Cuboidal oxalate cluster complexes with the Mo<Subscript>3</Subscript>CuQ<Subscript>4</Subscript><Superscript>5+</Superscript> cluster core (Q = S or Se): synthesis,structure, and electrochemical properties

The reactions of the [Mo₃(μ₃-Q)(μ₂-Q)₃(H₂O)₃(C₂O₄)₃]²⁻ complex (Q = S or Se) with CuX salts (X = Cl, Br, I, or SCN) in water produce the cuboidal heterometallic clusters [Mo₃(CuX)(μ₃-Q)₄(H₂O)₃(C₂O₄)₃]²⁻, which were isolated as the potassium and tetraphenylphosphonium salts. Two new compounds, K₂[Mo₃(CuI)(μ₃-S)₄(H₂O)₃(C₂O₄)₃]·6H₂O and (PPh₄)₂[Mo₃(CuBr)(μ₃-S)₄(H₂O)₃(C₂O₄)₃]·7H₂O, were structurally characterized. All compounds were characterized by elemental analysis and IR spectroscopy. The K₂[Mo₃(CuI)(μ₃-Se)₄(H₂O)₃(C₂O₄)₃] compound was characterized by the ⁷⁷Se NMR spectrum; the (PPh₄)₂[Mo₃(CuI)(μ₃-S)₄(H₂O)₃(C₂O₄)₃], (PPh₄)₂[Mo₃(CuI)(μ₃-Se)₄(H₂O)₃(C₂O₄)₃] and K₂[Mo₃(CuSCN)(μ₃-S)₄(H₂O)₃(C₂O₄)₃]·7H₂O compounds, by electrospray mass spectra. Dedicated to Academician G. A. Abakumov on the occasion of his 70th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1639–1644, September, 2007.     

Cluster complexes [Mo3O2S2(Acac)3(Amine)3]PF6

New mixed-ligand cluster complexes [Mo₃O₂S₂(Acac)₃(Amine)₃]PF₆ (Amine = morpholine (Mor), 4-cyanopyridine (PyCN), pyrazine (Pz)) have been synthesized. The compounds were characterized by IR spectroscopy and mass spectrometry (ESI-MS). The crystal structure of the Mor complex, which was isolated as [Mo₃(μ₃-S)(μ₂-O)₂(μ₂-S)(Acac)₃(Mor)₃]PF₆ · 0.5Mor · 0.3(CH₃)₂CO was determined. The stability of the complexes in methanolic solutions decreases in a row: Mor > PyCN > Pz.     

A New Molybdophosphate Constructed From {Mo<Stack><Subscript>2</Subscript><Superscript>V</Superscript></Stack>O<Subscript>4</Subscript>(H<Subscript>2</Subscript>O)<Subscript>6</Subscript>}<Superscript>2+</Superscript> and 1-Hydroxyethylidenediphosphonate

A new molybdophosphate (NH₄)₈{Mo₂^VO₄[(Mo₂^VIO₆)CH₃C(O)(PO₃)₂]₂}·14H₂O (1), has been synthesized by the reaction of {Mo₂^VO₄(H₂O)₆}²⁺ fragments with 1-hydroxyethylidenediphosphonate (hedp HOC(CH₃)(PO₃H₂)₂), and it is characterized by ³¹P NMR, IR, UV, element analysis, TG and single-crystal X-ray analysis. The structure analysis reveals that the polyoxoanion can be described as two {(Mo₂^VIO₆)(CH₃C(O)(PO₃)₂} units connected by a {Mo₂^VO₄}²⁺ moiety. In the structure, the six Mo atoms are arranged into a new “W-shaped” structure, which represents a new kind of molybdophosphate.     

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.     

