Diverse closed cavities in condensed rare earth metal-chalcogenide matrixes: Cs[Lu7Q11] and (ClCs6)[RE21Q34] (RE = Dy, Ho; Q = S, Se, Te)

Two types of novel ordered chalcogenids Cs[Lu(7)Q(11)] (Q = S, Se) and (ClCs(6))[RE(21)Q(34)] (RE = Dy, Ho; Q = S, Se, Te) were discovered by high-temperature solid state reactions. The structures were characterized by single-crystal X-ray diffraction data. Cs[Lu(7)Q(11)] crystallize in the orthorhombic Cmca (no. 64) with a = 15.228(4)-15.849(7) ?, b = 13.357(3)-13.858(6) ?, c = 18.777(5)-19.509(8) ?, and Z = 8. (ClCs(6))[RE(21)Q(34)] crystallize in the monoclinic C2/m (no. 12) with a = 17.127(2)-18.868(2) ?, b = 19.489(2)-21.578(9) ?, c = 12.988(9)-14.356(2) ?, β = 128.604(2)-128.738(4)°, and Z = 2. Both types of compounds feature 3D RE-Q network structures that embed with dual tricapped cubes Cs(2)@Se(18) in the former or unprecedented matryoshka nesting doll structure cavities of (ClCs(6))@Se(32) in the latter. The band gap, band structure, as well as a structure change trend of the majority of A/RE/Q compounds are presented.     

Aluminosilicate relatives: Chalcogenoaluminogermanates Rb(3)(AlQ(2))(3)(GeQ(2))(7) (Q = S, Se)

The new compounds Rb(3)(AlQ(2))(3)(GeQ(2))(7) [Q = S (1), Se (2)] feature the 3D anionic open framework [(AlQ(2))(3)(GeQ(2))(7)](3-) in which aluminum and germanium share tetrahedral coordination sites. Rb ions are located in channels formed by the connection of 8, 10, and 16 (Ge/Al)S(4) tetrahedra. The isostructural sulfur and selenium derivatives crystallize in the space group P2(1)/c. 1: a = 6.7537(3) ?, b = 37.7825(19) ?, c = 6.7515(3) ?, and β = 90.655(4)°. 2: a = 7.0580(5) ?, b = 39.419(2) ?, c = 7.0412(4) ?, β = 90.360(5)°, and Z = 2 at 190(2) K. The band gaps of the congruently melting chalcogenogermanates are 3.1 eV (1) and 2.4 eV (2).     

A morphotropic series of the cluster complexes [Ln(DMF)8][Re6Q7Br7] (Q = S, Se): Synthesis, structure, and thermal transformations

The reactions of the octahedral anionic complexes [Re₆Q₇Br₇]^3? (Q = S, Se) with lanthanide bromides in DMF were studied. The reactions gave a series of compounds [Ln(DMF)₈][Re₆Q₇Br₇] (Q = S, Se) containing [Ln(DMF)₈]³⁺ complex cations. The compounds were studied by single-crystal and powder X-ray diffraction and thermal analyses. The crystal structures of [Ln(DMF)₈][Re₆S₇Br₇] with Ln = La (I), Ce (II), Nd (III), Eu (IV), and Lu (V) and [Ln(DMF)₈][Re₆Se₇Br₇] with Ln = La (VI), Ce (VII), Pr (VIII), and Lu (IX) were determined. It was found that [Ln(DMF)₈][Re₆Q₇Br₇] (Q = S, Se) can be divided into three structural groups: I, II, and VI (type A), VII (type B), and III–V, VIII, IX (type C). The complex [Pr(DMF)₈][Re₆Se₇Br₇] was found to crystallize in two polymorphous modifications with type B and C structures. Presumably, the morphotropic transitions in the [Ln(DMF)₈][Re₆Q₇Br₇] series (Q = S, Se) are mainly related to the change in the configuration of the [Ln(DMF)₈]³⁺ cations, resulting in a change in the packing motif of large complex ions in the crystals. The compounds [Ln(DMF)₈][Re₆Se₇Br₇] decompose according to a stepwise pattern, which suggests an intermediate formation of the complexes [Ln(DMF)₆][Re₆Se₇Br₇] (this was proved for Ln = Yb, Lu) with subsequent more extensive transformations, which affect also the cluster anion.     

