Structure and luminescence of [Tb0.5(C6NO2H5)3(H2O)2]2n·(H3O)4n(ZnCl5)n(ZnCl4)2n

A novel bimetallic 4f-3d metal-isonicotinic acid inorganic-organic hybrid complex [Tb_0.5(C₆NO₂H₅)₃(H₂O)₂]_2n ·(H₃O)_4n (ZnCl₅) _n (ZnCl₄)_2n (1) is synthesized. It has a one-dimensional polycationic chain-like structure. Photoluminescent investigation reveals that it displays interesting emissions in the violet, blue, green, and yellow regions.     

Synthesis and characterization of [MCl2(nPr-N(Ph2P)2] (M?=?Pt, Pd) complexes and hydroformylation of 1-octene using [PtCl2(R-N(Ph2P)2)] (R?=?benzyl, 2-picolyl, nPr) complexes

The synthesis and characterization of platinum(II) and palladium(II) complexes of the type [PtX₂( ⁿ Pr-N(Ph₂P)₂)] (X = Cl, I) and [PdCl₂(R-N(Ph₂P)₂)] {R =  ⁿ Pr, p-OMe(C₆H₄)} containing aminodiphosphine P,P-bidentate ligands is described. Complexes of the type [PtCl₂(R-N(Ph₂P)₂)] (where R = benzyl, 2-picolyl and ⁿ Pr) catalyzed the hydroformylation of 1-octene, albeit at low activities and slightly elevated regioselectivities toward the linear aldehyde, when compared with analogous compounds containing small bite angles.     

Synthesis and structure of cobalt complexes [Ph3(n-Pr)P 2+ [CoI4]2? and [Ph3(n-Am)P 2+ [CoI4]2?

Complexes Ph₃(n-Pr)P₂⁺[CoI₄]²⁻ (I) and [Ph₃(n-Am)P]₂⁺ [CoI₄]²⁻ (II) were synthesized by reactions of triphenyl(alkyl)phosphonium iodide with cobalt(II) iodide in acetone. According to the X-ray diffraction data, complexes I and II consist of tetrahedral triphenyl(alkyl)phosphonium cations (for I, P-C is 1.787(4)–1.804(4) ? and CPC is 106.73(18)°–111.4(18)°; for II P-C is 1.786(6)–1.802(6) ? and CPC is 107.6(3)°–111.7(3)°) and [CoI₄]²⁻ anions (Co-I 2.5923(6)–2.6189(6) ?, ICoI 101.86(2)°–113.25(2)° for I; Co-I 2.5899(9)–2.6171(9) 107.01(3)°–110.47(3)° for II).     

Synthesis, crystal structure and properties of [Nd(C6NO2H5)3(H2O)2]2n · (nH5O2)(nHgCl5)(2nHgCl4) · (nH2O) with unprecedented polycationic chains

A novel inorganic-organic hybrid complex, [Nd [Nd (C₆NO₂H₅)₃(H₂O)₂]_2n · (nH₅O₂)(nHgCl₅)(2nHgCl₄) · (nH₂O)(1), was obtained by hydrothermal reactions and structurally characterized by X-ray diffraction. The unit cell parameters are as follows: a = 9.579(1), b = 21.462(2), c = 15.801(1) ?, β = 102.339(6)^ℴ, V = 3173.5(5) ?³, Z = 4, space group P2₁/c. The crystal structure analysis reveals that the title complex is characteristic of a novel polycationic [Nd(C₆NO₂H₅)₃(H₂O)₂]_2n ⁶ⁿ⁺ one-dimensional chain-like structure. Photoluminescent investigation shows that the title complex displays strong emission in blue region, which is attributed to the intraligand π-π*-transition of nicotinic ligands. Optical absorption spectra of 1 reveal the presence of an optical gap of 3.45 eV. The article is published in the original.     