Reactivity of triangular oxalate cluster complexes [M<Subscript>3</Subscript>Q<Subscript>7</Subscript>(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>3</Subscript>]<Superscript>2−</Superscript> (M = Mo or W; Q = S or Se)

The reactions of the oxalate complexes [M₃Q₇(C₂O₄)₃]²⁻ (M = Mo or W; Q = S or Se) with Mn^II, Co^II, Ni^II, and Cu^II aqua and ethylenediamine complexes in aqueous and aqueous ethanolic solutions were studied. The previously unknown heterometallic complexes [Mo₃Se₇(C₂O₄)₃Ni(H₂O)₅]·3.5H₂O (1) and K₃{[Cu(en)₂H₂O]([Mo₃S₇(ox)₃]₂Br)}·5.5H₂O (2) were synthesized. In these complexes, the oxalate clusters serve as monodentate ligands. The K(H₂en)₂[W₃S₇(C₂O₄)₃]₂Br·4H₂O salt (3) was isolated from solutions containing Co^II, Ni^II, or Cu^II aqua complexes and ethylenediamine. The reaction of [Mo₃Se₇(C₂O₄)₃]²⁻ with HBr produced the bromide complex [Mo₃Se₇Br₆]²⁻, which was isolated as (Bu₄N)₂[Mo₃Se₇Br₆] (4). Complexes 1–3 were characterized by X-ray diffraction, IR spectra, and elemental analysis. The formation of 4 was detected by electrospray mass spectrometry. Dedicated to Academician G. A. Abakumov on the occasion of his 70th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1645–1649, September, 2007.     

Reaction of Sulfur and Oxygen-Bridged 8-Quinolinolato Trinuclear Molybdenum Cluster [Mo<Subscript>3</Subscript>OS<Subscript>3</Subscript>(qn)<Subscript>3</Subscript>(H<Subscript>2</Subscript>O)<Subscript>3</Subscript>]<Superscript>+</Superscript> with Acetylene Carboxylic Acids

The reaction of a sulfur and oxygen-bridged 8-quinolinolato trinuclear molybdenum cluster [Mo₃OS₃(qn)₃(H₂O)₃]⁺ (3; Hqn = 8-quinolinol) with equimolar amounts of acetylene carboxylic acid, 4-pentynoic acid, 5-hexynoic acid, acetic acid, and pimelic acid gave clusters having μ-carboxylato groups, [Mo₃OS₃(qn)₃(H₂O)(μ-HC≡CCOO)] (6), [Mo₃OS₃(qn)₃(H₂O)(μ-HC≡C(CH₂)₂COO)] (7), [Mo₃OS₃(qn)₃(H₂O)(μ-HC≡C(CH₂)₃COO)] (8), [Mo₃OS₃(qn)₃(H₂O)(μ-CH₃COO)] (4), and [{Mo₃OS₃(qn)₃(C₂H₅OH)}₂(μ-C₇H₁₀O₄)] (5), respectively. X-ray structural analyses, ¹H NMR, and electronic spectra of these clusters made clear that each of the COO⁻ groups of the reagents bridges two Mo atoms in each cluster and that no adduct formation occurred at the sulfurs in the clusters. The reaction of 3 with a large excess-molar amount (50 times) of acetylene carboxylic acid gave [Mo₃OS(μ₃-SCH=C(COOH)S)(qn)₃(H₂O)(μ-HC≡CCOO)] (9) with two molecules of acetylene carboxylic acid, one acting as a carboxylato bridge and the other in adduct formation, as supported by the electronic and ¹H NMR spectra. The corresponding aqua cluster [Mo₃OS₃(H₂O)₉]⁴⁺ (1), on the contrary, reacts with acetylene carboxylic acid to give adduct [Mo₃OS(μ₃-SCH=C(COOH)S)(H₂O)₉]⁴⁺ (2). Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Synthesis and structure of an open-type trinuclear molybdenum cluster compound[Mo_3(μ_3-S)(μ-S)_2-(μ-OAc)(S_2CNC_4H_8)_3(O)_2]·0.5CH_2Cl_2·2H_2O