Elimination of HX (X = Cl,Br) from haloalkenes on the Ru2Q2 (Q = S,Se) core complex

Treatment of [[Ru(P(OCH3)3)2(CH3CN)3]2(mu-Q2)](CF3SO3)4 (1, Q = S; 2, Q = Se) with haloalkenes resulted in the formation of complexes carrying unsaturated C3Q2 five-membered or C4Q2 six-membered rings via elimination of HX (X = Cl, Br). The reactions of 1 and 2 with allyl bromide gave the corresponding addition products, [[Ru(P(OCH3)3)2(CH3CN)3]2(mu-QCH=CHCH2Q)](CF3SO3)4 (3, Q = S; 4, Q = Se), via elimination of HBr. The elimination process seems to be thermodynamically controlled and takes place at the final stage of the reaction. The steric effect of the halogen atoms seems more operative than the electronic one.     

Cluster oxalate complexes [M3(mu3-Q)(mu2-Q2)3(C2O4)3]2- and [Mo3(mu3-Q)(mu2-Q)3(C2O4)3(H2O)3]2- (M = Mo, W; Q = S, Se): mechanochemical synthesis and crystal structure

Mechanochemical reaction of cluster coordination polymers 1infinity[M3Q7Br4] (M = Mo, W; Q = S, Se) with solid K2C2O4 leads to cluster core excision with the formation of anionic complexes [M3Q7(C2O4)3]2-. Extraction of the reaction mixture with water followed by crystallization gives crystalline K2[M3Q7(C2O4)3].0.5KBr.nH2O (M = Mo, Q = S, n = 3 (1); M = Mo, Q = Se, n = 4 (2); M = W, Q = S, n = 5 (3)). Cs2[Mo3S7(C2O4)3].0.5CsCl.3.5H2O (4) and (Et4N)1.5H0.5K{[Mo3S7(C2O4)3]Br}.2H2O (5) were also prepared. Close Q...Br contacts result in the formation of ionic triples {[M3Q7(C2O4)3](2)Br}5- in 1-4 and the 1:1 adduct {[Mo3S7(C2O4)3]Br}3- in 5. Treatment of 1 or 2 with PPh(3) leads to chalcogen abstraction with the formation of [Mo3(mu3-Q)(mu2-Q)3(C2O4)3(H2O)3]2-, isolated as (Ph4P)2[Mo3(mu3-S)(mu2-S)3(C2O4)3(H2O)3].11H2O (6) and (Ph4P2[Mo3(mu3-Se)(mu2-Se)3(C2O4)3(H2O)3].8.5H2O.0.5C2H5OH (7). All compounds were characterized by X-ray structure analysis. IR, Raman, electronic, and 77Se NMR spectra are also reported. Thermal decomposition of 1-3 was studied by thermogravimetry.     

Synthesis and reactivity of W3Te74+ clusters and chalcogen exchange in the M3Q7 (M = Mo, W; Q = S, Se, Te) cluster family