Phenyltellurenyl halide complexes of ruthenium and rhenium (CO)2RuBr2(PhTeBr)2 and (CO)3Re(PhTeI)3(μ3-I): Synthesis and crystal and molecular structures

Reactions of Ru₃(CO)₁₂ with PhTeBr₃ and of Re(CO)₅Cl with PhTeI in benzene give the stable complexes (CO)₂RuBr₂(PhTeBr)₂ (I) and (CO)₃Re(PhTeI)₃(μ³-I) (II) containing two and three ligands PhTeX (X = Br or I), respectively. The bonds between these ligands and the central metal atom are fairly shortened (on average, Ru-Te, 2.608 ?; Re-Te, 2.7554(12)-2.7634(13) ?). The Te-X bonds in the ligands PhTeBr (2.5163(5) ?) and PhTeI (2.7893(15) ?) are not lengthened appreciably. In complex II, the iodide anion is not coordinated by rhenium, yet being attached through weak secondary bonds to three Te atoms of the three ligands PhTeI.     

Mixed-ligand complexes [Cd(DMSO)5(NCS)][Cr(NH3)2(NCS)4] · 3DMSO and [Mn(DMSO)4(H2O)2][Cr(NH3)2(NCS)4]2 · 6DMSO · 2H2O: Syntheses and crystal structures

New mixed-ligand coordination compounds[Cd(DMSO)₅(NCS)][Cr(NH₃)₂(NCS)₄] · 3DMSO (I) and [Mn(DMSO)₄(H₂O)₂][Cr(NH₃)₂(NCS)₄]₂ · 6DMSO · 2H₂O (II) have been synthesized and studied by IR spectroscopy and X-ray diffraction analysis. The crystals of compound I are monoclinic, a = 14.5275(7), b = 23.1692(11), c = 14.6969(6) ?, β = 97.057(2)°, V = 4909.4(4) ?³, space group P2₁/c, Z = 4, ρ_calcd = 1.507 g/cm³, R = 0.0556. The crystals of compound II are triclinic, a = 11.7784(3), b = 12.1760(3), c = 13.1922(2) ?, α = 85.5420(10)°, β = 87.9000(10)°, γ = 70.3680(10)°, V = 1776.46(7) ?³, space group P , Z = 1, ρ_calcd = 1.444 g/cm³, R = 0.0350. Original Russian Text ? E.A. Gerasimova, T.V. Utkina, E.V. Peresypkina, A.V. Virovets, T.G. Cherkasova, 2009, published in Zhurnal Neorganicheskoi Khimii, 2009, Vol. 54, No. 5, pp. 751–755.     

Stepwise addition of CuBr at [(dtc)2Mo2(S)2(μ-S)2] (dtc=diethyldithiocarbamate): syntheses and crystal structures of two Mo/Cu/S clusters [(dtc)2Mo2(μ3-S)(μ-S)3(CuBr)] and [(dtc)2Mo2(μ3-S)4(CuBr)2]

Reactions of [(dtc)₂Mo₂(S)₂(μ-S)₂] with one or two equivalents of CuBr in CH₂Cl₂ afforded two new heterobimetallic sulfide clusters, [(dtc)₂Mo₂(μ₃-S)(μ-S)₃(CuBr)] (1) and [(dtc)₂Mo₂(μ₃-S)₄(CuBr)₂] (2). Both compounds were characterized by elemental analysis, IR, UV-vis and X-ray analysis. Compound 1 contains a butterfly-shaped Mo₂S₄Cu core in which one CuBr unit is coordinated by one bridging S and two terminal S atoms of the [(dtc)₂Mo₂(S)₂(μ-S)₂] moiety. In the structure of 2, one [(dtc)₂Mo₂(S)₂(μ-S)₂] moiety and two CuBr units are held together by six Cu-μ₃-S bonds, forming a cubane-like Mo₂S₄Cu₂ core.     

