Synthesis of μ-diborolyl triple-decker complexes [CpCo(1,3-C<Subscript>3</Subscript>B<Subscript>2</Subscript>Me<Subscript>5</Subscript>)Ru(arene)]<Superscript>+</Superscript>

Cationic triple-decker complexes [CpCo(1,3-C₃B₂Me₅)Ru(arene)]PF₆ (arene is benzene (2a), p-cymene (2b)) with a bridging diborolyl ligand were synthesized by the reaction of the sand-wich anion [CpCo(1,3-C₃B₂Me₅)]⁻ (1) with [(arene)RuCl₂]₂. The structure of [2b]PF₆ was confirmed by X-ray diffraction analysis.     

Synthesis of dicationic μ-diborolyl triple-decker complexes [CpCo(μ-1,3-C<Subscript>3</Subscript>B<Subscript>2</Subscript>Me<Subscript>5</Subscript>)M(C<Subscript>6</Subscript>H<Subscript>6</Subscript>)]<Superscript>2+</Superscript> (M = Rh,Ir)

Dicationic triple-decker complexes [CpCo(μ-1,3-C₃B₂Me₅)M(C₆H₆)]²⁺ (M = Rh (3), Ir (4)) were synthesized by the reaction of [CpCo(μ-C₃B₂Me₅)MBr₂]₂ (M = Rh, Ir) with benzene in the presence of AgBF₄. The structure of 3(BF₄)₂ was determined by X-ray diffraction analysis.     

Photochemical replacement of benzene in the tetramethylcyclopentadienyl complex of iron, [η-C<Subscript>5</Subscript>Me<Subscript>4</Subscript>H)Fe(η-C<Subscript>6</Subscript>H<Subscript>6</Subscript>)]<Superscript>+</Superscript>

Irradiation of the cation [η-C₅Me₄H)Fe(η-C₆H₆)]⁺+ (1) and Bu^tNC with visible light in acetonitrile results in the displacement of the benzene ligand, giving [(η-C₅Me₄H)Fe(Bu^tNC)₃]+ (2). Reactions of complex 1 with P(OR)₃ and dppe in M_eCN yield the complexes [(η-C₅Me₄H)-Fe(M_eCN)P(OR)_{3 2}]+ (R = Me (3) and Et (4)) and [(η-C₅Me₄H)Fe(MeCN)(dppe)]+ (5) containing two Fe—P bonds. The same reactions in CH₂Cl₂ give the tris(phosphite) complexes [(η-C₅Me₄H)FeP(OR)_{3 3}]+ (6, 7). A photochemical reaction of complex 1 with pentaphos-phaferrocene Cp*Fe(η-cyclo-P₅) yields the triple-decker cation [(η-C₅Me₄H)Fe(μ-η:η-cyclo-P₅)FeCp*]+ (8) with a bridging pentaphospholyl ligand. Structures [2]PF₆ and [3]PF₆ were identified by X-ray diffraction.     

Thermal arene exchange in the naphthalene complex [CpRu(η<Superscript>6</Superscript>-C<Subscript>10</Subscript>H<Subscript>8</Subscript>)]<Superscript>+</Superscript>

Naphthalene in the [CpRu(⁶−C₁₀H₈)]⁺ complex (1) is substituted for other arenes under reflux in 1,2-dichloroethane to form the [CpRu(⁶-arene)]⁺ cations (arene = C₆H₆, 1,2-C₆H₄Me₂, 1,2,4,5-C₆H₂Me₄, or C₆Me₆) in 70–80% yields. The reaction is accelerated in the presence of a catalytic amount of acetonitrile. The structure of [1]PF₆ was established by X-ray diffraction.     

Routes to Higher Nuclearity Mixed-Metal Carbonyl Clusters Using the [Rh(η<Superscript>5</Superscript>-C<Subscript>5</Subscript>Me<Subscript>5</Subscript>)(NCMe)<Subscript>3</Subscript>]<Superscript>2+</Superscript> Dication as a Building Block

