Showing papers by "Brian W. Skelton published in 2008"
TL;DR: The application of solvent-assisted mechanochemical synthesis to the study of metal complex formation is illustrated by examples involving complexes of silver halides with ethylenethiourea.
Abstract: The application of solvent-assisted mechanochemical synthesis to the study of metal complex formation is illustrated by examples involving complexes of silver halides with ethylenethiourea.
78 citations
TL;DR: Spectro-electrochemical studies of the ruthenium aryl and arylene alkynyl complexes indicate that perfluorination of the aromatic ring compounds has little effect on the appreciable diet orbit and the electronic character of the compounds is reported.
Abstract: Transition metal alkynyl complexes containing perfluoroaryl groups have been prepared directly from trimethylsilyl-protected mono- and di-ethynyl perfluoroarenes by simple desilylation/metallation reaction sequences. Reactions between Me3SiCCC6F5 and RuCl(dppe)Cp′ [Cp′ = Cp, Cp*] in the presence of KF in MeOH give the monoruthenium complexes Ru(CCC6F5)(dppe)Cp′ [Cp′ = Cp (2); Cp* (3)], which are related to the known compound Ru(CCC6F5)(PPh3)2Cp (1). Treatment of Me3SiCCC6F5 with Pt2(μ-dppm)2Cl2 in the presence of NaOMe in MeOH gave the bis(alkynyl) complex Pt2(μ-dppm)2(CCC6F5)2 (4). The Pd(0)/Cu(I)-catalysed reactions between Au(CCC6F5)(PPh3) and Mo(≡CBr)(CO)2Tp* [Tp* = hydridotris(3.5-dimethylpyrazoyl)borate], Co3(μ3-CBr)(μ-dppm)(CO)7 or ICCFc [Fc = (η5-C5H4)FeCp] afford Mo(≡CCCC6F5)(CO)2Tp* (5), Co3(μ3-CCCC6F5)(μ-dppm)(CO)7 (6) and FcCCCCC6F5 (7), respectively. The diruthenium complexes 1,4-{Cp′(PP)RuCC}2C6F4 [(PP)Cp′ = (PPh3)2Cp (8); (dppe)Cp (9); (dppe)Cp* (10)] are prepared from 1,4-(Me3SiCC)2C6F4 in a manner similar to that described for the monoruthenium complexes 1–3. The non-fluorinated complexes 1,4-{Cp′(PP)RuCC}2C6H4 [(PP)Cp′ = (PPh3)2Cp (11); (dppe)Cp (12); (dppe)Cp* (13)], prepared for comparison, are obtained from 1,4-(Me3SiCC)2C6H4. Spectro-electrochemical studies of the ruthenium aryl and arylene alkynyl complexes 2–3 and 8–13, together with DFT-based computational studies on suitable model systems, indicate that perfluorination of the aromatic ring has little effect on the electronic structures of these compounds, and that the frontier orbitals have appreciable diethynylphenylene character. Molecular structure determinations are reported for the fluoroaromatic complexes 1, 2, 3, 6 and 10.
61 citations
TL;DR: In this article, three new polymorphs of the highly active organic nonlinear optical (NLO) material 3-methyl-4methoxy-4′-nitrostilbene (MMONS) have been discovered during crystallization experiments.
Abstract: During crystallization experiments two new polymorphs of the highly-active organic nonlinear optical (NLO) material 3-methyl-4-methoxy-4′-nitrostilbene (MMONS) have been discovered Crystallization conditions of all three polymorphs and their characterization via crystal structure determination from single crystal X-ray diffraction data at 100 K have been discussed in detail Two of the polymorphs exhibit different conformations, while a third polymorph incorporates both conformers as well as disorder Comparisons between various types of intermolecular contacts in these three polymorphic forms have been quantified via Hirshfeld surface analysis
45 citations
TL;DR: The potent immucillin purine nucleoside phosphorylase (PNP) inhibitors F-DADMe-ImmH [(3S,4S)-3], and [(3R,4R)-3] are synthesized in seven steps by use of a three-component Mannich reaction.