Synthesis,structure characterization and thermal properties of [Zr6(μ3-O)4(μ3-OH)4(OOCCH2Bu)9(μ2-OH)3]2

Oxo/hydoxo zirconium(IV) complex of the general formula [Zr₆(μ₃-O)₄(μ₃-OH)₄(OOCCH₂^tBu)₉(μ₂-OH)₃]₂ has been isolated, when Zr(OⁱPr)₄ reacted with a 2-fold excess of 3,3-dimethylbutyric acid. Single crystal X-ray diffraction data, collected at 103 and 153 K, showed that the studied compound crystallizes in hexagonal system (P6₃/m (no. 176)). Structure consists of dimers composed of [Zr₆(μ₃-O)₄(μ₃-OH)₄(OOCCH₂^tBu)₉] sub-units, linked by six μ₂-OH bridges. Infrared spectroscopic studies proved the presence of hydroxo groups in the structure of studied clusters and formation of different types of oxo/hydroxo bridges. The application of variable temperature infrared spectroscopy and differential scanning calorimetry revealed that the structure of this complex undergoes the phase transitions at 143–183 and 203–293 K. Comparison of spectral and crystallographic data suggests that these phase transitions might be related to changes in the strength of Zr–O bonds of μ₂-OH bridges linking complex sub-units, and change in symmetry of the crystal lattice (from hexagonal to trigonal). Analysis of thermogravimetric data showed that decomposition of [Zr₆(μ₃-O)₄(μ₃-OH)₄(OOCCH₂^tBu)₉(μ₂-OH)₃]₂ proceeds with complete conversion to ZrO₂ (monoclinic form) between 603 and 803 K.     

Synthesis and crystal structure of new one-dimensional copper(II) complex [Cu4(En)2(μ1,1-N3)4(μ1,1,1-N3)2(μ1,3-N3)2]n

A new polymer azido-bridged copper(II) complex [Cu₄(En)₂(μ_1,1-N₃)₄(μ_1,1,1-N₃)₂(μ_1,3-N₃)₂] _n (I) (En = ethylenediamine) has been synthesized and crystallography characterized. Complex I shows one-dimensional coordination polymeric structure based on a tetranuclear cluster unit [Cu₄(En)₂(μ_1,1-N₃)₄(μ_1,1,1-N₃)₂(μ_1,3-N₃)₂], in which the azido ions display three different bridging modes.     

Formation of the silylene-bridged complex Fe2(CO)6(μ2-SiCl2)3 from cis-Fe(CO)4(SiCl3)2: an experimental and computational study

Abstract  

Thermolysis of cis-Fe(CO)₄(SiCl₃)₂ results in the formation of the novel compound Fe₂(CO)₆(μ₂-SiCl₂)₃, which was characterized by single crystal X-ray diffraction. Density functional theory calculations were carried out to elucidate possible reaction steps leading to the formation of Fe₂(CO)₆(SiCl₂)₃, including CO dissociation and chlorine abstraction by a SiCl₃ radical generated from homolytic Fe–Si bond cleavage involving a singlet–triplet intersystem crossing.     

Lanthanide nitrate complexes of the redox active ligand (ηC5H4P(O)Ph2)2Fe

The synthesis of complexes of (η⁵C₅H₄P(O)Ph₂)₂Fe = L with lanthanide nitrates is described. The single crystal X-ray structures for La(NO₃)₃L(μ-L)La(NO₃)₃L (1), [Eu(NO₃)₂L₂]₂[Eu(NO₃)₅] (2), [Ho(NO₃)₂L₂]₂[Ho(NO₃)₅] (3) and [Lu(NO₃)₂L₂] NO₃ (4) are reported. Trends in Ln–O bond distances cannot be explained by the lanthanide contraction alone. The cyclic-voltammetric (CV) oxidation–reduction behaviour of 1, 2, 4 and Dy(NO₃)₃L₂ · 2H₂O is described. This was reversible on a timescale of a few seconds in all cases. In our hands the CV behaviour of L also seemed reversible on this timescale, although attempted chemical oxidation of L led to the isolation of [FeL₂(NO₃)₂]NO₃ (5) which was characterised by X-ray crystallography.     