Reaction of the [Rh(η⁵-C₅Me₅)(NCMe)₃]²⁺ (1) dication with the hexaosmium [Os₆(CO)₁₇]²⁻ (2) dianion leads to the initial formation of [Os₆(CO)₁₇Rh(η⁵-C₅Me₅)] (3). This cluster readily adds CO to form [Os₆(CO)₁₈Rh(η⁵-C₅Me₅)] (4) which has been characterised crystallographically. 3 also adds dihydrogen to give [Os₆H₂(CO)₁₇Rh(η⁵-C₅Me₅)] (5) and undergoes a substitution reaction with PPh₃ to form [Os₆(CO)₁₆(PPh₃)Rh(η⁵-C₅Me₅)] (6). With the [Ru₆(CO)₁₈]²⁻ (7) dianion, [Rh(η⁵-C₅Me₅)(NCMe)₃]²⁺ (1) reacts to form three mixed-metal clusters [Ru₅(CO)₁₅Rh(η⁵-C₅Me₅)] (8), [Ru₆(CO)₁₈Rh(η⁵-C₅Me₅)] (9) and [Ru₆(CO)₁₈Rh₂(η⁵-C₅Me₅)₂] (10). The clusters have been characterised spectroscopically and the structures of 8 and 10 have been confirmed crystallographically. The cluster 8 undergoes a substitution reaction with P(OMe)₃ to form the disubstituted product [Ru₅(CO)₁₃(P(OMe)₃)₂Rh((η⁵-C₅Me₅)] (11) which has also been characterised crystallographically.     

Sb(III) fluoride complexes with DL-valine. Crystal structure of molecular complex SbF<Subscript>3</Subscript>{(CH<Subscript>3</Subscript>)<Subscript>2</Subscript>CHCH(<Superscript>+</Superscript>NH<Subscript>3</Subscript>)COO<Superscript>−</Superscript>}

Preparative method in combination with X-ray diffraction and IR spectroscopy is used to study reaction of Sb(III) fluoride with -aminoisovaleric acid (DL-valine) in an aqueous solution in the range of the molar ratios of components (0.25–2) : 1 in the presence of hydrofluoric acid. The molecular complex of Sb(III) fluoride with valine (1 : 1) of the composition SbF₃{(CH₃)₂CHCH(⁺NH₃)COO^–}(I) and valinium tetrafluoro-antimonate(III) monohydrate {(CH₃)₂CHCH(₊NH₃)COOH}SbF₄· H₂O (II) are synthesized for the first time. Crystal structure was determined for the molecular complex I consisting of SbF₃ groups and valine molecules united into polymer chains through bidentate bridging carboxylate groups of amino acid molecules.Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 2, 2005, pp. 125–131.Original Russian Text Copyright © 2005 by Zemnukhova, Davidovich, Udovenko, Kovaleva.     

Photochemical arene exchange in the naphthalene complex [CpRu(η<Superscript>6</Superscript>-C <Subscript>10</Subscript>H<Subscript>8</Subscript>)]<Superscript>+</Superscript>

The cation [CpRu(η⁶-C₁₀H₈)]⁺ was shown to exchange naphthalene for other arenes under visible-light irradiation to form the complexes [CpRu (η⁶-arene)]⁺ (arene = C₆H₆, 1,4-C₆H₄Me₂, 1,3,5-C₆H₃Me₃, or 1,2,4,5-C ₆H₂Me₄) in 70–95% yields. The reaction rate of exchange decreases in the series arene = 1,4-C₆H₄Me₂ > C₆H₆ > 1,3,5-C₆H₃Me₃ > 1,2,4,5-C ₆H₂Me₄ >> C₆Me₆ and increases with the coordinating ability of the solvent in the order CH₂Cl₂ < THF—CH₂Cl₂ mixture (1: 1) < acetone.     

(Indenyl)iridacarborane (η<Superscript>5</Superscript>-indenyl)Ir(η-7,8-C<Subscript>2</Subscript>B<Subscript>9</Subscript>H<Subscript>11</Subscript>): synthesis,structure, and bonding

A reaction of iodide [(η⁵-indenyl)IrI₂]_n (1) with thallium dicarbollide Tl[Tl(η-7,8-C₂B₉H₁₁)] leads to (indenyl)iridacarborane (η⁵-indenyl)Ir(η-7,8-C₂B₉H₁₁) (2) in 32% yield. The X-ray diffraction study showed that in the structure of 2, the five-membered rings C₅ and C₂B₃ have a cisoid conformation, in which the bridgehead carbon atoms of the indenyl ligand are arranged opposite to the carborane cage carbon atoms. The DFT calculations showed that the Ir—indenyl bond in compound 2 is weaker than the Ir—Cp bond in the complex (η-7,8-C₂B₉H₁₁)IrCp.     

