Showing papers by "Brian W. Skelton published in 1983"
91 citations
TL;DR: In this paper, the structure of 1.5 Cu : halide : base stoicheiometry with 2-methylpyridine (2Me-py) was determined using a single-crystal X-ray diffraction.
Abstract: Crystallization of copper(I) iodide from triethylamine–acetone yields a white crystalline solid of novel stoicheiometry [Cu4I4(NEt3)3]; its structure determination by single-crystal X-ray diffraction shows trigonal symmetry [space group P3, a= 19.46(2), c= 7.119(7)A, and Z= 3] and polymeric strings of Cu4I4‘cubane’ units, oriented with one body diagonal of each unit along c and linked to the next unit generated by the unit c translation by a copper–iodine interunit bond [2.930A(mean)]. There are three independent such polymeric strings in the unit cell. R was 0.074 for 2 942 ‘observed’ reflections. The structures of the 1 : 1 complexes of copper(I) iodide with 2-methylpyridine, (2Me-py)(2), 2,2,6,6-tetramethylpiperidine, (tmpip)(3), and acridine, (4), have also been determined. Each crystallizes in a structural form determined by the steric properties of the ligand. Crystals of (2) are tetragonal, space group I4cm, with a= 20.10(2) and c= 15.94(1)A; R= 0.055 for 782 independent observed reflections. The structure is a ‘cubane’-type tetramer, [Cu4I4(2Me-py)4], with Z= 8. Crystals of (3) are orthorhombic, space group Cmca, with a= 12.43(2), b= 9.964(7), and c= 19.30(3)A; R= 0.071 for 278 independent observed reflections. The structure is a di-µ-iodo-bridged dimer [Cu2I2(tmpip)2], with four molecules in the unit cell. Crystals of (4) are triclinic, space group P, with a= 14.381(4), b= 9.888(3), c= 4.117(1)A, α= 83.96(2), β= 81.57(2), and γ= 86.03(2)°; R= 0.078 for 2 649 observed reflections. The structure is a ‘split stair’ polymer, (–CuL–I–)∞. The structures of (3) and (4) are unsymmetrical as a consequence of ligand steric effects. The synthesis and structure determination at 295 K of [Cu4I4(2Me-py)6] are also reported. Crystals are triclinic, space group P, with a= 12.856(8), b= 9.736(7), c= 9.472(7), A, α= 105.38(5), β= 98.68(5), γ= 104.90(5)°, and Z= 1; 4 010 observed reflections were refined to a residual of 0.034. The molecule is centrosymmetric and based on the ‘step’ structure well known for Cu4I4L4 species; however, the copper atoms at the periphery of the chair are co-ordinated by a pair of ligands, giving rise to the first known examples of 1 : 1 : 1.5 Cu : halide : base stoicheiometry observed in nitrogen-base systems, and the first example of this stoicheiometry based on the ‘step’ array.
55 citations
TL;DR: In this paper, the crystal structures of the 1 : 1 adducts of FeCl3 with 2,2'-bipyridine (bpy) (1) and 1,10-phenanthroline (phen) (2), as recrystallized from nitromethane, have been determined by single-crystal X-ray diffraction methods at 295 K, being refined by least squares to residuals of 0.038 and 0.032.
Abstract: The crystal structures of the 1 : 1 adducts of FeCl3 with 2,2'-bipyridine (bpy) (1) and 1,10-phenanthroline (phen) (2), as recrystallized from nitromethane, have been determined by single-crystal X-ray diffraction methods at 295 K, being refined by least squares to residuals of 0.038 and 0.032 for 1341 and 3968 'observed' reflections; the result for (2) is a redetermination. Crystals of (1) are orthorhombic, Pbnb, a 15.013(4), b 13.510(5), c 12.471(3) Ǻ, Z 4. Crystals of (2) are triclinic, P1, a 15.823(5), b 11.021(5), c 8.200(3) Ǻ, α 80.27(3), β 76.78(3), γ 89.64(3)°, Z 2. Both complexes haw the stoichiometry (FeCl3)1(bpy,phen)1, but are formulated as cis-[Fe(bpy,phen)2Cl2] [FeCl4]; in both compounds, the Fe-N distance is c. 2.20, (trans to Cl), 2.1, Ǻ(cis to Cl), while Fe-Cl, c. 2.2, Ǻ, is short. The structure determinations of Fe2Cl6(phen,bpy)3 as [Fe(phen)2Cl2]+ [Fe(phen)Cl4]- (3) and [Fe(bpy)2Cl2]+ [Fe(bpy)Cl4]- (4) are also reported. Compound (3) (from acetonitrile solution) is triclinic, P1, a 16.502(5), b 11.857(3), c 10.653(3) Ǻ, α 84.92(2), β 72.66(2), γ 74.80(2)°, Z 2, and was refined to a residual of 0.034 for 5540 'observed' reflections. The cation geometry is similar to that of (2); in the anion, the two Fe-CI bonds trans to each other are long [2.377(1) and 2.365(1) Ǻ] while those trans to the Fe-N bonds are short [2.287(1) and 2.318(1) Ǻ]. Fe-N distances are 2.216(3) and 2.220(3) A. Compound (4) (as its nitromethane solvate) is also triclinic, P1, a 14.480(7), b 12.645(5), c 10.678(4) Ǻ, α 95.68(3), β 109.21(3), γ 9258(3)°, Z 2; a residual of 0.042 was obtained for 4962 'observed' reflections. Cation and anion metal geometries are similar to those of (3).