The title compound was prepared by the reaction of Mo_3S_4(dtp)_4(H_2O)[ctp=S_2P(OEt)_2]with NaOAc·3H_2O and C_4H_8NCS_2NH_4.Crystallographic data:[Mo_3(μ_3-S)(μ-S)_2(μ-OAc)-(S_2CNC_4H_8)_3(O)_2]·0.5CH_2CI_2·2H_2O,Mr=980.18,triclinic,space group P,α=12.360(3),b=16.653(6),c=9.206(2)A,α=101.97(2),β=108.32(2),γ=86.14(3)°.V=1759.6(9)A~3,Z=2,Dc=1.85 g/cm~3,F(000)=962,μ(Mo K_α)=16.53 cm~(-1).Final R=0.044 for 4301 reflections with I≥3σ(I).This compoundmay be regarded as a mixed-valent trinuclear molybdenum cluster{Mo_2(V)Mo(Ⅳ)(μ_3-S)(μ-S)_2-(μ-OAc)(S_2CNC_4H_8)_3(O)_2}.The Mo-Mo distances are 2.783(1),2.833(1)and 3.374(2)A in the Mo_3non-equilateral triangle and there exist only two Mo-Mo bonds.The cluster was obtained by oxi-dation and ligand substitution of{Mo_3(μ_3-S)(μ-S)_3[μ-S_2P(OEt_2)][S_2P(OEt)_2]_3(H_2O)}.     

Electroneutral coordination frameworks based on octahedral [Re<Subscript>6</Subscript>(μ<Subscript>3</Subscript>-Q)<Subscript>8</Subscript>(CN)<Subscript>6</Subscript>]<Superscript>4−</Superscript> complexes (Q = S,Se, Te) and the Mn<Superscript>2+</Superscript> cations

The novel coordination polymers, [{Mn(DMF)₃}₂{Re₆S₈(CN)₆}] (I), [{Mn(DMF)₂(H₂O)}₂{Re₆S₈(CN)₆}] · 2DMF (II), [{Mn(DMF)₃}₂{Re₆Se₈(CN)₆}] (III), [{Mn(DMF)₂(H₂O)}₂{Re₆Se₈(CN)₆}] · 2DMF (IV), and [{Mn(DMF)₂(H₂O)}₂{Re₆Te₈(CN)₆}] · 2DMF (V), were synthesized by interaction of the octahedral cluster complexes [Re₆(μ₃-Q)₈(CN)₆]^4? (Q = S, Se, Te) with the Mn²⁺ cations in the H₂O-DMF mixture. The crystal structures of compounds I, II, IV, and V were determined by X-ray diffraction analysis. The structural analogies between mononuclear cyanometallates and the obtained cluster coordination polymers were discussed.     

Complexes based on the anionic octahedral rhenium chalcogenide clusters and [M(En)<Subscript>2</Subscript>]<Superscript>2+</Superscript> (M = Ni,Cu) cations

The compounds [Ni(H₂O)₂(En)₂][{Ni(En)₂}Re₆S₈(OH)₆] · 7H₂O (I), [{Cu(En)₂}Re₆S₈(H₂O)₂(OH)₄] · 4H₂O (II), and [Ni(H₂O)₂(En)₂]_0.5[Re₆Se₈(H₂O)₃(OH)₃] · 10H₂O (III) were synthesized by layering aqueous solutions of Ni(En)₂Cl₂ or Cu(En)₂Cl₂ (En is ethylenediamine) onto aqueous solutions of the potassium salts of the corresponding octahedral chalcohydroxo rhenium cluster complexes [Re₆Q₈(OH)₆]⁴⁻ (Q = S, Se). The structure of the obtained compounds was determined by X-ray diffraction analysis.     

Capping [H<Subscript>8−n</Subscript>Ni<Subscript>42</Subscript>C<Subscript>8</Subscript>(CO)<Subscript>44</Subscript>]<Superscript>n−</Superscript> (n = 6, 7, 8) Octa-carbide Carbonyl Nanoclusters with [Ni(CO)] and [CuCl] Fragments