Crystal structure of [(C<Subscript>6</Subscript>H<Subscript>5</Subscript>)<Subscript>4</Subscript>P][Ni(B<Subscript>9</Subscript>C<Subscript>2</Subscript>H<Subscript>11</Subscript>)<Subscript>2</Subscript>]·CCl<Subscript>4</Subscript>

A new compound containing the tetraphenylphosphonium cation and the nickel(III) bisdicarbollyl anion, [(C₆H₅)₄P][Ni(B₉C₂H₁₁)₂]·CCl₄, was synthesized and investigated by XRD at room temperature (295 K). Crystal data: C₂₉H₄₂B₁₈PCl₄Ni, M = 816.69, monoclinic, space group P2/c; unit cell parameters a = 13.5873(6) Å, b = 7.1475(2) Å, c = 20.7829(8) Å, β = 94.4595(13)°, V = 2012.2(2) ų, Z = 2, d _calc = 1.348 g/cm³. The structure was solved by direct and Fourier methods and refined by the full-matrix least squares method in an anisotropic (isotropic for H) approximation to the final R ₁ = 0.0466 for 3055 I _hkl ≥ 2σ _I of 23,655 reflections collected and 5618 independent I _hkl (Bruker X8 APEX diffractometer, λMoK _α).     

Mercury complex [(HOCH<Subscript>2</Subscript>)<Subscript>3</Subscript>CNH<Subscript>3</Subscript>]<Stack><Subscript>2</Subscript><Superscript>+</Superscript></Stack> [HgI<Subscript>4</Subscript>]<Superscript>2−</Superscript>: Synthesis and structure

The complex [(HOCH₂)₃CNH₃] ₂ ⁺ [HgI₄]^2? (I) was synthesized by reacting (trioxymethyl)methylammonium iodide with mercury dioide (2: 1 mol/mol) in acetone. X-ray crystallography shows that the complex consists of two types of crystallographically independent [(HOCH₂)₃CNH₃]⁺ cations and tetrahedral anions [HgI₄]^2? (IHgI, 106.49(2)°–113.99(4)°; Hg-I, 2.7849(8)-2.8105(8) Å. [(HOCH₂)₃CNH₃]⁺ cations are linked via hydrogen bonds O…H-N and O-H…N (O…N, 2.84–2.92 Å) to form polymer chains, which are cross-linked with one another via anions (I…H, 2.81, 2.82 Å).     

Stable cyclopentadienyl-type fullerenyl radical Me<Subscript>5</Subscript>C<Stack><Subscript>60</Subscript><Superscript>•</Superscript></Stack>: experimental detection by EPR spectroscopy and quantum chemical calculations

A paramagnetic compound was detected in the synthesis of a hydride (Me)₅C₆₀H with an isolated cyclopentadienyl ring. The EPR spectrum of this compound corresponds to free radical (Me)₅C₆₀• with nonequivalent Me-group protons. The structure of the radical was confirmed by quantum chemical calculations. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1597–1599, August, 2008.     

Stabilization of [Sc(NCS)<Subscript>6</Subscript>]<Superscript>3−</Superscript> anion by [M(18C6)]<Superscript>+</Superscript> complexes in solvation systems

The [M(18C6)]₄[Sc(NCS)₆]Cl · nH₂O complexes were established to form in the solutions ScCl _x -Solv-MNCS-18C6, where Solv is ethanol, THF, acetonitrile, or isopropyl alcohol; M = Na, K; 18C6 is 1,4,7,10,13,16-hexaoxocyclooctadecane. X-ray diffraction analysis of [K(18K6)]₄[Sc(NCS)₆]Cl · 3.33H₂O showed that the thiocyanate ion was coordinated by Sc through the N atom. The structure consists of octahedral Sc(NCS) ₆ ^3? that are united via nonvalent K-S interaction with macrocyclic dimers [M(18C6)]₂ into chains. Each 18C6 molecule coordinates one K atom.     

Reaction of the [B<Subscript>10</Subscript>H<Subscript>9</Subscript>O<Subscript>2</Subscript>C<Subscript>4</Subscript>H<Subscript>8</Subscript>]<Superscript>–</Superscript> anion with C-nucleophiles

The reactions of 1,4-dioxane-substituted closo-decaborate anion ([B₁₀H₉O₂C₄H₈]^–) with metal acetylenides, diethyl malonate, ethyl acetoacetate, triethyl orthoformate, acetylacetone, and malonodinitrile were studied. The reactions were shown to be accompanied with substituent ring opening and attachment of the corresponding pendant functional group. The obtained compounds were characterized by various physicochemical methods (IR and polynuclear NMR spectroscopy, ESI mass spectrometry).     