Synthese und Reaktionsverhalten von Platin(II) und Kupfer(I) Koordinationspolymeren; die Festkörperstruktur von {trans-(Ph3P)2Pt[(η-CCPh)CuBr]2}n und trans-(Ph3P)2Pt[(η-CCPh)CuNO3]2

The title complex {trans-(Ph₃P)₂Pt[(η²-CCPh)CuX]₂}_n (3a, X=Cl; 3b, X=Br) can be prepared by treatment of trans-(Ph₃P)₂Pt(CCPh)₂ (1) with two equivalents of [CuX] (2a, X=Cl; 2b, X=Br) in quantitative yield. The reaction chemistry of 3b towards organic chelating molecules is reported. Treatment of 3b with, for example, 2,2^′-bipy (4) produces the chelated copper(I) species [(bipy)CuBr]₂ (6) along with 1. However, if 3b is reacted with the silver(I) salt [AgNO₃] (5a) then trimetallic trans-(Ph₃P)₂Pt [(η²-CCPh)CuNO₃]₂ (7) is formed in which each phenylethynyl ligand is η²-coordinated to a copper(I) nitrate unit. This complex is also obtained, when 1 is reacted with two equivalents of [Cu(NCMe)₄]NO₃ (5b).The solid-state structures of 3b and 7 are reported. Polymeric 3b crystallises in the triclinic space group with cell parameters a=11.5958(3) Å, b=13.3491(3) Å, c=15.4875(4) Å, α=81.755(1)°, β=87.324(1)°, γ=85.472(1)°, V=2363.66(10) ų, Z=2 and ρ=1.818 g mol⁻¹. Complex 7: monoclinic space group P2_/n with a=9.8971(1), b=14.2324(3), c=16.6957(2) Å, β=105.478(1)°, V=2266.46(6) ų, Z=2 and ρ=1.719 g mol⁻¹.In 3b a linear polymeric structure is adopted. 3 contains two crystallographic independent trans-Pt(CCPh)₂ units which are linked by 4-membered Cu₂(μ-Br)₂ cycles at which the respective PhCC units are η²-coordinated to the copper(I) ions. In 7 each of the two PhCC entities is π-bound to a mononuclear CuNO₃ moiety of which the NO₃ ligand is chelate-bound to copper(I).     

Synthesis and crystal structure of [W3S4(Acac)3(PPh3)3]PF6 · 0.5CHCl3 and [W3S4(Hfac)3(PPh3)2Br] · 2CHCl3

New cluster complexes [W₃S₄(Acac)₃(PPh₃)₃]PF₆ · 0.5CHCl₃ (Acac = CH₃C(O)CHC(O)CH₃) (I) and [W₃S₄(Hfac)₃(PPh₃)₂Br] · 2CHCl₃ (Hfac = CF₃C(O)CHC(O)CF₃) (II) were synthesized. Their molecular and crystal structures were determined by X-ray diffraction. The cis-cis type of coordination of acetylacetonate and hexafluoroacetylacetonate ligands in I and II, respectively, was established, and the PPh₃ ligands were found in the trans-positions with respect to the “capping” sulfide ligand (μ³-S).     

Pyridine-2-thione (pySH) derivatives of silver(I): Synthesis and crystal structures of dinuclear [Ag2Cl2(μ-S-pySH)2(PPh3)2] and [Ag2Br2(μ-S-pySH)2(PPh3)2] complexes

Reaction of silver(I) halides with PPh₃ in acetonitrile and then with pyridine-2-thione (pySH) chloroform (1:1:1 molar ratio) has yielded sulfur bridged dimers of general formula, [Ag₂X₂(μ-S-pySH)₂(PPh₃)₂] (X = Cl, 1, Br, 2). Both these complexes have been characterized using analytical data, NMR spectroscopy and single crystal X-crystallography. The central Ag₂S₂ cores form parallelograms with unequal Ag–S bond distances (2.5832(8), 2.7208(11) Å) in 1 and (2.6306(4), 2.6950(7) Å) in 2, respectively. The Ag?Ag contacts of compounds 1 and 2 are 3.8425(8) and 3.8211(4) Å, respectively. The angles around Ag (in the range 87.19(2)–121.71(2)° in 1 and 87.81(2)–121.53(2)° in 2) reveal highly distorted tetrahedral geometry. There are inter dimer π–π stacking interactions between pyridyl rings (inter ring distances of 3.498 and 3.510 Å in complexes 1 and 2, respectively). The solution state ³¹P NMR spectroscopy has shown the existence of both monomers and dimers. The studies reveal relatively weaker intramolecular –NH?Cl hydrogen bonding in case of AgCl vis-à-vis that in CuCl which favored both a monomer and a dimer with AgCl, and only a monomer with CuCl.     