Heating WTe(2), Te, and Br(2) at 390 degrees C followed by extraction with KCN gives [W(3)Te(7)(CN)(6)](2-). Crystal structures of double salts Cs(3.5)K{[W(3)Te(7)(CN)(6)]Br}Br(1.5).4.5H(2)O (1), Cs(2)K(4){[W(3)Te(7)(CN)(6)](2)Cl}Cl.5H(2)O (2), and (Ph(4)P)(3){[W(3)Te(7)(CN)(6)]Br}.H(2)O (3) reveal short Te(2)...X (X = Cl, Br) contacts. Reaction of polymeric Mo(3)Se(7)Br(4) with KNCSe melt gives [Mo(3)Se(7)(CN)(6)](2-). Reactions of polymeric Mo(3)S(7)Br(4) and Mo(3)Te(7)I(4) with KNCSe melt (200-220 degrees C) all give as final product [Mo(3)Se(7)(CN)(6)](2)(-) via intermediate formation of [Mo(3)S(4)Se(3)(CN)(6)](2-)/[Mo(3)SSe(6)(CN)(6)](2-) and of [Mo(3)Te(4)Se(3)(CN)(6)](2-), respectively, as was shown by ESI-MS. (NH(4))(1.5)K(3){[Mo(3)Se(7)(CN)(6)]I}I(1.5).4.5H(2)O (4) was isolated and structurally characterized. Reactions of W(3)Q(7)Br(4) (Q = S, Se) with KNCSe lead to [W(3)Q(4)(CN)(9)](5-). Heating W(3)Te(7)Br(4) in KCNSe melt gives a complicated mixture of W(3)Q(7) and W(3)Q(4) derivatives, as was shown by ESI-MS, from which E(3)[W(3)(mu(3)-Te)(mu-TeSe)(3)(CN)(6)]Br.6H(2)O (5) and K(5)[W(3)(mu(3)-Te)(mu-Se)(3)(CN)(9)] (6) were isolated. X-ray analysis of 5 reveals the presence of a new TeSe(2-) ligand. The complexes were characterized by IR, Raman, electronic, and (77)Se and (125)Te NMR spectra and by ESI mass spectrometry.     

Selective detection of Zn2+ and Cd2+ ions in water using a host-guest complex between chromone and Q[7]

In this paper, the host-guest interaction of cucurbit[7]uril (Q[7]) and chromone (CMO) has been developed as a fluorescent probe for the highly selective detection of Zn²⁺ and Cd²⁺ in water based on a chelation-enhanced fluorescence (CHEF) mechanism. There was a good linear relationship between the fluorescence intensity of the CMO@Q[7] probe and the concentration of Zn²⁺ or Cd²⁺ in the range of 0–3.0 × 10^–5 mol/L and the detection limit for Zn²⁺ and Cd²⁺ was found to be 2.03 × 10^–6 mol/L and 1.89 × 10^–6 mol/L, respectively. The X-ray crystal structure indicated that different coordination fashions were triggered by Zn²⁺ and Cd²⁺ in the CMO@Q[7] complexes, respectively. However, both metal ions coordinated with the carbonyl oxygen of CMO, which was encapsulated in the cavity of Q[7], thus leading to the enhancement of recognition fluorescence emission of CMO.     

The intricate paramagnetic state of [Os(Q)(2)(bpy)](+), Q = 4,6-di-tert-butyl-o-iminobenzoquinone

The combination of two highly non-innocent ligands with a third-row transition metal produces the title complex ion which was crystallised as [Os(Q)(2)(bpy)](ClO(4))·C(6)H(6) (Q = 4,6-di-tert-butyl-o-iminobenzoquinones, bpy = 2,2(')-bipyridine) and could be structurally characterised to exhibit a tris-chelate situation at the metal with trans-positioned N and cis-positioned O donor atoms. The metrical ligand parameters are in agreement with two partially reduced ligands. A 3-spin interaction (Q˙(-))Os(III)(Q˙(-)) can rationalise the observed S = 1/2 situation with ligand-centred resulting spin. Ligand-based spin is confirmed by DFT (calculated spin populations Q: 1.113; Os: -0.113; bpy: 0.001) and is also apparent from the EPR signal (g(1) 1.981, g(2) 1.955, g(3) 1.803, Δg 0.178, ?g? 1.915) which is influenced by the high spin-orbit coupling constant of the osmium centre. The susceptibility measurements reveal antiferromagnetic behaviour. A one-electron oxidation and two one-electron reductions could be monitored spectroelectrochemically (UV-VIS-NIR) and analysed by TD-DFT, in comparison with the results from the ruthenium analogue. The analysis reflects the strong orbital mixing between the metal and the two Q-ligand MOs.     