39 citations
TL;DR: One of the products from reactions between Ru3(CO)12 and C2(CO2Me)2 is Ru2( CO)6[C4(CO 2Me)4].
39 citations
TL;DR: The crystal structure of [Fe(bpy)3] [CI3FeOFeCI3] (1) has been determined by single-crystal X-ray diffraction at 295 K, and refined by least squares to a residual of 0.058 for 2002 'observed' reflections as mentioned in this paper.
Abstract: The crystal structure of [Fe(bpy)3] [CI3FeOFeCI3] (1) has been determined by single-crystal X-ray diffraction at 295 K, and refined by least squares to a residual of 0.058 for 2002 'observed' reflections. Crystals are monoclinic, P21/c, a 9.616(3), b 26.264(6), c 13.821(7) Ǻ, β 99.68(2)°, Z4. In the cation, Fe-N distances range from 1.956(9) to 1 .989(10) Ǻ; in the anion, Fe-Cl distances range from 2.196(5) to 2.225(5) Ǻ. Fe-O distances are 1.763(11) and 1.740(11) Ǻ, and the Fe-O-Fe angle is 148.9(7)°. Recrystallization of 'compound A' from methanolic aqueous solution yields crystals with stoichiometry [{cis-Fe(phen)2Cl}2O]Cl2.nH2O( n ≈ 4.5) as established by structure determination (hampered by serious disorder); R is 0.09 for 749 'observed' reflections. Crystals are orthorhombic, Pcn2, a 18.05(1), b 13.83(1), c 10.481(6) Ǻ, Z 2. The Fe-N distances trans to each other are 2.12(3) and 2.13(3) Ǻ; Fe-N distances trans to Cl and O are 2.20(2) and 2.28(2) Ǻ, respectively. Fe-CI is 2.34(1) and Fe-O 1.787(6) A; Fe-O-Fe is 161(1)°. For crystals from aqueous solution, an isomorphous but larger unit cell is obtained [2754(7), cf. 2616(3) Ǻ3]; it is believed that this is a consequence of variable occupancy of the disordered solvent layers which lie parallel to bc between the ionic species.
32 citations
TL;DR: In this article, the structure determinations of the alums CsM[SO4]2·12H2O have been carried out for M = rhodium(III) and iridium(III), providing the first structurally characterized examples of the hexa-aqua-rhodium-III and -iridium-III species.
Abstract: Structure determinations of the alums CsM[SO4]2·12H2O have been carried out for M = rhodium(III) and iridium(III), providing the first structurally characterized examples of the hexa-aqua-rhodium(III) and -iridium(III) species. Structures were determined at 295(1) K and refined to R= 0.034 and 0.028 for 546 and 696 independent ‘observed’ reflections for Rh and Ir respectively. Crystals are cubic, space group Pa3 with a= 12.357(5) and 12.395(3)A respectively; Rh–O is 2.016(3) and Ir–O 2.041(3)A. Both alums are of the α type. Single-crystal Raman spectra of the S–O stretching vibrations are reported which distinguish between the α and β caesium alums.
28 citations
TL;DR: The structure determinations and a comparison of the molecular core geometries of the complexes [M3(μ3-C6H4)(μ-PPh2)2(CO)7] (M � Ru and Os) are reported in this paper.
27 citations
TL;DR: In this paper, the formation d'aggregats dimeres a l'etat solide was discussed in le groupe P1 avec a=14,887, b=11,737 and c=8,631 A, α=73,43°, β=77,64° and γ=80,93°, Z=2 dimeres
Abstract: Formation d'aggregats dimeres a l'etat solide. Cristallisation dans le groupe P1 avec a=14,887, b=11,737 et c=8,631 A, α=73,43°, β=77,64° et γ=80,93°, Z=2 dimeres
22 citations
TL;DR: The crystal structures of three iron complexes [FeCI3(phen)(MeOH) and [FeCl4(phen)] have been determined by single-crystal X-ray diffraction methods at 295(1) K, and refined by least squares to residuals of 0.044 (1600 'observed' reflections), 0.040 (806) and 0.050 (2496) respectively.