Abstract: The potent immucillin purine nucleoside phosphorylase (PNP) inhibitors F-DADMe-ImmH [(3S,4S)-3], and [(3R,4R)-3] are synthesized in seven steps. Cycloaddition to a fluoroalkene and an enzymic resolution are the key features of the construction of the fluoropyrrolidines 11, from which the immucillins are assembled by use of a three-component Mannich reaction. Slow-onset binding constants (Ki∗) for [(3S,4S)-3] and [(3R,4R)-3] with human PNP are 0.032 and 1.82 nM, respectively. F-DADMe-ImmH [(3S,4S)-3] exhibits oral availability in mice at doses as low as 0.2 mg/kg.
44 citations
TL;DR: The role of short-range diffusion in solvent-assisted mechanochemical synthesis is demonstrated in studies of a polymorphic transition and a ligand dissociation reaction involving copper(I) thiocyanate complexes.
Abstract: The role of short-range diffusion in solvent-assisted mechanochemical synthesis is demonstrated in studies of a polymorphic transition and a ligand dissociation reaction involving copper(I) thiocyanate complexes.
44 citations
TL;DR: In this article, the effect of a pair of nitrogen donors, both unidentate and chelate, on the bonding parameters of the mixed N,P-donor complexes of copper(I) thiocyanate was investigated.
Abstract: The syntheses, spectroscopic characterization (IR, 1H and 31P NMR, ESI-MS) and conductivity studies of the mixed N,P-donor complexes of copper(I) thiocyanate: [Cu(NCS)(py)2(PPh3)], (2), [Cu(NCS)(Mepy)(PPh3)]2, (3), [Cu(NCS)(phen)(PPh3)], (4), [Cu(NCS)(bpy)(PPh3)], (5), [Cu(NCS)(bpy)(PPh2py)], (6), [Cu(NCS)(py)(PPh2py)], (7), (py = pyridine; Mepy = 2-methylpyridine; phen = 1,10-phenanthroline, bpy = 2,2′-bipyridyl), together with single-crystal X-ray structural characterizations of 2, 3, 4 (new polymorph), 5 and 6 are reported, which provides an opportunity to study the effect of the introduction of a pair of nitrogen donors, both unidentate and chelate, on the bonding parameters of the Cu/NCS/P system. Cu–P and Cu–N2(ar) are found to be similar [2.1974(5) and 2.091(2), 2.070(1) A for py2 adduct 2, cf. 2.1748(9)–2.200(1) and 2.071(2)–2.106(4) A for the counterpart values for bidentate adducts 4–6]. However, Cu–N(CS) and Cu–N–C are 2.013(2) A and 157.4(2)° for py2 adduct 2 and 1.946(2)–1.981(8) A and 166.7(2)–176.58(2)° for bidentate counterparts 4–6. The change is attributed primarily to the closure in the N–Cu–N angle [99.58(8)° for py22; 77.7(6)–80.5(3)° for N∧N-bidentate donors 4–6]. In consequence of the increased steric profile of the Mepy ligand, we find the stoichiometry diminished to 1:1:1, which resulted in theformation of [(Ph3P)MepyCu(SCNNCS)Cu(Mepy)(PPh3)] dimers.TDDFT/CPCM calculations were used to clarify the type of transitions involved in the UV/Vis absorption spectra, and the corresponding experimental photoemission data wereacquired. The 31P CPMAS spectra of the copper derivatives exhibit distorted quartets that afford values for 1JCu,P. Furthermore, the quadrupole-induced distortion factors were calculated, and in the cases of 2, 4 and 5, the quadrupole coupling constants were obtained, on the basis of the X-ray structures.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
38 citations
TL;DR: In this paper, the Cp analogue 2 and Co3(CO)9 cluster analogue 3 were obtained via three routes that involve assembly of the C7 chain by combination of appropriate C1 + C6, C2 + C5, or C3 + C4 precursors.
32 citations
TL;DR: The oxidative coupling of polysubstituted electron-rich indoles mediated by thallium trifluoroacetate was found to be a facile, clean, and high yielding reaction as mentioned in this paper.
31 citations
TL;DR: The addition of alkyl/alkoxy chains to the cyclophane chains allows for studies in chlorinated solvents, whereas previous solution studies of azolium cyclophanes have generally required highly polar solvent studies.