The reactions of [Ni₁₆(C₂)₂(CO)₂₃]^4? and [Ni₃₈C₆(CO)₄₂]^6? with CuCl afforded mixtures of the previously reported [HNi₄₂C₈(CO)₄₄(CuCl)]^7? bimetallic octa-carbide cluster and the new [HNi₄₃C₈(CO)₄₅]^7? and [HNi₄₄C₈(CO)₄₆]^7? homo-metallic octa-carbides. The three species have very similar properties resulting always in co-crystals such as [NMe₄]₇[HNi_42+2xC₈(CO)_44+2x(CuCl)_1?x]·6.5MeCN (x = 0.14) (86% [HNi₄₂C₈(CO)₄₄(CuCl)]^7?, 14%[HNi₄₃C₈(CO)₄₅]^7?/[HNi₄₄C₈(CO)₄₆]^7?) and [NMe₄]₇[HNi_42+2xC₈(CO)_44+2x(CuCl)_1?x]·5.5MeCN (x = 0.30) (70% [HNi₄₂C₈(CO)₄₄(CuCl)]^7?, 30% [HNi₄₃C₈(CO)₄₅]^7?/[HNi₄₄C₈(CO)₄₆]^7?). The new homo-metallic octa-carbides can be obtained free from the Ni–Cu octa-carbido cluster by reacting [Ni₁₀(C₂)(CO)₁₆]^2? in thf with a stoichiometric amount of CuCl, and crystals of [NMe₄]₆[H₂Ni_43+xC₈(CO)_45+x]·6MeCN (x = 0.72), which contain [H₂Ni₄₄C₈(CO)₄₆]^6? (72%) and [H₂Ni₄₃C₈(CO)₄₅]^6? (28%), have been obtained. Despite the different charges and compositions, these anions display almost identical structures, which are also closely related to those previously reported for the bimetallic Ni–Cd octa-carbido clusters [Ni_42+xC₈(CO)_44+x(CdCl)]^7? and [HNi_42+xC₈(CO)_44+x(CdBr)]^6?. Indeed, all these clusters are based on the same Ni₄₂C₈ cage decorated by miscellaneous [CdX]⁺ (X = Cl, Br), [CuCl] and [Ni(CO)] fragments.     

The Reactions of Two New Alkoxy-silyl Functionalized Alkynes with M<Subscript>3</Subscript>(CO)<Subscript>12</Subscript> {M = Fe,Ru} and Co<Subscript>2</Subscript>(CO)<Subscript>8</Subscript>. Spectroscopic Identification of the Products

The new alkoxysilyl-functionalized alkynes [HC≡CCH₂N(H)C(=O)N(H)(CH₂)₃Si(OEt)₃] and [HC≡C(C₆H₄)–N(H)C(=O)N(H)(CH₂)₃Si(OEt)₃] have been synthesized using literature methods. These have been reacted with Fe₃(CO)₁₂, Ru₃(CO)₁₂ and Co₂(CO)₈. With the iron carbonyl only decomposition was observed: with Ru₃(CO)₁₂ splitting of the alkynes into their parent components and formation of the complexes (μ-H)Ru₃(CO)₉[HC=N(CH₂)₃Si(OEt)₃], (μ-H)Ru₃(CO)₉[C–C(C₆H₄)NH₂] and (μ-H)₂Ru₃(CO)₉[HC–CCH₃] occurred. Finally, with Co₂(CO)₈ formation of complexes Co₂(CO)₆(HC₂R) R=(C₆H₄)NH₂, CH₂NH(CO)NH(CH₂)₃Si(OEt)₃, (C₆H₄)NH(CO)NH(CH₂)₃Si(OEt)₃ containing the intact alkynes could be obtained.     

Studies on reactivities of molybdenum clusters — The additive reaction of SbCl3 to trimolybdenum clusters with loose coordination sites and the crystal structure of the reaction product