Abstract: The crystal structures of three iron complexes [FeCI3(phen)(MeOH)].MeOH (I), [FeCl3(phen)(H2O)] (2) and [phenH]+ [FeCl4(phen)]- (3) have been determined by single-crystal X-ray diffraction methods at 295(1) K, and refined by least squares to residuals of 0.044 (1600 'observed' reflections), 0.040 (806) and 0.050 (2496), respectively. Crystals of (1) are monoclinic, P21/c, a 8.005(9), b 14.805(11), c 14.830(12) A, P 101.03(7)°, Z 4; for (2), triclinic, space group P1 , a 10.591(8), b 10.227(7), c 6.613(3) Ǻ, α 108.21(5), β 100.69(5), γ 91.98(6)°2, 2 ; for (3), triclinic, P1, a 18.560(8), b 10.302(5), c 6.981(3) Ǻ, α 106.79(4), β 94.50(4), γ 103.15(4)°, Z 2. In all structures, the iron atoms are six-coordinate, with the disposition of the three chlorine atoms being fac in (1) and (2).
21 citations
TL;DR: A series of derivatives of pentakis(methoxycarbonyl)cyclopentadiene have been prepared (from the diene and silver acetate), including [Ag[C5(CO2Me)5](OH2)n]·1.5nH2O, [{Ag[c5(C5-me)-5]-PPh3}2], [Ag{C-me-5]-pPh3]2, [Ag-me]-5}(dppe)][dppe = 1,2-bis(dip
Abstract: A series of silver(I) derivatives of pentakis(methoxycarbonyl)cyclopentadiene has been prepared (from the diene and silver acetate), including [{Ag[C5(CO2Me)5](OH2)}n]·1.5nH2O, [{Ag[C5(CO2Me)5](PPh3)}2], [Ag{C5(CO2Me)5}(PPh3)2], [Ag{C5(CO2Me)5}(dppe)][dppe = 1,2-bis(diphenylphosphino)ethane], and [Ag{C5(CO2Me)5}(tppme)][tppme = 1,1,1 -tris(diphenylphosphinomethyl)ethane]. In polar solvents, some of these complexes form conducting solutions. Structural studies by single-crystal X-ray diffraction have given the following results: [{Ag[C5(CO2Me)5](OH2)}n]·1.5nH2O forms a one-dimensional polymer, centrosymmetrically related silver atoms being bridged by a similarly related pair of water molecules [Ag–O 2.450(5), 2.437(5)A], and also by a C5(CO2Me)5 ligand, alternately bonded through a pair of carboxylate oxygen atoms [Ag–O 2.391 (5), 2.417(6)A] and an interaction with two of the C5(CO2Me)5ring carbons [2.586(7), 2.807(7)A]; in [{Ag[C5(CO2Me)5](PPh3)}2], the silver atom is essentially four-co-ordinated by a phosphine ligand [Ag–P 2.397(1)A], a chelating C5(CO2Me)5 ligand [Ag–O 2.415(3), 2.613(3)A], and an interaction with one of the π bonds in the C5ring of the C5(CO2Me)5ligand [Ag–C 2.632(4), 2.472(4)A], the whole species being bridged by C5(CO2Me)5ligands to give a centrosymmetric dimer; [Ag{C5(CO2Me)5}(PPh3)2] is monomeric, with silver four-co-ordinated by two phosphine ligands [Ag–P 2.428(2), 2.414(2)A] and a chelating C5(CO2Me)5 ligand [Ag–O 2.465(4), 2.594(5)A].
18 citations
TL;DR: In this paper, the crystal structures of [Ru3(CO)12 −n(CNBut)n] have been determined by X-ray diffraction studies, and refined to residuals of 0.035 (4 561 ‘observed’ reflections) and 0.043 (2 849 'observed' reflections) respectively.
Abstract: Reactions between [Ru3(CO)12] and isocyanides CNR have given the complexes [Ru3(CO)12 –n(CNR)n](R = But, n= 1, 2, or 3; R = C6H11, n= 1; R = C6H4OMe-p, n= 1 or 2; and R = CH2SO2C6H4Me-p, n= 3) as orange to red crystalline solids. The crystal structures of [Ru3(CO)12 –n(CNBut)n](n= 1 or 2) have been determined by X-ray diffraction studies, and refined to residuals of 0.035 (4 561 ‘observed’ reflections) and 0.043 (2 849 ‘observed’ reflections) respectively. Crystals of [Ru3(CO)11(CNBut)] are monoclinic, space group P21/c with a= 11.948(5), b= 12.108(4), c= 16.621(4)A, β= 112.74(2)°, and Z= 4; crystals of [Ru3(CO)10(CNBut)2] are monoclinic, space group P21/a with a= 11.910(10), b= 12.831(17), c= 9.565(16)A, β= 111.84(10)°, and Z= 2. In the latter derivative, the ligand array is ‘centrosymmetric’ about a crystallographic special position, with the two isocyanide ligands in axial sites; the Ru3 triangle is disposed about a pair of equally populated centrosymmetrically related dispositions within the ligand array. In [Ru3(CO)11(CNBut)] the isocyanide substituent is also axial; the Ru3 triangle is similarly disordered but only to the extent of ca. 14% within the ligand array. A method for the almost quantitative conversion of RuCl3·xH2O to [Ru3(CO)12] has been developed consisting of carbonylation of 1% methanol solutions (50–60 atm CO, 125 °C, 16–18 h), recycling the mother-liquors with fresh RuCl3·xH2O.