Abstract: This paper describes the synthesis, structural characterization, and solution behavior of some xylyl-linked imidazolium and benzimidazolium cyclophanes decorated with alkyl or alkoxy groups. The addition of alkyl/alkoxy chains to the cyclophanes allows for studies in chlorinated solvents, whereas previous solution studies of azolium cyclophanes have generally required highly polar solvents. The azolium cyclophanes may exist in a syn/syn conformation (azolium rings mutually syn, arene rings mutually syn) or a syn/anti conformation (azolium rings mutually syn, arene rings mutually anti). The preferred conformation is significantly affected by (i) binding of bromide (ion pairing) to the protons on the imidazolium or benzimidazolium rings, which occurs in solutions of bromide salts of the cyclophanes in chlorinated solvents, and (ii) the addition of alkoxy groups to the benzimidazolium cyclophanes. These structural modifications have also led to cyclophanes that adopt conformations not previously identified f...
30 citations
TL;DR: In this article, a series of complexes with π-conjugated carbon chains terminated by bipyridyl moieties has been prepared, and the effect of the variation in metal and ligand on electronic and electrochemical characteristics of these complexes has been investigated by using UV-vis, solution electrochemistry, and a combination of these techniques in spectroelectrochemical experiments.
29 citations
TL;DR: A network of weak N-HS hydrogen bonds, involving the terminal NCS ligands and NH2-groups of en, links the infinite chains and results in the formation of an extended supramolecular three-dimensional framework.
Abstract: A novel heterometallic 1D coordination polymer [{Ni(en)2}2(µ-NCS)4Cd(NCS)2]n·nCH3CN (en = ethylenediamine) has been prepared using the self-assembly process in a one-pot reaction of cadmium oxide, nickel and ammonium thiocyanates with an acetonitrile solution of ethylenediamine. The complex consists of an uncommon cis-Cd(SCN)4(NCS)24− fragment and a rare combination of cis-Ni(en)22+ and trans-Ni(en)22+ building blocks linked by µ1,3-NCS bridges into a double-stranded zigzag chain structure. Each chain is comprised of [Ni2Cd2(µ-NCS–N,S)4)] macrocycles with chair-like and rectangular-like shapes arrayed alternately. The shortest intrachain Cd⋯Cd separations are 9.535(1) and 10.868(2) A, while the nearest Ni⋯Ni distances are 5.418(1) and 6.612(2) A. A network of weak N–H⋯S hydrogen bonds, involving the terminal NCS ligands and NH2-groups of en, links the infinite chains and results in the formation of an extended supramolecular three-dimensional framework. Variable-temperature (1.8–300 K) magnetic susceptibilities show a slight change of the µB value at low temperature, indicative of weak antiferromagnetic interactions (J = 1.55 cm−1) between magnetic canters. High-field, high-frequency (100–400 GHz) EPR spectra were simulated using S = 1 ground state for separate Ni2+ ions with the spin Hamiltonian parameters g = 2.165, D = 0.45 cm−1 and E = 0.03 cm−1. According to DFT calculations, the D and E parameters are −0.35 cm−1 and 0.049 cm−1 for the cis arrangement of Ni2+ and 0.58 cm−1 and 0.012 cm−1 for trans.
TL;DR: Several bis-cluster complexes containing Co3 carbonyl clusters endcapping carbon chains of various lengths are described in this paper, including the longest cluster-capped Cx chains so far described.
TL;DR: Anhydrous rare earth tris(cinnamates) as mentioned in this paper were prepared by metathesis in water and by direct reaction of the metal with cinnamic acid in a 1,2,4,5-tetramethylbenzene flux at ca. 200 °C. X-ray crystal structure determinations and Xray powder data show that, in the solid state, the larger lanthanoids (La−Dy) form an isomorphous polymeric series consisting of homoleptic nine-coordinate metal centres bonded to three chel
Abstract: Anhydrous rare earth tris(cinnamates) [RE(cinn)3] (RE = La–Lu, Y and Sc and cinnH = trans-cinnamic acid) were prepared by metathesis in water and by direct reaction of the metal with cinnamic acid in a 1,2,4,5-tetramethylbenzene flux at ca. 200 °C. X-ray crystal structure determinations and X-ray powder data show that, in the solid state, the larger lanthanoids (La–Dy) form an isomorphous polymeric series consisting of homoleptic nine-coordinate metal centres bonded to three chelating and bridging tridentate cinnamates. The late REIII cinnamate (RE = Dy, Ho–Lu, Y) complexes also form linear one-dimensional polymeric chains with all RE metal atoms being seven-coordinate. The cinnamates are either bound tridentate bridging in a μ-η2:η1 fashion, or μ-η1:η1syn-syn bidentate bridging. A structural break occurs at dysprosium which has been characterised in both crystallographic forms, and gives solely the late RE form when precipitated at 80 °C. ScIII cinnamate was also isolated as an analytically pure precipitate which was, again, found to be anhydrous in nature. A structural change was identified by powder XRD between the late REIII cinnamates and ScIII cinnamate.