The additive reaction of SbCl₃ to trimolybdenum clusters with loose coordination sites, Mo₃(μ₃-S) (μ-S)₃ [S₂P (OEt)₂]₄ · L' (1 L' ? H₂O; 2, L' ? C₃H₃ON), in a C₂H₅OH-HCl medium yields complexes {Mo₃ (μ₃-S) [(μ-S)₃ · SbCl₃] [S₂P (OEt)₂]₄ · (C₂H₅OH)} (C₂H₅OH) (3) and {Mo₃ (μ₃-S) [(μ-S)₃ · SbCl₃] [S₂P (OEt)₂]₃ [SXP (OEt)₂] · (C₃H₃ON)} (X ? S,O) (4), respectively. The crystal and molecular structures of these two compounds have been determined by single crystal X-ray crystallography: crystal 3 belongs to the monoclinic system, P2₁,/n, while crystal 4 belongs to the triclinic system, P 1, The intensity data were collected on an Enraf-Nonius CAD-4 diffractometer with graphite-monochromatized MoKα radiation by using the ω-2θ technique. The structures were solved by the Patterson method as well as direct methods and refined by full matrix least-squares method. Final R values were 0.078 for crystal 3 and 0.068 for crystal 4, respectively. The result of the structure determination showed that the two molecular structures are practically formed by connecting a trimolybdenum clusters with loose coordination sites, {Mo₂(μ₃-S)- (μ-S)₃[S₂P(OEt)₂]₄ · L (L ? C₂H₅OH, C₃H₃ON), with a SbCl₃ molecule through three (μ-S) atoms to form the {Mo SbS₄} core of a cubane-like type. There are relatively weak coordination bonds between the Sb and the three (μ-S) atoms, while no bonding interaction between the Sb and the three Mo atoms is found. In the additive compounds the structural character of the trimolybdenum clusters with loose coordination sites has significantly been changed. In addition, 3 still has the reactivity for the loosely coordinated EtOH to be replaced by an oxazole ring to form crystal 4. However, the three (μ-S) atoms may be regarded as triple bridging S atoms each connecting two Mo atoms and a Sb atom. The information obtained serves as an evidence that the tetranuclear clusters might be formed by a [3 + 1] reaction mode.     

Coordination Chemistry of the Magic Inorganic Building Block {Fe<Superscript>II</Superscript>[Mo<Subscript>6</Subscript>P<Subscript>4</Subscript>O<Subscript>31</Subscript>]<Subscript>2</Subscript>}: Hydrothermal Synthesis and Crystal Structure of a New Reduced Ferrous Molybdophosphate

A new reduced ferrous molybdophosphate composite solid of the formula, [(C₁₀H₁₄N₂)H]₄[Fe^II ₁₀Mo^V ₂₄(H₂PO₄)₄(HPO₄)₁₂(PO₄)₄(H₂O)₁₆(OH)₁₆O₄₄]·12H₂O, has been synthesized from a reaction mixture of MoO₃, FeSO₄·7H₂O, C₂H₂O₄·2H₂O, nicotine, H₃PO₄, and H₂O under hydrothermal conditions. The crystal data: monoclinic, space group C2/m, a = 24.4349(124), b = 12.9935(66), c = 14.7281(74) Å, β = 104.87(1) Å, V = 4520(4) Å³, Z = 2, R ₁  = 0.0874, wR ₂  = 0.2179. The structure is built from the building blocks of the formula, {Fe^II[Mo₆P₄O₃₁]₂}, consisting of a network of MO₆ (M = Fe, Mo) octahedral and PO₄ tetrahedral linked through their vertices. The connectivity of the building blocks with two pairs of face-sharing dinuclear Fe(II) clusters of the formula of [Fe^II ₂(H₂O)₄O₅] on which a phosphate group is hanging gives rise to one-dimensional chains with eight-membered apertures. The remarkable hydrogen bonded interactions between the chains form a unique and interesting framework with three-dimensional intersecting tunnels where the protonated nicotine molecules as structuring templates and crystallization water molecules are situated.     