TL;DR: The crystal and molecular structures of the title complexes are reported in this paper, and they are triclinic, space group P21/n, with a= 20.474(9), b= 12.339(5), c= 11.976(6)A, β= 90.80(4)°, and Z= 4.049.
Abstract: The crystal and molecular structures of the title complexes are reported. Crystals of the complex [Ru3(CO)11{P(C6H11)3}] are triclinic, space group P, with a= 17.58(1), b= 17.50(1), c= 12.023(8)A, α= 69.80(5), β= 88.19(5), γ= 82.32(5)°, and Z= 4. Refinement of 7 382 data gave residuals R,R′= 0.042, 0.049. Crystals of [Ru3(CO)10{P(OMe)3}2] are triclinic, space group P, with a= 10.569(4), b= 8.588(3), c= 8.362(3)A, α= 68.45(3), β= 83.07(3), γ= 77.06(3)°, and Z= 1. Refinement of 2 773 data gave R,R′= 0.039, 0.048. Crystals of [Ru3(CO)9(PMe3)3] are monoclinic, space group P21/n, with a= 20.474(9), b= 12.339(5), c= 11.976(6)A, β= 90.80(4)°, and Z= 4. Refinement of 5 014 data gave R,R′= 0.037, 0.046. All complexes contain an Ru3 core bearing the tertiary phosphine or phosphite ligands in equatorial positions on different metal atoms. The P(OMe)3 and PMe3 complexes are disordered according to a model in which the central Ru3 cluster occupies two positions related by a 60° rotation about the inversion centre, while the peripheral atom polyhedron (constructed from the O of CO, and P of the phosphite or phosphine) remains essentially unchanged.
TL;DR: In this article, an X-ray structural study showed that the Au(PPh3)[Au-P 2.253(1)A] moiety interacts with three carbons of the C5ring [Au−C 2.199(4), 2.705(4, and 2.813(4)A], such that the coordination is intermediate between σ and η3.
Abstract: Pentakis(methoxycarbonyl)cyclopentadiene reacts with [Au(O2CMe)(PPh3)] to give [Au{C5(CO2Me)5}(PPh3)]; an X-ray structural study shows that the Au(PPh3)[Au–P 2.253(1)A] moiety interacts with three carbons of the C5ring [Au–C 2.199(4), 2.705(4), and 2.813(4)A] such that the co-ordination is intermediate between σ and η3. The complex reacts with a second molecule of PPh3 to give [Au(PPh3)2][C5(CO2Me)5]·MeOH; in the crystal, the gold is bonded to the two PPh3ligands [Au–P 2.297(3), 2.300(3)A; P–Au–P 170.4(2)°], and interacts weakly with an ester carbonyl group of the C5(CO2Me)5anion, and with the oxygen of a methanol solvate molecule.
TL;DR: In this article, the crystal structure of RuCl(PPh3)2(η-C5H5)] was determined by single-crystal X-ray diffraction methods at 295 K, being refined to a residual of 0.026 for 6 438 ‘ observed ’ reflections.
Abstract: The salt Tl[C5(CO2Me)5] reacts with [RuCl(PPh3)2(η-C5H5)] in acetonitrile to give the complex [Ru(NCMe)(PPh3)2(η-C5H5)][C5(CO2Me)5]; in air the reaction affords [Ru(η-C5H5){η-C5(CO2Me)5}]. The crystal structure of the latter has been determined by single-crystal X-ray diffraction methods at 295 K, being refined to a residual of 0.026 for 6 438 ‘ observed ’ reflections. Crystals are triclinic, space group P, with a= 15.790(5), b= 8.968(4), c= 7.947(3)A, α= 67.52(3), β= 89.52(3), γ= 80.90(3)°, and Z= 2. Both ligands have an η5 relationship to the ruthenium in what is essentially an eclipsed sandwich compound. For the C5H5 ring, Ru–C is 2.178(2)–2.186(3)A, while for the C5(CO2Me)5 ligand, Ru–C is 2.157(2)–2.178(2)A; although these distances are uncorrected for libration, their relativity seems valid. The C5(CO2Me)5 ligand is displaced in reactions with tertiary phosphines in nitrite solvents, and this reaction forms the basis of a process for the oxidation of PPh3 catalysed by the metallocene. The protonation of [RuH(PPh3)2(η-C5H5)] by HC5(CO2Me)5 is also described.
TL;DR: In this paper, the first cyclopentadienyl complex of copper(II) was obtained, which contained Mn, Fe, Co, Ni, or Cu, and was shown to be octahedrally co-ordinated by two solvent molecules, and two pairs of chelating carbonyl oxygens.