TL;DR: Pyrido- and pyrrolo[2,3-d]oxazoles can be conveniently prepared in high yield from the Ritter reaction of nitriles and in situ generated chiral cyclic N-acyliminium ions.
Abstract: Pyrido- and pyrrolo[2,3-d]oxazoles can be conveniently prepared in high yield from the Ritter reaction of nitriles and in situ generated chiral cyclic N-acyliminium ions. cis-4-Hydroxy-5-acylaminopyrrolidines and cis-5-hydroxy-6-acylaminopiperidines can be readily obtained by acid hydrolysis of these bicyclic heterocyclic compounds, respectively.
TL;DR: In this article, a transmetallation reagent, SnMe2(Ph2pz)2, was used to obtain the first trace of tin-containing products.
Abstract: Reaction of SnMe2Cl2 with [Li(Ph2pz)] (Ph2pz = 3,5-diphenylpyrazolate) in diethyl ether in a 1:2 ratio afforded the new transmetallation reagent [SnMe2(Ph2pz)2]. Treatment of [SnMe2(Ph2pz)2] with Ln metals in either 1,2-dimethoxyethane (dme) or tetrahydrofuran (thf) provided a new route to the divalent [Ln(Ph2pz)2(dme)2] (Ln = Sm, Eu, Yb) and the trivalent [La(Ph2pz)3(dme)2] and [Yb(Ph2pz)3(thf)2] complexes in comparable yields to those from alternative methods. These reactions enabled isolation of the highly reactive [Sm(Ph2pz)2(dme)2] complex in good yield, in addition to the new cis isomer of [Eu(Ph2pz)2(dme)2], thereby establishing a rare case of geometric isomerism in lanthanoid chemistry. 1H and 119Sn NMR spectral studies and EDAX measurements were performed on the reaction mixture and/or residue to identify the tin-containing products and suggest formation of SnMe4, Sn2Me6, tin metal and two other SnMe3 species, which plausibly result from decomposition of unstable "SnMe2". Treatment of [Yb(Ph2pz)2(dme)2] with [SnMe2(Ph2pz)2] or [Tl(Ph2pz)] resulted in the isolation of [Yb(Ph2pz)3(thf)2]·2C6D6 and [Yb(Ph2pz)3(dme)]·0.5dme complexes, the structures of which have eight-coordinate Yb atoms and contrast nine-coordination observed for previous [Ln(Ph2pz)3(thf or dme)n] complexes.
TL;DR: Single-crystal structural characterizations confirm the existence of the unusual 1 : 4 copper(I) halide : unidentate ligand adducts and Metal-carbon and metal-halogen bands are assigned in the far-IR spectra, which indicate a binuclear double halogen-bridged structure for the 1 : 1.5 complexes.
Abstract: Single-crystal structural characterizations confirm the existence of the unusual 1 : 4 copper(I) halide : unidentate ligand adducts [Cu(CNt-Bu)4]X for X = Cl, Br (two forms), I (the chloride and one form of the bromide being solvated) with crystal packing dominated by stacks of interleaving cations. Cu–C range between 1.941(2) and 1.972(4) A. The structure of the 1 : 2 chloride complex is also recorded, being [ClCu(CNt-Bu)2], with the copper(I) atom environment trigonal planar, while CuCN : (CNt-Bu) (1 : 1) is a single-stranded polymer which spirals about a crystallographic 3-axis (CN scrambled), the ligands being pendant from the …CuCNCuCN… string. The 65Cu static broadline NMR spectra of [Cu(CNt-Bu)4]I and [Cu(CNt-Bu)4]Br·H2O in the solid state exhibit dominant, narrow −1/2 ↔ +1/2 central transition resonances and associated ±1/2 ↔ ±3/2 satellite transition resonances which are characteristic of first-order quadrupole broadened systems, while associated high-resolution 65Cu MAS NMR data provide accurate measurement of the 65Cu isotropic chemical shifts. Both approaches provide complete data on the quadrupole and chemical shift interactions which contribute to these spectra. Far-IR spectra of products of reactions involving a range of CuX : t-BuNC ratios reveal the existence of 1 : 1.5 adducts for X = Br, I. Metal–carbon and metal-halogen bands are assigned in the far-IR spectra, which indicate a binuclear double halogen-bridged structure for the 1 : 1.5 complexes.