Two decomposition mechanisms of nitrosyl iron complexes [Fe<Subscript>2</Subscript>(μ-SR)(NO)<Subscript>4</Subscript>]

Two decomposition mechanisms of nitrosyl iron complexes (NICs) [Fe₂(μ-SR)(NO)₄] in aqueous medium are known. One mechanism (for instance, in the case of complex [Fe₂(μ-SC₄H₃N₂)₂(NO)₄]) involves irreversible and rapid hydrolysis of NIC with the NO release accompanied with the formation of the products of further NO transformations. In the other mechanism (for instance, in the case of complexes [Fe₂(μ-S(CH₂)₂NH₃)₂(NO)₄]SO₄? ?2.5H₂O and [Fe₂(μ-SC₅H₁₁NO₂)₂(NO)₄]SO₄?5H₂O), no hydrolysis occurs but NICs reversibly dissociate to release both NO and thiolate ligand into the medium. In the present work, the difference in the mechanisms of the NIC decomposition is explained by the difference in the NIC redox potentials. The experimental evidences of this fact are given.     

Macrocyclic‐ligand Induced Synthesis of Aryl Ethynides with Divergent Silver(I) Clusters

Two structurally characterized metal‐cluster‐centered supramolecular architectures named [Ag₈(1,2‐(C ≡ C)₂‐C₆H₄ )( Py[6] )(CF₃CO₂ )₆] · 2.5MeOH ( 1 ) and [Ag₁₂(1,2,4,5‐(C ≡ C)₄C₆H₂ )( Py[6] )₂(CF₃SO₃ )₈]·4MeOH ·3H₂O ( 2 ) are synthesized through the interaction with a bowl‐shaped macrocyclic ligand Py[6] . Particularly, two dissimilar silver(I) clusters are resulted in 2 within the structure under the influence of the macrocyclic ligand Py[6] . Such dissimilarity of the silver(I) cluster is also reflected on the structural and photophysical differences between 1 and 2 .     

Novel bimetallic Cr<Subscript>3</Subscript>Yb<Subscript>3</Subscript> mixed salt containing a 3<Emphasis Type="Italic">d</Emphasis>-4<Emphasis Type="Italic">f</Emphasis> heterometallic Cr<Subscript>2</Subscript>Yb<Subscript>3</Subscript> cluster

A novel bimetallic Cr₃Yb₃ coordination compound containing a 3d-4f heterometallic Cr₂Yb₃ cationic cluster has been synthesized and structurally characterized. The crystal structure was determined by X-ray analysis. Results denote that the complex consists of an original [Cr ₂ ^III Yb ₃ ^III ]³⁺ moiety with a trigonal-bipyramidal topology of the [Cr₂Yb₃(μ-OOCCH₃)₆(μ-OH)₆(H₂O)₆]³⁺ core, an isolated [Cr^III(CN)₆]^3? anion, and four molecular neutral 4,4′-bipyridene (Bipy) ligands, namely, [Cr₂Yb₃(μ-OOCCH₃)₆(μ-OH)₆(H₂O)₆][Cr(CN)₆] · 4Bipy · 13H₂O.     

Reactions of [Cp*Ru(H<Subscript>2</Subscript>O)(NBD)]<Superscript>+</Superscript> with diynes