Synthesis and crystal structure of Rb<Subscript>2</Subscript>[(UO<Subscript>2</Subscript>)<Subscript>2</Subscript>(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>2</Subscript>(SeO<Subscript>4</Subscript>)] · 1.33H<Subscript>2</Subscript>O

The single crystals of Rb₂[(UO₂)₂(C₂O₄)₂(SeO₄)] · 1.33H₂O were synthesized and studied by X-ray diffraction. The crystals are monoclinic, space group P2₁/m, Z= 2, the unit cell parameters: a = 5.6537(8), b = 18.736(3), c = 9.4535(15) Å, β = 98.440(5)°, V = 990.6(3) ų, R ₁ = 0.0506. The main structural units of the crystal are infinite layers of [(UO₂)₂(C₂O₄)₂(SeO₄)]^2?, corresponding to the crystal chemical group A₂K ₂ ⁰² B² (A = UO ₂ ²⁺ , K⁰² = C₂O ₄ ^2? , B² = SeO ₄ ^2? ) of uranyl complexes. The uranium-containing layers are united into a three-dimensional framework through the electrostatic interactions with the outer-sphere rubidium ions and the hydrogen bonding system involving the outer-sphere water molecules.     

Thermogravimetric analysis of wheatleyite Na<Subscript>2</Subscript>Cu<Superscript>2+</Superscript>(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>2</Subscript>·2H<Subscript>2</Subscript>O

Evidence for the existence of primitive life forms such as lichens and fungi can be based upon the formation of oxalates. These oxalates form as a film like deposit on rocks and other host matrices. The anhydrous oxalate mineral moolooite CuC₂O₄ as the natural copper(II) oxalate mineral is a classic example. Another example of a natural oxalate is the mineral wheatleyite Na₂Cu²⁺(C₂O₄)₂·2H₂O. High resolution thermogravimetry coupled to evolved gas mass spectrometry shows decomposition of wheatleyite at 255°C. Two higher temperature mass losses are observed at 324 and 349°C. Higher temperature mass losses are observed at 819, 833 and 857°C. These mass losses as confirmed by mass spectrometry are attributed to the decomposition of tennerite CuO. In comparison the thermal decomposition of moolooite takes place at 260°C. Evolved gas mass spectrometry for moolooite shows the gas lost at this temperature is carbon dioxide. No water evolution was observed, thus indicating the moolooite is the anhydrous copper(II) oxalate as compared to the synthetic compound which is the dihydrate.     

Synthesis and structure of novel coordination compounds based on [Re<Subscript>6</Subscript>Q<Subscript>8</Subscript>(CN)<Subscript>6</Subscript>]<Superscript>4–</Superscript> (Q = S,Se) and (SnMe<Subscript>3</Subscript>)<Superscript>+</Superscript>

The reactions of SnMe₃Cl with salts of the cluster anionic complexes [Re₆Q₈(CN)₆]^4? (Q = S, Se) gave novel complexes [{(SnMe₃)₂(OH)}₂{SnMe₃}₂{Re₆S₈(CN)₆}] (I), (Me₄N)₂[{SnMe₃(H₂O)}₂{Re₆Se₈(CN)₆}] (II), [{(SnMe₂)₄(μ₃-O)}₂{Re₆Se₈(CN)₆}] (III), and [(SnMe₂)₄(μ₃-O)₂(μ₂-OH)₂(H₂O)₂][{SnMe_{3 2}{Re₆Se₈(CN)₆}] (IV). The structures of I–IV were determined by X-ray diffraction. Compounds I, IV have the chain structures with the CN-SnMe₃-NC bridges between the cluster anions [Re₆Q₈(CN)₆]^4?. Compound II contains isolated fragments {SnMe₃(H₂O)}₂{Re₆Se₈(CN)₆}^2?. In the polymer framework of compound III, the cluster anionic complexes [Re₆Se₈(CN)₆]^4? are bound by the complex cations [(SnMe₂)₄(μ₃-O)₂]⁴⁺ formed due to the hydrolysis of the initial (SnMe₃)Cl.     