TL;DR: In this paper, the iodovinylidene [Ru(C CHI)(dppe)Cp∗]BF4 1, which could be deprotonated to Ru(C CI)CAu(PPh3)cpi∗ 2 by formal replacement of I+ by [Au(pPh3)]+.
TL;DR: The structural characterizations of the potassium complexes of a pair of dianionic bisphenolate ligands are recorded, showing them to take the binuclear form [K2LR(DME)3].
Abstract: The structural characterizations of the potassium complexes of a pair of dianionic bis(phenolate) ligands, {LR = [−OC6H2(2,4-But)(6-CH2)]2NCH2CH2R} R = NMe2, OMe, crystallized from 1,2,-dimethoxyethane (DME) are recorded, showing them to take the binuclear form [K2LR(DME)3]. A pair of neutral binuclear heterobimetallic isotypic complexes are defined with ytterbium(III), with phenol, as sodium salts, of the form [Yb(LR)(OPh)2Na(DME)(HOPh)], and a further array with samarium(III), of the (partially protonated) form [Sm(LOMe)2Na(OH2)]. A further complex, [Na(DME)3][Yb(*Lpy)2], results from an unusual ligand reduction by an ytterbium(II) species to give a new dianionic Schiff base ligand which is coordinated to ytterbium(III) {*Lpy = −OC6H2(2,4-But)(6-CH=N-CH-2-C6H4N)}.
TL;DR: In this article, a three-step synthesis of a new fused bisindole system isomeric with the heterocyclic skeleton present in the marine natural product iheyamine A has been achieved.
TL;DR: In this paper, the structure determination of a 1:4 adduct of a silver salt with a (substituted) thiourea ligand is also reported, for silver(I) nitrate with ‘ethylenethIourea’, (‘etu’ = SC(NHCH2)2), as a monohydrate [Ag(etu)4](NO3)·H2O, wherein Ag-S range between 2.544-2.637(2), 2.59(4) A, S
Abstract: In a low-temperature redetermination of improved precision of the structure of [Cu(tu)4]2(SiF6) (‘tu’ = thiourea, SC(NH2)2), Cu–S range between 2.3173–2.3433(8), 2.336(11) A, with S–Cu–S 92.72(3)–118.75(12)°. The first structure determination of a 1:4 adduct of a silver(I) salt with a (substituted) thiourea ligand is also reported, for silver(I) nitrate with ‘ethylenethiourea’, (‘etu’ = SC(NHCH2)2), as a monohydrate [Ag(etu)4](NO3)·H2O, wherein Ag–S range between 2.544–2.637(2), 2.59(4) A, S–Ag–S 87.88–117.57(7)°. Bands in the far-IR spectra of these compounds are assigned to ν(MS) modes, and the frequencies are compared with those predicted by previously established correlations between ν(MS) and the M–S bond length d(MS) for copper or silver complexes with tu or etu ligands.
TL;DR: In this paper, the X-ray crystal structures of the metallocene dichlorides were reported, and their reactivity patterns and solution fluxional properties were discussed, as well as their properties.
TL;DR: Several gold-containing cluster complexes have been obtained from the reactions of gold alkynyl complexes, including the bis-cluster complex 1,4-{AuRu3(CO)9(PPh3)(μ3-C2C]-C[Ru(PP)Cp′]}.