trans-dinitro- and trans-dinitratoruthenium complexes [RuNO(NH3)2(NO2)2(OH)] and [RuNO(NH3)2(H2O)(NO3)2]NO3·H2O

Methods for the synthesis of trans-diammino complexes [RuNO(NH₃)₂(NO₂)₂(OH)] (I) and [RuNO(NH₃)₂(H₂O)(NO₃)₂](NO₃)·H₂O (II) are suggested. The compounds were studied by IR spectroscopy and X-ray phase and X-ray structural analyses. Crystal data: space group P-1; a = 6.2328(2) ?, b = 11.0488(3) ?, c = 11.0981(4) ?, α = 71.942(1)°, β = 83.291(1)°, γ = 86.877(1)° (I); space group P2₁; a = 6.6290(2) ?, b = 13.4389(5) ?, c = 7.0180(2) ?, β 114.281(1)° (II). Complex II readily lost some part of crystal water on storage in open air. Original Russian Text Copyright ? 2009 by M. A. Il’in, E. V. Kabin, V. A. Emel’yanov, I. A. Baidina, and V. A. Vorob’yov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 50, No. 2, pp. 341–348, March–April, 2009.     

Binuclear ruthenium complexes of fluorous phosphine ligands: Synthesis, properties, and biphasic catalytic activity. Crystal structure of [Ru(μ-O2CMe)(CO)2P(CH2CH2(CF2)5CF3)3]2

The fluorocarbon soluble, binuclear ruthenium(I) complexes [Ru(μ-O₂CMe)(CO)₂L^F]₂, where L^F is the perfluoroalkyl substituted tertiary phosphine, P(C₆H₄-4-CH₂CH₂(CF₂)₇CF₃)₃, or P(CH₂CH₂(CF₂)₅CF₃)₃, were synthesized and partition coefficients for the complexes in fluorocarbon/hydrocarbon biphases were determined. Catalytic hydrogenation of acetophenone to 1-phenylethanol in benzotrifluoride at 105 °C occured in the presence of either [Ru(μ-O₂CMe)(CO)₂P(C₆H₄-4-CH₂CH₂(CF₂)₇CF₃)₃]₂ (1) or [Ru(μ-O₂CMe)(CO)₂P(CH₂CH₂(CF₂)₅CF₃)₃]₂ (2). The X-ray crystal structure of [Ru(μ-O₂CMe)(CO)₂P(CH₂CH₂(CF₂)₅CF₃)₃]₂ was determined. The compound exhibited discrete regions of fluorous and non-fluorous packing.     

Synthesis,X-ray crystal structure and thermal decomposition of two peroxovanadium complexes with coordinated ammonia molecules: [{VO(O2)2(NH3)}2{μ-Cu(NH3)4}] and [Zn(NH3)4][VO(O2)2(NH3)]2