Trinuclear Metal Clusters with Three Different Metal Atoms from the Insertion of CpCo and Cp*Rh Groups into the S–S Bonds of [CpFeMn(CO)<Subscript>5</Subscript>(μ-S<Subscript>2</Subscript>)]<Subscript>2</Subscript><Superscript>†</Superscript>

Two cobalt containing products CpCoMn₂(CO)₆(μ₃-S)₂, 2 and Cp₂FeCoMn(CO)₃(μ₃-S)₂, 3 were obtained from the reaction of [CpFeMn(CO)₅(μ-S₂)]₂, 1 with CpCo(CO)₂ at room temperature. The two rhodium containing products: Cp*RhMn₂(CO)₆(μ₃-S)₂, 4 (11% yield) and CpFeCp*RhMn(CO)₃(μ₃-S)₂, 5 (9% yield), were obtained from the reaction of 1 with Cp*Rh(CO)₂. Compounds 3 and 5 were characterized structurally by single crystal X-ray diffraction methods. Compounds 3 and 5 both contain triangular clusters of three different types of metal atoms and have triply bridging sulfido ligands on each side of the cluster. A mechanism for their formation from 1 is proposed.^†Dedicated to F. A. Cotton on the occasion of his 75th birthday.     

A theoretical study on the dynamics of the gas phase reaction of NH<Subscript>2</Subscript>(<Superscript>2</Superscript>B<Subscript>1</Subscript>) with HO<Subscript>2</Subscript>(<Superscript>2</Superscript>A″)

Quasi-classical trajectory calculations and stochastic one-dimensional chemical master equation simulation methods are used to study the dynamics of the reaction of amidogen radical [NH₂(²B₁)] with hydroperoxyl radical [HO₂(²A″)] on the lowest singlet electronic state. The title complex reaction takes place on a multi-well multichannel potential energy surface consisting of three deep potential wells and one van der Waals complex. In quasi-classical trajectory calculations a new analytical potential energy surface based on CCSD(T)/aug-cc-pVTZ//MPW1K/6-31+G(d,p) ab initio method was driven and used to study the dynamics of the title reaction. In quasi-classical trajectory calculations, the reactive cross sections and reaction probabilities are determined for 200–2000 K relative translational energies to calculate the rate constants. The same ab initio method was used to have the necessary data for solving the one-dimensional chemical master equation to calculate the rate constants of different channels. In solving the master equation, the Lennard-Jones potential model was used to form the collision between the collider gases. The fractional populations of different intermediates and products in the early stages of the reaction were examined to determine the role of the energized intermediates and the van der Waals complex on the dynamics of the title reaction. Although the calculated total rate constants from both methods are in good agreement with the reported experimental values in the literature, the quasi-classical trajectory simulation predicts the formation of NH₂O + OH as the major channel in the title reaction in accordance with the previous studies (Sumathi and Peyerimhoff, Chem. Phys. Lett., 263:742–748, 1996), while the stochastic master equation simulation predicts the formation of HNO + H₂O as the major products.     

Structural investigation of salts containing ions [Pd(NH<Subscript>3</Subscript>)<Subscript>4</Subscript>]<Superscript>2+</Superscript> and [IrF<Subscript>6</Subscript>]<Superscript>2–</Superscript>

Double complex salts (DCS) α-[Pd(NH₃)₄][IrF₆]·H₂O (P2₁/m, a = 6.3181(3) Å, b = 10.8718(5) Å, с = 7.4526(4) Å, β = 103.568(2)°), β-[Pd(NH₃)₄][IrF₆]·H₂O (P2₁/с, a = 8.5773(3) Å, b = 10.8791(4) Å, с = = 12.6741(3) Å, β = 122.497(2)°), [Pd(NH₃)₄]₃[IrF₆]₂Cl₂·H₂O (P-1, a = 7.6080(2) Å, b = 7.6274(2) Å, с = 11.8070(3) Å, β = 122.497(2)°), and [Pd(NH₃)₄]₂[IrF₆]NO₃ (Fm-3m, a = 11.21210(10) Å) have been synthesized and structurally characterized for the first time. The existence of polymorphs for the DCS has been revealed. The influence of the chemical composition of the initial reagents on the reaction course and, respectively, the products, has been demonstrated. A hypothesis on the influence of the second coordination sphere on the formation of one or the other polymorph of the DCS has been suggested. It has been shown that the series α-[Pd(NH₃)₄][МF₆]·H₂O (M = Pt, Pd) exhibits isostructurality.