Abstract: Several new gold-containing cluster complexes have been prepared from the reactions of gold alkynyl complexes, L
n
M-C
x
-Au(PPh3), (x = 3, 4, 6) with Ru3(CO)10(NCMe)2. The bis-cluster complex 1,4-{AuRu3(CO)9(PPh3)(μ3-C2)}2C6H4 was obtained from Ru3(CO)10(NCMe)2 and 1,4-{(Ph3P)Au(C≡C)}2C6H4. The complexes Ru3(μ-H){μ3-C2C≡C[Ru(PP)Cp′]}(CO)9 [PP = (PPh3)2, Cp′ = Cp; PP = dppe, Cp′ = Cp*] were also obtained as minor by-products and synthesised independently from Ru(C≡CC≡CH)(PP)Cp′. A reaction between Co3{μ3-CC≡CC≡CAu(PPh3)}(μ-dppm)(CO)7 and Ru3(CO)12 afforded {(Ph3P)(OC)9AuRu3}C≡CC≡CC{Co3(μ-dppm)(CO)7} 7. Related complexes AuRu3{μ3-C2C≡[M(CO)2Tp]}(CO)9(PPh3) (M = Mo 8, W 9) were obtained from {Tp(OC)2M}≡CC≡C{Au(PPh3)}, while the mixed metal cluster complexes MoM2(C2Me)(CO)8Tp (M = Ru 13, Fe 14) were obtained from M(≡CC≡CSiMe3)(CO)2Tp (M = Mo, W) with Fe2(CO)9 and Ru3(CO)12, respectively. Reactions of the Mo carbyne complex with Co2(LL)(CO)6 [LL = (CO)2, μ-dppm] or nickelocene afforded complexes 15–17 in which Co2 and Ni2 fragments, respectively, had coordinated to the C≡C triple bond. XRD structural determinations of 7, 8, 14, 16 and {Tp(OC)2W}≡CC≡CC≡{Co3(μ-dppm)(CO)7} (18-W) are reported.
TL;DR: In this paper, a cycloaddition of the resulting cyclobutenyl (not detected) and displacement of a PPh 3 ligand was reported. But the results were not analyzed.
TL;DR: In this paper, a single crystal X-ray structure determination is recorded for CuNO3:dmp:MeCN (1: 1:1), showing it to be isomorphous with its previously studied tetrafluoroborate, perchlorate and hexafluorophosphate, and silver(I) perchlorates counterparts, the metal atom lying in a trigonal planar [(N∧N)Cu(NCMe)] coordination environment, the anion not being coordinated.
TL;DR: In this paper, the authors characterized the properties of the ligands in the trimetallic clusters [Ru{sub 3}(CO){sub 10}(dppm), [RuCo{sub 2](CO)] and [RuSub 3} (CO) under various conditions which have been characterized by spectroscopic and crystallographic means.
TL;DR: In this article, the neutral mer-triaquatrichloroiron(III) molecule, mer-[(H2O)3FeCl3], has been structurally defined, co-crystallized with a pair of organic-cation/chloride salts, from hydrochloric acid solution in each case.
Abstract: The neutral mer-triaquatrichloroiron(III) molecule, mer-[(H2O)3FeCl3], has been structurally defined, co-crystallized with a pair of organic-cation/chloride salts, from hydrochloric acid solution in each case. The array {[HN(CH2CH2)3NH]Cl2}{mer-[(H2O)3FeCl3]}, (1) has been previously described in a room-temperature study in terms of orthorhombic Pnma symmetry; here, at low-temperature (ca. 153 K), the description is in terms of P212121, with the complex of quasi-m symmetry. Full m symmetry is achieved in the second complex, {[H2N(CH2CH2)2NH2]Cl2}{mer-[(H2O)3FeCl3]}, (2) which crystallizes in space group P21/m. Fe–Cl and Fe–O(H2) are very tightly ranged in 1, 2.3359(6), 2.051(5) A, respectively, less so in 2 (2.326(1), 2.340(1); 2.049(2)–2.080(2) A), despite strong hydrogen-bonding in the lattice between the hydrogen atoms of the coordinated water molecules and the uncoordinated chloride ions. A redetermination of the structure of FeCl3·6H2O (3), trans-tetraquadichloroiron(III) chloride dihydrate, is also recorded; at 100 K,Fe–Cl,O are 2.2830(4), 2.0543(9) A.
TL;DR: In this article, the first examples of metalated 6-alkylthio-6-azafulvenes, Ru{C═CRC(SMe)═C(CN)C═N(SME), were described.
TL;DR: In this article, the reaction between RuCl(PPh 3 ) 2 Cp ∗ and {Cu(CCPh)} n in refluxing benzene afforded Ru 2 Cu 2 (C 2 Ph) 5 H 2 (Cl) ∗ 2, which contains an unusual tetramer of the phenylethynyl group which interacts with an Ru…Cu…Cu/Ru chain.