Abstract: Bivalent transition-metal derivatives of pentakis(methoxycarbonyl)cyclopentadiene have been obtained, which contain Mn, Fe, Co, Ni, or Cu : the latter is the first cyclopentadienyl complex of copper(II). These complexes are soluble in water or alcohols to give solutions containing [C5(CO2Me)5]– anions and solvated M2+ cations. Structural studies of the Fe and Cu complexes show the metal ion to be octahedrally co-ordinated by two solvent molecules, and two pairs of chelating carbonyl oxygens from each C5(CO2Me)5 anion; the two salts, trans-[M{C5(CO2Me)5}2(MeOH)2](M = Fe or Cu) are isomorphous, monoclinic, space group P21/c with a∼ 8.3, b∼ 20.2, c∼ 11.9 A, β∼ 108°, and Z= 2, with the molecule lying on a crystallographic centre of symmetry. For the iron(II) salt, Fe–O[C5(CO2Me)5] are 2.065(3) and 2.050(2)A and Fe–O(MeOH) 2.151(2)A, while in the copper(II) salt, Cu–O[C5(CO2Me)5] are 1.946(2) and 1.962(2)A and Cu–O(MeOH) 2.314(3)A. The cobalt hydrate analogue, [Co{C5(CO2Me)5}2(OH2)2] has also been studied structurally and the molecule lies on a two-fold axis in space group C2/c with a= 17.151(7), b= 14.722(5), c= 15.026(6)A, β=108.65(3)°, and Z= 4. The Co–OH2bond is 2.054(4)A; Co–O[C5(CO2Me)5] are 2.043(4) and 2.068(4)A. Residuals are 0.039, 0.044, and 0.043 respectively for the Fe, Cu, and Co complexes from 2 075, 3 018, and 1 430 ‘observed’ reflections. Unlike the iron and copper derivatives, the cobalt(II) complex is cis.
TL;DR: In this paper, the crystal and molecular structures of the title complexes are reported, and the relationship between the i.r. frequencies and the co-ordination geometry of oxygen-bound nitrite groups is discussed.
Abstract: The crystal and molecular structures of the title complexes are reported. The overall geometry of the three complexes is similar, with the amine ligands in each case occupying cis co-ordination sites. However, the ways in which the nitrite groups are bound to the metal ions differ considerably, these chelating approximately symmetrically in the nickel compound, but with a marked asymmetry in the compound [Zn(pyridine)2(NO2)2]. In [Zn(2-methylpyridine)2(NO2)2] the nitrite groups are best thought of as unidentate nitrito-ligands with the second oxygen atom semico-ordinated to the metal :[graphic omitted]. The variation in the manner of nitrite co-ordination is probably influenced both by the electronic structure of the metal ions and the steric requirements of the amine ligands. The relationship between the i.r. frequencies and the co-ordination geometry of oxygen-bound nitrite groups is discussed, and it is shown that it is impossible to distinguish h between syn M–[graphic omitted] and anti M–[graphic omitted] nitrito-groups unambiguously using this technique.
TL;DR: The crystal and molecular structure of the title complex, cis-[Ru(CO)Cl2(dmso)(opmpp)] (1) (dmso ≡ dimethyl sulfoxide, Me2SO; opmpp ≡ (±)-ortho-phenylenebis {methyl(phenyl)phosphine},[o-C6H4(PMePh)2]), has been determined by a single-crystal X-ray diffraction study at 295(1) K, being refined to a residual of 0.036 for 6115 independent 'observed
Abstract: The crystal and molecular structure of the title complex, cis-[Ru(CO)Cl2(dmso)(opmpp)] (1) (dmso ≡ dimethyl sulfoxide, Me2SO; opmpp ≡ (±)-ortho-phenylenebis {methyl(phenyl)phosphine},[o-C6H4(PMePh)2]), has been determined by a single-crystal X-ray diffraction study at 295(1) K, being refined to a residual of 0.050 for 6115 independent 'observed' reflections. Crystals are monoclinic, P21/c, a 11.180(7), b 12.957(6), c 17.567(9) A, β 90.88(5)o, Z 4. The ruthenium-chlorine distances, trans to phosphine and carbonyl ligands, respectively, are 2.469(2), 2.446(2) A; the ruthenium-phosphine distances, trans to the chloride and dimethyl sulfoxide ligands, respectively, are 2.292(1), 2.313(2) A. Ruthenium-sulfur (dmso) is 2.380(2) A, while the ruthenium-carbon(CO) is c. 1.72 A. For cis-[Ru(CO)2Cl2(opmpa)] (2) (opmpa ≡ (±)-ortho-phenylenebis{methyl(phenyl)- arsine}, [o-C6H4(AsMePh)2]), refinement led to a residual of 0.036 for 2423 independent 'observed' reflections. Crystals are monoclinic, P21/c, a 10.497(3), b 11.586(7), c 20.341(9) A, β 105.31(4)o, Z 4. Ruthenium-arsine distances, trans to carbonyl and chlorine ligands, respectively, are 2.404(1), 2.455(1) A. Ruthenium-chlorine distances, trans to arsine and carbonyl ligands, respectively, are 2.443(3), 2.433(2) A, while ruthenium-carbon(CO) distances, trans to arsine and chlorine ligands, respectively, are 1 .920(8), 1 .872(8) A.