七、八元瓜环对萘二胺异构体相互作用的考察

利用紫外吸收光谱、荧光光谱以及¹H NMR方法考察了七、八元瓜环(Q[7], Q[8])与1,8-萘二胺(g1), 2,3-萘二胺(g2), 1,5-萘二胺(g3)的相互作用. 实验结果表明: Q[7]与客体g1发生端口作用, 作用比为1∶1; Q[7]与客体g2, g3相互作用也形成1∶1的包结配合物. Q[8]与三种客体相互作用情况各不相同, 除Q[8]与客体g2相互作用形成1∶2的包结配合物; Q[8]与客体g1或g3可发生相互作用, 形成溶解性较差的作用产物, 其表观相互作用的比例为1∶1. 考察溶液酸度对主客体相互作用的影响还表明: 当pH大于某一值之后, 如Q[7]主客体体系, pH大于6.0; Q[8]主客体体系, pH大于12.0, 用光谱方法观察不到瓜环与客体的相互作用. Q[7], Q[8]为主体的上述主客体作用产物分别与金刚烷胺盐酸盐、1,10-癸二胺盐酸盐的竞争反应结果表明, 已作用的萘二胺异构体容易被所选用的竞争客体所取代, 只有g2与Q[8]形成的包结配合物被1,10-癸二胺盐酸盐部分取代.     

七元瓜环作为5-氨基水杨酸结肠给药载体可行性考察

利用荧光光谱法考察了七元瓜环(Q[7])和5-氨基水杨酸(5-ASA)在不同pH条件下的相互作用. 在pH＝2.0, 4.0时, Q[7]与5-ASA可形成1∶1(物质的量比)的包合物; 而在pH＝5.0, 6.0, 7.4 时未观察到两者之间有明显的相互作用. 利用¹H NMR 技术研究了Q[7]-5-ASA固体包合物不同pH值的存在形式. 当体系的pH＜6.0, 5-ASA以包合物的形式存在. 而当pH＞6.0, 包合物的稳定性下降, 5-ASA被释放出来以游离的药物分子形式存在, 说明5-ASA与Q[7]之间的相互作用依赖于体系的pH值, Q[7]可作为5-ASA结肠给药的一种潜在载体; 热动力学的研究表明包合作用主要受到体系焓变的影响; 红外光谱, DSC和TG的分析进一步证实了Q[7]-5-ASA固体包合物的形成.     

Cucurbituril binding of trans-[{PtCl(NH3)2}2(micro-NH2(CH2)8NH2)]2+ and the effect on the reaction with cysteine

The effect of encapsulation by cucurbiturils Q[7] and Q[8] on the rate of reaction of the anti-cancer dinuclear platinum complex trans-[{PtCl(NH3)2}2(micro-NH2(CH2)8NH2)]2+ with the model biological nucleophiles glutathione and cysteine has been examined by NMR spectroscopy. It was expected that the octamethylene linking chain would fold inside the cucurbituril host and hence position the reactive platinum centres close to the cucurbituril portals, and thereby, confer resistance to degradation by biological nucleophiles. The upfield shifts of the resonances from the methylene protons in the linking ligand observed in 1H NMR spectra of the platinum complex upon addition of either Q[7] or Q[8] indicate that the cucurbituril is positioned over the linking ligand, with the Pt(II) centres projecting out of the portal. Furthermore, the relative changes in chemical shift of the methylene resonances suggest that the octamethylene linking chain folds within the cucurbituril cavity, particularly in Q[8]. Simple molecular models, based on the observed relative changes in chemical shift, could be constructed that were consistent with the proposed folding of the linking ligand within the cucurbituril cavity. Encapsulation by Q[7] was found to reduce the rate of reaction of the platinum complex with glutathione. Encapsulation by Q[7] and Q[8] was also found to reduce the rate of reaction of the platinum complex with cysteine, with Q[8] slowing the reaction to a greater extent than Q[7], consistent with the inferred encapsulation geometries. Encapsulation of dinuclear platinum complexes within the cucurbituril cavity may provide a novel way of reducing the reactivity and degradation of these promising chemotherapeutic agents with blood plasma proteins.     