TL;DR: In this article, a tetragonal series of isotypic, isotype-based structure determinations of complex thiosulfate/univalent coinage metal anions was presented.
Abstract: Building on previous single crystal X-ray structure determinations for the group 1 salts of complex thiosulfate/univalent coinage metal anions previously defined for (NH4)9AgCl2(S2O3)4, NaAgS2O3·H2O and Na4[Cu(NH3)4][Cu(S2O3)2]·NH3, a wide variety of similar salts, of the form , M1 = group 1 metal cation, M2 = univalent coinage metal cation (Cu, Ag), (X = univalent anion), most previously known, but some not, have been isolated and subjected to similar determinations. These have defined further members of the isotypic, tetragonal series, for M1 = NH4, M2 = Cu, Ag, X = NO3, Cl, Br, I, together with the K/Cu/NO3 complex, all containing the complex anion [M2(SSO3)4]7− with M2 in an environment of symmetry, Cu, Ag-S typically ca. 2.37, 2.58A, with quasi-tetrahedral S-M-S angular environments. Further salts of the form , n = 1-3, have also been defined: For n = 3, M2 = Cu, M1/x = K/2.25 or 1 5/6, NH4/6, (and also for the (NH4)4Na/4H2O·MeOH adduct) the arrays take the form with distorted trigonal planar CuS3 coordination environments, Cu-S distances being typically 2.21A, S-Cu-S ranging between 105.31(4)–129.77(4)°; the silver counterparts take the form for M1 = K, NH4. For n = 2, adducts have only been defined for M2 = Ag, the anions of the M1 = Na, K adducts being dimeric and polymeric respectively: Na6[(O3SS)2Ag(μ-SSO3)2Ag(SSO3)]·3H2O, K3[Ag(μ-SSO3)2](∞|∞)·H2O; a polymeric copper(I) counterpart of the latter is found in Na5Cu(NO3)2(S2O3)2 ≡ 2NaNO3·Na3[Cu(μ-SSO3)2](∞|∞). For n = 1, NaAgS2O3, the an- and mono- hydrates, exhibit a two-dimensional polymeric complex anion in both forms but with different contributing motifs. (NH4)13Ag3(S2O3)8·2H2O takes the form (NH4)13[{(O3SS)3Ag(μ-SSO3)}2Ag], a linearly coordinated central silver atom linking a pair of peripheral [Ag(SSO3)4]7− entities. In Na6[(O3SS)Ag(μ-SSO3)2Ag(SSO3)]·3H2O, the binuclear anions present as Ag2S4 sheets, the associated oxygen atoms being disposed to one side, thus sandwiching layers of sodium ions; the remarkable complex Na5[Ag3(S2O3)4](∞|∞)·H2O is a variant, in which one sodium atom is transformed into silver, linking the binuclear species into a one-dimensional polymer. In (NH4)8[Cu2(S2O3)5]·2H2O a binuclear anion of the form [(O3SS)2Cu(μ-S.SO3)Cu(SSO3)2]8− is found; the complex (NH4)11Cu(S2O3)6 is 2(NH4)2(S2O3)·(NH4)7[Cu(SSO3)4]. A novel new hydrate of sodium thiosulfate is described, 4Na4S2O3·5H2O, largely describable as sheets of the salt, shrouded in water molecules to either side, together with a redetermination of the structure of 3K2S2O3·H2O.
TL;DR: In this article, the R = Ph derivative was found to be isotypic with its C6F5 analogue, presenting an unusual opportunity for a comparative structural study, both structures being (re-)determined at low temperature.
Abstract: Complexes of the form [Ru3(μ-H)(μ3-C2X)(μ-dppm)(CO)7] have been widely characterized structurally for diverse R = H, tBu, CMePh(OH), CPhCH2, C5H7, C5H6Me, C6F5, as well as being studied theoretically. The R = Ph derivative was found to be isotypic with its C6F5 analogue, presenting an unusual opportunity for a comparative structural study, both structures being (re-)determined at ‘low’-temperature, whereupon the unit cell of the Ph derivative was found to double. The structure of [AuRu3(μ-C2C6F5)(CO)9(PPh3)] is also recorded.