TL;DR: The structure of a new sesterterpene metabolite isolated from an unclassified Carteriospongia sp. has been assigned from X-ray crystallographic evidence as discussed by the authors.
Abstract: The structure of a new sesterterpene metabolite isolated from an unclassified Carteriospongia sp. has been assigned from X-ray crystallographic evidence. The compound has been indentified as (20S,24S)-20-acetoxy-12β-hydroxy-20,24-dimethyl-25-norscalar-17-ene-18,24-carbolactone (4). The absolute configuration is taken to be that found for other scalaranes from Phyllospongia spp.
TL;DR: In this paper, a series of Hg-Mo bonded complexes [Hg(CN){trans-Mo(CO)2L(η5-C5H5)] have been prepared from Hg (CN)2 and the salts Na[Mo(Co) 2L (η 5-C4H5) or dimers [Hm{trans-C3H5H1H5]2]2], where L = AsMe2Ph, PMe2Ph or PPh3.
Abstract: The series of Hg–Mo bonded complexes [Hg(CN){trans-Mo(CO)2L(η5-C5H5)}](where L = AsMe2Ph, PMe2Ph, PMePh2, or PPh3) have been prepared from Hg(CN)2 and the salts Na[Mo(CO)2L(η5-C5H5)] or dimers [Hg{trans-Mo(CO)2L(η5-C5H5)}2]. The cyanomercury complexes are extremely useful intermediates for the facile synthesis of the derivatives [HgX{trans-Mo(CO)2L(η5-C5H5)}](where X = Cl, Br, I, NO3, O2CMe, OCN, SCN, or S2CNEt2). The molecular structure of the complex [Hg(CN){trans-Mo(CO)2(AsMe2Ph)(η5-C5H5)}] has been determined by single-crystal X-ray analysis. The crystals are monoclinic, space group P21/c, with a= 14.570(4), b= 12.457(3), c= 10.783(3)A, β= 114.04(2)°, and Z= 4. The structure was solved by heavy-atom methods and refined by least squares to a residual of 0.037 for 2 218 reflections with |I0| > 3σ(I). The Hg–Mo bond length [2.654(1)A] is the shortest hitherto observed.
TL;DR: The crystal structures of 4,4,6,6'-tetra-t-butyl-2',8-dimethoxy-1,1'-bisdibenzofuran-2,8'-diol have been determined.
Abstract: In solution in non-polar solvents the title compound undergoes photochemical ring opening to its hydroxyphenylquinone tautomer. Oxidation of 3,3'-di-t-butyl-5,5'-dimethoxybiphenyl-2,2'-diol withvanadium oxytrifluoride in the presence of trifluoroacetic acid yields bisdibenzofurans. The crystal structures of 4,4',6,6'-tetra-t-butyl-2',8-dimethoxy-1,1'-bisdibenzofuran-2,8'-diol and of 4,6-di-t-butyl-4a-hydroxy-8-methoxydibenzofuran-2(4aH)-one have been determined.
TL;DR: The crystal and molecular structure of the title complex, trans-[RuH(CO)(opmpp)2]+ (PF6)-.2(CH3)2- CO [opm pp ≡ (±)-ortho-phenylenebis {methyl(phenyl)phosphine), o-C6H4(PMePh)2], has been established by a single-crystal X-ray diffraction study at 295(1) K, being refined to a residual of 0.066 for 2293 independent 'observed' reflections as mentioned in this paper
Abstract: The crystal and molecular structure of the title complex, trans-[RuH(CO)(opmpp)2]+ (PF6)-.2(CH3)2- CO [opmpp ≡ (±)-ortho-phenylenebis {methyl(phenyl)phosphine) , o-C6H4(PMePh)2], has been established by a single-crystal X-ray diffraction study at 295(1) K, being refined to a residual of 0.066 for 2293 independent 'observed' reflections. Crystals are monoclinic, C2/c, a 11.943(4), b 26.151(9), c 15.974(6) A, β 90.97(7)o, Z 4. In the model adopted, the ruthenium atom is located on a crystallographic twofold axis; the carbonyl and hydrido ligands lie trans to each other and are disordered about the ruthenium atom. The ruthenium-phosphorus distances are 2.320(2) and 2.317(2)A.
TL;DR: In this article, the structure of 1.5 Cu : halide : base stoicheiometry with 2-methylpyridine (2Me-py) was determined using a single-crystal X-ray diffraction.