The compounds [{VO(O₂)₂(NH₃)}₂{μ-Cu(NH₃)₄}] (1) and [Zn(NH₃)₄][VO(O₂)₂(NH₃)]₂ (2) were prepared and characterized by elemental analysis and infrared spectra. The single crystal X-ray study revealed that the structure of 1 consists of trinuclear complex molecules [(NH₃)OV(O₂)₂{μ-Cu(NH₃)₄}(O₂)₂VO(NH₃)] with a rare heterobimetalic peroxo bridge: copper(II)–peroxo ligand–vanadium(V). The structure of 2 is composed of tetraamminezinc(II) cations and ammineoxodiperoxovanadate(V) anions. In course of thermal decomposition of 1 performed up to 620 °C, the following intermediate products: [Cu(NH₃)₂(VO₃)₂], and subsequently a mixture of V₂O₅ with monoclinic β-Cu₂V₂O₇, were gradually formed. The final product of decomposition is Cu(VO₃)₂. The thermal decomposition of 2 is a two-step process. In the first stage, [Zn(NH₃)₃(VO₃)₂] as supposed intermediate was formed, which transformed at higher temperatures by release of ammonia molecules to the monoclinic modification of Zn(VO₃)₂.     

Synthesis and structural characterisation of the palladium N-heterocyclic carbene cluster complexes [Pd3(μ-CO)3(NHC)3] and [Pd3(μ-SO2)3(NHC)3]

The reduction of trans-[Pd(NHC)₂Cl₂] (NHC = IMes, 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene; IⁱPr₂ = 1,3-bis-isopropylimidazol-2-ylidene) with potassium graphite under an atmosphere of CO affords the palladium NHC carbonyl clusters [Pd₃(μ-CO)₃(NHC)₃] (NHC = IMes, 1; IⁱPr₂, 3). Treatment of 1 with SO₂ at room temperature yields the bridging SO₂ complex [Pd₃(μ-SO₂)₃(IMes)₃] (4) in quantitative yield. Complexes 1, 3 and 4 have been structurally characterised by X-ray crystallography.     

Synthesis and crystal structure of one-dimensional heterotrimetallic coordination polymer {[(Dipic)2Cu]4 · Mg(H2O)2Na4(H2O)14}n · nNa2(H2O)10 · 2nCH3OH

A novel heterotrimetallic complex {[(Dipic)₂Cu]₄ · Mg(H₂O)₂Na₄(H₂O)_{14 n} · nNa₂(H₂O)₁₀ · 2nCH₃OH (H₂Dipic = pyridine-2,6-dicarboxylic acid) has been synthesized and structurally determined by X-ray diffraction method. The compound crystallizes in the triclinic system, space group P [`1]\bar 1, with a = 13.5523(13), b = 14.1859(13), c = 14.3213(14) ?, α = 62.6160(10)°, β = 68.2540(10)°, γ = 89.7110(10)°, V = 2224.7(4)?³, F(000) = 1144, M _r = 2237.70, Z = 1, ρ _c = 1.670 g cm⁻³, μ = 1.095 mm⁻¹, final R = 0.0507, wR = 0.1418 for 8042 independent reflections with R _int = 0.0228. According to the structure determination, the complex is composed of novel one-dimensional (1D) alternating chains, dinuclear Na(I) units, and lattice methanol molecules. The infinite 1D chain structure is built up with many of polymeric [(Dipic)₂Cu]₄ · Mg(H₂O)₂Na₄(H₂O)₁₄ units, which consists of four six-coordinated Cu²⁺ ions, one six-coordinated Mg²⁺ ion, two five-coordinated Na⁺ ions, and two six-coordinated Na⁺ ions. The 1D alternating chains are linked with another dinuclear Na(I) units by extensive hydrogen bonds to form a three-dimensional (3D) supramolecular structure in which uncoordinated methanol molecules act as space filling particles.     

Crystal structure of [Pd(NH3)4]3[Ir(NO2)6]2·H2O

A single crystal of [Pd(NH₃)₄]₃[Ir(NO₂)₆]₂·H₂O double complex salt is studied by X-ray diffraction. Crystallographic characteristics are as follows: a = 21.0335(5) ?, b = 8.0592(2) ?, c = 21.3452(5) ?, β = 91.254(1)°, V = 3617.43(15) ?³, P2₁/c space group, Z = 4, d _x = 2.714 g/cm³. Single-layer pseudohexagonal packing of complex anions is determined along the [−1 0 1] direction in the structure. Complex cations and crystallization water molecules are located between the mentioned layers.