Stabilization of the previously unknown tautomer HP(OH)2 of hypophosphorous acid as ligand; preparation of [W3(Ni(HP(OH)2))Q4(H2O)9]4+ (Q = S,Se) complexes

Bis(hydroxy)phosphine, the isomer of hypophosphorous acid which remained elusive for a long time, coordinates to the Ni site of heterometallic clusters with a W3NiQ4 core (Q = S, Se) to give [W3(Ni(HP(OH)2))Q4(H2O)9]4+ (Q = S, Se).     

Ruthenium(II) ammine and hydrazine complexes with [N(Ph2PQ)2]- (Q = S, Se) ligands

Reactions of coordinatively unsaturated Ru[N(Ph2PQ)2]2(PPh3) (Q = S (1), Se (2)) with pyridine (py), SO2, and NH3 afford the corresponding 18e adducts Ru[N(Ph2PQ)2]2(PPh3)(L) (Q = S, L = NH3 (5); Q = Se, L = py (3), SO2 (4), NH3 (6)). The molecular structures of complexes 2 and 6 are determined. The geometry around Ru in 2 is pseudo square pyramidal with PPh3 occupying the apical position, while that in 6 is pseudooctahedral with PPh3 and NH3 mutually cis. The Ru-P distances in 2 and 6 are 2.2025(11) and 2.2778(11) A, respectively. The Ru-N bond length in 6 is 2.185(3) A. Treatment of 1 or 2 with substituted hydrazines L or NH2OH yields the respective adducts Ru[N(Ph2PQ)2]2(PPh3)(L) (Q = S, L = NH2NH2 (12), t-BuNHNH2 (14), l-aminopiperidine (C5H10NNH2) (15); Q = Se, L = PhCONHNH2 (7), PhNHNH2 (8), NH2OH (9), t-BuNHNH2 (10), C5H10NNH2 (11), NH2NH2 (13)), which are isolated as mixtures of their trans and cis isomers. The structures of cis-14 and cis-15 are characterized by X-ray crystallography. In both molecular structures, the ruthenium adopts a pseudooctahedral arrangement with PPh3 and hydrazine mutually cis. The Ru-N bond lengths in cis-14.CH2Cl2 and cis-15 are 2.152(3) and 2.101(3) A, respectively. The Ru-N-N bond angles in cis-14.CH2Cl2 and cis-15 are 120.5(4) and 129.0(2) degrees, respectively. Treatment of 1 with hydrazine monohydrate leads to the isolation of yellow 5 and red trans-Ru[N(Ph2PS)2]2(NH3)(H2O) (16), which are characterized by mass spectrometry, 1H NMR spectroscopy, and elemental analyses. The geometry around ruthenium in 16 is pseudooctahedral with the NH3 and H2O ligands mutually trans. The Ru-O and Ru-N bond distances are 2.118(4) and 2.142(6) A, respectively. Oxidation reactions of the above ruthenium hydrazine complexes are also studied.     