Abstract  Formal [2 + 2 + 2] addition reaction of [Cp*Ru(H₂O)(NBD)][BF₄] (NBD = norbornadiene) with 4,4′-Diethynylbiphenyl generates [C₉H₉-η⁶-C₆H₄(RuCp*)–C₆H₄(RuCp*)-η⁶-C₉H₉][BF₄]₂. The reaction of [Cp*Ru(H₂O)(NBD)][BF₄] with 1,4-diphenylbutadiyne generates the unusual [2 + 2 + 2] additional organic compound Ph–C≡C–C₉H₈–Ph in addition to the organometallic compound [Cp*Ru(η⁶-C₆H₅–C≡C–C≡C–Ph)][BF₄]. [C₉H₉-η⁶-C₆H₄(RuCp*)–C₆H₄(RuCp*)-η⁶-C₉H₉][BPh₄]₂ is generated after the reaction of compound [C₉H₉-η⁶-C₆H₄(RuCp*)–C₆H₄(RuCp*)-η⁶-C₉H₉][BF₄]₂ with Na[BPh₄]. The structure of this compound was confirmed by X-ray diffraction. A possible approach to form Ph–C≡C–C₉H₈–Ph and [Cp*Ru(η⁶-C₆H₅–C≡C–C≡C–Ph)][BF₄] is suggested. Graphical Abstract  Formal [2 + 2 + 2] addition reaction of [Cp*Ru(H₂O)(NBD)]BF₄ (NBD = norbornadiene) with 4,4′-Diethynylbiphenyl generates [C₉H₉-η⁶-C₆H₄(RuCp*)–C₆H₄(RuCp*)-η⁶-C₉H₉][BF₄]₂. The reaction of [Cp*Ru(H₂O)(NBD)][BF₄] with 1,4-diphenylbutadiyne simply generates unusual [2 + 2 + 2] additional organic compound Ph–C≡C–C₉H₈–Ph in addition to the organometallic compound [Cp*Ru(η⁶-C₆H₅–C≡C–C≡C–Ph)][BF₄]. [C₉H₉-η⁶-C₆H₄(RuCp*)–C₆H₄(RuCp*)-η⁶-C₉H₉][BPh₄]₂ is generated after the reaction of compound [C₉H₉-η⁶-C₆H₄(RuCp*)–C₆H₄(RuCp*)-η⁶-C₉H₉][BF₄]₂ with Na[BPh₄]. The structure of this compound was confirmed by X-ray diffraction. And the possible approach to form Ph–C≡C–C₉H₈–Ph and [Cp*Ru(η⁶-C₆H₅–C≡C–C≡C–Ph)][BF₄] was suggested. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Green,purple, blue — [Cu(N-Methylimidazole)<Subscript>n</Subscript> (OOCCH<Subscript>3</Subscript>)<Subscript>2</Subscript>]<Subscript>m</Subscript>, what is in a colour

Starting from the paddlewheel complex copper(II)acetate, the green N-methylimidazole adduct of copper(II)acetate is formed and transformed into the monomeric and dimeric N-methylimidazole adducts of copper(II)acetate [Cu(C₄H₆N₂)₂(CH₃COO)₂]_n·xH₂O (n = 1,2; x = 0, 6). The formation of the blue dimer or the purple monomer depends on the solvent and the presence or absence of water.     

Synthesis,crystal structure of a new tetranuclear Ni<Stack><Subscript>2</Subscript><Superscript>II</Superscript></Stack>Cu<Stack><Subscript>2</Subscript><Superscript>II</Superscript></Stack> complex containing a macrocyclic ligand

The first inorg/organic hybrid complex incorporating the macrocyclic oxamide, of formula [(NiL)₂Cu₂(μ-NSC)₂(NSC)₂] (1), (NiL, H₂L = 2, 3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-dien), have been synthesized and structurally characterized. The crystals crystallize in the triclinic system, space group P-1, for (1) a = 8.319(3) Å, b = 10.434(4) Å, c = 14.166(5) Å, a = 107.030(5)°, β  =  91.257(5)°, γ = 107.623(5)°. The complex involved both bridging N, S-ligand, and oxamide ligand, C–H?S interactions and NCS → Ni weak coordination interactions making the complex superamolecular.     

Structures and mutual transformations of isomers of germylium ions (CH<Subscript>3</Subscript>)H<Subscript>2</Subscript>Ge<Superscript>+</Superscript> and (CH<Subscript>3</Subscript>)<Subscript>2</Subscript>HGe<Superscript>+</Superscript> and their silicon analogs

The potential energy surfaces of the (CH₃)_nH_3?n M⁺ ions, where n = 1, 2; M = Si, Ge, were scanned using the B3LYP method with 6–31G* and aug-cc-pVDZ basis sets. The major attention was given to isomeric species having the form of complexes of the HM⁺ and CH₃M⁺ ions with hydrogen, methane, and ethane molecules. These species were characterized previously neither by experimental nor by theoretical methods. It was found that these species become more stable in going from Si to Ge; the complex [CH₃Ge⁺CH₄] is the second isomer in the energy after (CH₃)₂HGe⁺. However, the heights of the activation barriers to formation of these complexes from the most stable isomer, though decreasing in going from Si to Ge, remain relatively high and, what is particularly important, somewhat exceed the activation barrier to formation of the complex [H₃Ge⁺·C₂H₄].