Abstract: Crystallization of copper(I) iodide from triethylamine–acetone yields a white crystalline solid of novel stoicheiometry [Cu4I4(NEt3)3]; its structure determination by single-crystal X-ray diffraction shows trigonal symmetry [space group P3, a= 19.46(2), c= 7.119(7)A, and Z= 3] and polymeric strings of Cu4I4‘cubane’ units, oriented with one body diagonal of each unit along c and linked to the next unit generated by the unit c translation by a copper–iodine interunit bond [2.930A(mean)]. There are three independent such polymeric strings in the unit cell. R was 0.074 for 2 942 ‘observed’ reflections. The structures of the 1 : 1 complexes of copper(I) iodide with 2-methylpyridine, (2Me-py)(2), 2,2,6,6-tetramethylpiperidine, (tmpip)(3), and acridine, (4), have also been determined. Each crystallizes in a structural form determined by the steric properties of the ligand. Crystals of (2) are tetragonal, space group I4cm, with a= 20.10(2) and c= 15.94(1)A; R= 0.055 for 782 independent observed reflections. The structure is a ‘cubane’-type tetramer, [Cu4I4(2Me-py)4], with Z= 8. Crystals of (3) are orthorhombic, space group Cmca, with a= 12.43(2), b= 9.964(7), and c= 19.30(3)A; R= 0.071 for 278 independent observed reflections. The structure is a di-µ-iodo-bridged dimer [Cu2I2(tmpip)2], with four molecules in the unit cell. Crystals of (4) are triclinic, space group P, with a= 14.381(4), b= 9.888(3), c= 4.117(1)A, α= 83.96(2), β= 81.57(2), and γ= 86.03(2)°; R= 0.078 for 2 649 observed reflections. The structure is a ‘split stair’ polymer, (–CuL–I–)∞. The structures of (3) and (4) are unsymmetrical as a consequence of ligand steric effects. The synthesis and structure determination at 295 K of [Cu4I4(2Me-py)6] are also reported. Crystals are triclinic, space group P, with a= 12.856(8), b= 9.736(7), c= 9.472(7), A, α= 105.38(5), β= 98.68(5), γ= 104.90(5)°, and Z= 1; 4 010 observed reflections were refined to a residual of 0.034. The molecule is centrosymmetric and based on the ‘step’ structure well known for Cu4I4L4 species; however, the copper atoms at the periphery of the chair are co-ordinated by a pair of ligands, giving rise to the first known examples of 1 : 1 : 1.5 Cu : halide : base stoicheiometry observed in nitrogen-base systems, and the first example of this stoicheiometry based on the ‘step’ array.
TL;DR: In this paper, a single-crystal X-ray structure determination of the Diels-Alder dimer was performed and it was shown that two benzofuranone moieties are situated so as to be vicinal spiro substituents of the cyclohexene formed in the diels-alder addition and the shielding of one aromatic hydrogen in the n.m.r. spectrum of the dimer results from the disposition of the two aromatic systems.
Abstract: (Z)-7-t-Butyl-5 methoxy-3-[(Z)-2?-methoxy-5,5'-dimethyl-4'-oxohex-2'-enylidene]benzofuran-2(3H)-one has been found to undergo Diels-Alder dimerization in which the exocyclic double bond adds to the s-cis diene moiety. The stereochemistry of the Diels-Alder dimer was established by a single-crystal X-ray structure determination. Crystals of the dimer, C44H56O10, are monoclinic, P21/n, a 12.23(1), b 19.43(2), c 18.71(2) A, β 107.76(7)o, Z 4; a residual of 0.046 was obtained for the 2519 'observed' reflections. In the dimer, two benzofuranone moieties are situated so as to be vicinal spiro substituents of the cyclohexene formed in the Diels-Alder addition. The bond between the two benzofuranone units is unusually long [1.597(6)A]. The shielding of one aromatic hydrogen in the n.m.r. spectrum of the dimer results from the disposition of the two aromatic systems.