The photodissociation reaction dynamics of CF(3)I at 304 nm ((3)Q(0+), (1)Q(1)<--(3)Q(0+), and (3)Q(1))

The photodissociation of CF(3)I at 304 nm has been studied using long time-delayed core-sampling photofragment translational spectroscopy. Due to its capability of detecting the kinetic energy distribution of iodine fragments with high resolution, it is able to directly assign the vibrational state distribution of CF(3) fragments. The vibrational state distributions of CF(3) fragments in the I(*)((2)P(12)) channel, i.e., (3)Q(0+) state, have a propensity of the nu(2) (') umbrella mode with a maximum distribution at the vibrational ground state. For the I((2)P(32)) channel, i.e., (1)Q(1)<--(3)Q(0+), the excitation of the nu(2) (') umbrella mode accounts for the majority of the vibrational excitation of the CF(3) fragments. The 1 nu(1) (') (symmetric CF stretch) +nnu(2) (') combination modes, which are associated with the major progression of the nu(2) (') umbrella mode, are observed for the photodissociation of CF(3)I at the I channel, i.e., (3)Q(1) state. The bond dissociation energy of the CI bond of CF(3)I is determined to be D(0)(CF(3)-I)相似文献   

Adduct between quadricyclane and (η-cyclopentadienyl)(1,2-benzenedithiolato)cobalt(III): formation and structure

The reaction of (η⁵-cyclopentadienyl)(1,2-benzenedithiolato)cobalt(III) (1) in quadricyclane (Q) at 90°C gives 1:1 adducts of 1 and Q. The main adduct (40% yield) has a unique structure, in which the 5-and 7-positions of norbornene are bonded to Co and S of 1. A mechanism of the formation of the adduct (by the use of deuterium-labeled Q), including a skeletal rearrangement of Q, is proposed.     

七元瓜环对2'-羟基查尔酮溶解性、稳定性及抗氧化活性的影响

利用~1H NMR、紫外吸收光谱和荧光光谱等方法考察了七元瓜环(Q[7])对2'-羟基查尔酮(CET)的包结作用.结果表明,Q[7]与CET形成了摩尔比为1∶1的包结配合物,紫外吸收光谱和荧光光谱测得的结合稳定常数分别为1.0248×10~6和1.253×10~6.相溶解度法研究结果表明,当Q[7]的浓度为1×10~(-3)mol/L时,可使CET在水中的溶解度增加52倍.紫外吸收光谱随时间变化的研究结果表明,Q[7]使CET的稳定性增加3.5倍.采用体外抗氧化活性测定(ABTS法)考察了Q[7]对CET抗氧化活性的影响,发现CET@Q[7]包结配合物以及游离CET均对ABTS自由基有较好的清除作用.IC50值分别为3.4×10~(-5)和2.4×10~(-5)mol/L,表明Q[7]不仅能增加CET的溶解性和稳定性,同时对CET抗氧化活性的影响不大.     

Water Activity Regulates the Q(A)(-) to Q(B) electron transfer in photosynthetic reaction centers from Rhodobacter sphaeroides

We report on the effects of water activity and surrounding viscosity on electron transfer reactions taking place within a membrane protein: the reaction center (RC) from the photosynthetic bacterium Rhodobacter sphaeroides. We measured the kinetics of charge recombination between the primary photoxidized donor (P(+)) and the reduced quinone acceptors. Water activity (aW) and viscosity (eta) have been tuned by changing the concentration of cosolutes (trehalose, sucrose, glucose, and glycerol) and the temperature. The temperature dependence of the rate of charge recombination between the reduced primary quinone, Q(A)(-), and P(+) was found to be unaffected by the presence of cosolutes. At variance, the kinetics of charge recombination between the reduced secondary quinone (Q(B)(-)) and P(+) was found to be severely influenced by the presence of cosolutes and by the temperature. Results collected over a wide eta-range (2 orders of magnitude) demonstrate that the rate of P(+)Q(B)(-) recombination is uncorrelated to the solution viscosity. The kinetics of P(+)Q(B)(-) recombination depends on the P(+)Q(A)(-)Q(B) <--> P(+)Q(A)Q(B)(-) equilibrium constant. Accordingly, the dependence of the interquinone electron transfer equilibrium constant on T and aW has been explained by assuming that the transfer of one electron from Q(A)(-) to Q(B) is associated with the release of about three water molecules by the RC. This implies that the interquinone electron transfer involves at least two RC substates differing in the stoichiometry of interacting water molecules.     

