resultant copolymer is 1090 g/mol. The copolymer was characterized with various techniques such as FT-IR, ¹HNMR, ¹³CNMR, TGA, and DSC. The infrared spectrum of the product includes two features at 1697 and 1732 cm⁻¹ for the NBE/CO copolymer in CH₃OH that are attributed to carbonyl groups in ketones (repeating unit) and esters (end group), respectively. Due to the tension of the ring of norbornene, the degree of copolymerization is not high. Published in Russian in Kinetika i Kataliz, 2007, Vol. 48, No. 1, pp. 51–58. This article was submitted by the authors in English.     

A study of complexation between crystalline <Emphasis Type="Italic">trans</Emphasis>-[Pd(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>(NO<Subscript>3</Subscript>)<Subscript>2</Subscript>] and acetylacetone

Complexation between crystalline trans-[Pd(H₂O)₂(NO₃)₂] and acetylacetone was studied. The complexes Pd₂(Acac)₂(μ-NO₃)₂(I) and Pd₂(Acac)₂(μ-Acac)(μ-NO₃)(II) were obtained and examined by elemental analysis, X-ray powder diffraction analysis, differential scanning calorimetry, simultaneous thermal analysis, mass spectrometry, and vibrational spectroscopy.     

Synthesis and characterization of the [Ru<Subscript>3</Subscript>O(CH<Subscript>3</Subscript>COO)<Subscript>6</Subscript>(py)<Subscript>2</Subscript>(BPE)Ru(bpy)<Subscript>2</Subscript>Cl](PF<Subscript>6</Subscript>)<Subscript>2</Subscript> dimer

The polymetallic [Ru₃O(CH₃COO)₆(py)₂(BPE)Ru(bpy)₂Cl](PF₆)₂ complex (bpy = 2,2′-bipyridine, BPE = trans-1,2-bis(4-pyridil)ethylene and py = pyridine) was assembled by the combination of an electroactive [Ru₃O] moiety with a [Ru(bpy)₂(BPE)Cl] photoactive centre, and its structure was determined using positive ion electrospray (ESI-MS) and tandem mass (ESI-MS/MS) spectrometry. The [Ru₃O(CH₃COO)₆(py)₂(BPE)Ru(bpy)₂Cl]²⁺ doubly charged ion of m/z 732 was mass-selected and subject to 15 eV collision-induced dissociation, leading to a specific dissociation pattern, diagnostic of the complex structure. The electronic spectra display broad bands at 409, 491 and 692 nm ascribed to the [Ru(bpy)₂(BPE)] charge-transfer bands and to the [Ru₃O] internal cluster transitions. The cyclic voltammetry shows five reversible waves at −1.07 V, 0.13 V, 1.17 V, 2.91 V and −1.29 V (vs SHE) assigned to the [Ru₃O]^{−1/0/+1/+2/+3} and to the bpy^0/−1 redox processes; also a wave is observed at 0.96 V, assigned to the Ru^+2/+3 pair. Despite the conjugated BPE bridge, the electrochemical and spectroelectrochemical results indicate only a weak coupling through the π-system, and preliminary photophysical essays showed the compound decomposes under visible light irradiation.     

Synthesis of pyridyl derivatives for the future functionalization of biomolecules labeled with the fac-[<Superscript>188</Superscript>Re(CO)<Subscript>3</Subscript>(H<Subscript>2</Subscript>O)<Subscript>3</Subscript>]<Superscript>+</Superscript> precursor

In this paper, we investigated three ligand systems, symmetric and asymmetric pyridyl-containing tridentate ligands (L¹NH₂ = (bis(2-pyridylmethyl)-amino)-ethylamine, L²H = (bis(2-pyridylmethyl)-amino)-acetic acid, L³NH₂ = [(6-amino-hexyl)-pyridyl-2-methyl-amino]-acetic acid) as bifunctional chelating agents for labeling biomolecules. These ligands reacted with the precursor fac-[¹⁸⁸Re(CO)₃(H₂O)₃]⁺ and yielded the radioactive complexes fac-[¹⁸⁸Re(CO)₃L] (L = three ligands), which were identified by RP-HPLC. The corresponding stable rhenium tricarbonyl complexes (1–3) were allowed for macroscopic identification of the radiochemical compounds. ¹⁸⁸Re tricarbonyl complexes, with log P _o/w values ranging from −1.36 to −0.32, were obtained with yields of ≥90% using ligand concentrations within the 10⁻⁶−10⁻⁴M range. Challenge studies with cysteine and histidine revealed the high stability properties of these radioactive complexes, and biodistribution studies in normal mice indicated a fast rate of blood clearance and high rate of total radioactivity excretion, primarily through the renal-urinary pathway. In summary, these asymmetric and symmetric pyridyl-containing tridentate ligands are potent bifunctional chelators for the future biomolecules labeling of fac-[¹⁸⁸Re(CO)₃(H₂O)₃]⁺.     

Synthesis and structure of the polymeric complex [Ag<Subscript>2</Subscript>(Ph<Subscript>3</Subscript>P)<Subscript>2</Subscript>B<Subscript>10</Subscript>H<Subscript>10</Subscript>]<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript>

A method for the synthesis of the silver(I) complex with the closo-decaborate anion and triphenylphosphine [Ag₂(Ph₃P)₂B₁₀H₁₀] _n was developed and the structure of this complex was studied. The polymeric chain of the complex is formed with participation of Ag(I) atoms, which coordinate the B₁₀H₁₀²⁻ anions through the apical (B(1)–B(2), B(9)–B(10)) and equatorial (B(3)–B(6), B(5)–B(8)) edges, the metalligand bonding occurring through three-center two-electron bonds (MHB). The P atoms of two triphenylphosphine molecules are also incorporated in the inner coordination sphere of the metal: the CN of the silver atom is 4 + 1.