TL;DR: A series of derivatives of pentakis(methoxycarbonyl)cyclopentadiene have been prepared (from the diene and silver acetate), including [Ag[C5(CO2Me)5](OH2)n]·1.5nH2O, [{Ag[c5(C5-me)-5]-PPh3}2], [Ag{C-me-5]-pPh3]2, [Ag-me]-5}(dppe)][dppe = 1,2-bis(dip
Abstract: A series of silver(I) derivatives of pentakis(methoxycarbonyl)cyclopentadiene has been prepared (from the diene and silver acetate), including [{Ag[C5(CO2Me)5](OH2)}n]·1.5nH2O, [{Ag[C5(CO2Me)5](PPh3)}2], [Ag{C5(CO2Me)5}(PPh3)2], [Ag{C5(CO2Me)5}(dppe)][dppe = 1,2-bis(diphenylphosphino)ethane], and [Ag{C5(CO2Me)5}(tppme)][tppme = 1,1,1 -tris(diphenylphosphinomethyl)ethane]. In polar solvents, some of these complexes form conducting solutions. Structural studies by single-crystal X-ray diffraction have given the following results: [{Ag[C5(CO2Me)5](OH2)}n]·1.5nH2O forms a one-dimensional polymer, centrosymmetrically related silver atoms being bridged by a similarly related pair of water molecules [Ag–O 2.450(5), 2.437(5)A], and also by a C5(CO2Me)5 ligand, alternately bonded through a pair of carboxylate oxygen atoms [Ag–O 2.391 (5), 2.417(6)A] and an interaction with two of the C5(CO2Me)5ring carbons [2.586(7), 2.807(7)A]; in [{Ag[C5(CO2Me)5](PPh3)}2], the silver atom is essentially four-co-ordinated by a phosphine ligand [Ag–P 2.397(1)A], a chelating C5(CO2Me)5 ligand [Ag–O 2.415(3), 2.613(3)A], and an interaction with one of the π bonds in the C5ring of the C5(CO2Me)5ligand [Ag–C 2.632(4), 2.472(4)A], the whole species being bridged by C5(CO2Me)5ligands to give a centrosymmetric dimer; [Ag{C5(CO2Me)5}(PPh3)2] is monomeric, with silver four-co-ordinated by two phosphine ligands [Ag–P 2.428(2), 2.414(2)A] and a chelating C5(CO2Me)5 ligand [Ag–O 2.465(4), 2.594(5)A].
TL;DR: In this article, the first cyclopentadienyl complex of copper(II) was obtained, which contained Mn, Fe, Co, Ni, or Cu, and was shown to be octahedrally co-ordinated by two solvent molecules, and two pairs of chelating carbonyl oxygens.
Abstract: Bivalent transition-metal derivatives of pentakis(methoxycarbonyl)cyclopentadiene have been obtained, which contain Mn, Fe, Co, Ni, or Cu : the latter is the first cyclopentadienyl complex of copper(II). These complexes are soluble in water or alcohols to give solutions containing [C5(CO2Me)5]– anions and solvated M2+ cations. Structural studies of the Fe and Cu complexes show the metal ion to be octahedrally co-ordinated by two solvent molecules, and two pairs of chelating carbonyl oxygens from each C5(CO2Me)5 anion; the two salts, trans-[M{C5(CO2Me)5}2(MeOH)2](M = Fe or Cu) are isomorphous, monoclinic, space group P21/c with a∼ 8.3, b∼ 20.2, c∼ 11.9 A, β∼ 108°, and Z= 2, with the molecule lying on a crystallographic centre of symmetry. For the iron(II) salt, Fe–O[C5(CO2Me)5] are 2.065(3) and 2.050(2)A and Fe–O(MeOH) 2.151(2)A, while in the copper(II) salt, Cu–O[C5(CO2Me)5] are 1.946(2) and 1.962(2)A and Cu–O(MeOH) 2.314(3)A. The cobalt hydrate analogue, [Co{C5(CO2Me)5}2(OH2)2] has also been studied structurally and the molecule lies on a two-fold axis in space group C2/c with a= 17.151(7), b= 14.722(5), c= 15.026(6)A, β=108.65(3)°, and Z= 4. The Co–OH2bond is 2.054(4)A; Co–O[C5(CO2Me)5] are 2.043(4) and 2.068(4)A. Residuals are 0.039, 0.044, and 0.043 respectively for the Fe, Cu, and Co complexes from 2 075, 3 018, and 1 430 ‘observed’ reflections. Unlike the iron and copper derivatives, the cobalt(II) complex is cis.
TL;DR: In this paper, a single-crystal X-ray structure determination of the Diels-Alder dimer was performed and it was shown that two benzofuranone moieties are situated so as to be vicinal spiro substituents of the cyclohexene formed in the diels-alder addition and the shielding of one aromatic hydrogen in the n.m.r. spectrum of the dimer results from the disposition of the two aromatic systems.
Abstract: (Z)-7-t-Butyl-5 methoxy-3-[(Z)-2?-methoxy-5,5'-dimethyl-4'-oxohex-2'-enylidene]benzofuran-2(3H)-one has been found to undergo Diels-Alder dimerization in which the exocyclic double bond adds to the s-cis diene moiety. The stereochemistry of the Diels-Alder dimer was established by a single-crystal X-ray structure determination. Crystals of the dimer, C44H56O10, are monoclinic, P21/n, a 12.23(1), b 19.43(2), c 18.71(2) A, β 107.76(7)o, Z 4; a residual of 0.046 was obtained for the 2519 'observed' reflections. In the dimer, two benzofuranone moieties are situated so as to be vicinal spiro substituents of the cyclohexene formed in the Diels-Alder addition. The bond between the two benzofuranone units is unusually long [1.597(6)A]. The shielding of one aromatic hydrogen in the n.m.r. spectrum of the dimer results from the disposition of the two aromatic systems.