Inclusion complexes of the antitumour metallocenes Cp(2)MCl(2) (M = Mo, Ti) with cucurbit[n]urils

The encapsulation of the aquated forms of molybdocene dichloride and titanocene dichloride by cucurbit[n]uril (Q[n], where n = 7 and 8) at different pD values has been studied by (1)H NMR spectroscopy and molecular modelling. (1)H NMR titration experiments indicate that both metallocenes form 1 : 1 host-guest complexes with both Q[7] and Q[8]. In these complexes, both the cyclopentadienyl ligands and metal centre are positioned deep within the cucurbituril cavity. In vitro cell proliferation studies using the cancer cell lines MCF-7 and 2008 showed that the encapsulated molybdocene complex was more active than the corresponding free metallocene, with GI(50) values of 210 and 400 muM respectively. However, unexpectedly the encapsulation of Cp(2)MoCl(2(aq))at pD 7 catalysed significant degradation of the cucurbituril framework in the presence of oxygen. Encapsulation of Cp(2)TiCl(2(aq)) by Q[7] greatly slowed the protonolysis of the cyclopentadienyl ligands in aqueous phosphate buffer (pD 7), while encapsulation in Q[8] only slightly retarded the hydrolytic degradation of the metallocene.     

Simple preparations of Pd6Cl12, Pt6Cl12, and Qn[Pt2Cl8+n], n=1, 2 (Q=TBA+, PPN+) and structural characterization of [TBA][Pt2Cl9] and [PPN]2[Pt2Cl10].C7H8

The hexanuclear Pd6Cl12, i.e., the crystal phase classified as beta-PdCl2, was obtained by reacting [TBA]2[Pd2Cl6] with AlCl3 (or FeCl3) in CH2Cl2. The action of AlCl3 on PtCl42-, followed by digestion of the resulting solid in 1,2-C2H4Cl2 (DCE), CHCl3, or benzene, produced Pt6Cl12.DCE, Pt6Cl12.CHCl3, or Pt6Cl12.C6H6, respectively. Treating [TBA]2[PtCl6] with a slight excess of AlCl3 afforded [TBA][Pt2Cl9], whose anion was established crystallographically to be constituted by two "PtCl6" octahedra sharing a face. Dehydration of H2PtCl6.nH2O with SOCl2 gave an amorphous compound closely analyzing as PtCl4, reactive with [Q]Cl in SOCl2 to yield [Q][Pt2Cl9] or [Q]2[Pt2Cl10], depending on the [Q]Cl/Pt molar ratio (Q=TBA+, PPN+). A single-crystal X-ray diffraction study has shown [PPN]2[Pt2Cl10].C7H8 to contain dinuclear anions formed by two edge-sharing PtCl6 octahedra.     

Mechanochemical synthesis and crystal structure of acetylacetonate complexes with the triangular Mo3Q7 4+ core (Q = S or Se)

Mechanochemical reactions of inorganic polymers ¹ _∞[Mo₃Q₇Br₄] (Q = S or Se) with sodium acetylacetonate hydrate lead to excision of the Mo₃Q₇ ⁴⁺ cluster core giving rise to the cationic complexes [Mo₃Q₇(acac)₃]⁺. Extraction of the reaction mixture with acetone followed by recrystallization from a benzene-hexane mixture afforded the {[Mo₃S₇(CH₃COCHCOCH₃)₃]Br}·2C₆H₆ (1) and {[Mo₃Se₇(CH₃COCHCOCH₃)₃]Br}· · 2C₆H₆ (2) complexes. The structures of complexes 1 and 2 were studied by IR and ¹H NMR spectroscopy and X-ray diffraction. Compound 1 was characterized by electrospray mass spectrometry. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1895–1898, November, 2006.