The synthesis and structure of bis(acetonitrile)nitrosyl tris(3,5-dimethylpyrazolyl)borato molybdenum hexafluorophosphate

Summary Treatment of [Mo{HB(3,5-Me₂C₃HN₂)₃}(NO)I₂] with one or two moles of AgPF₆ in acetonitrile afforded the paramagnetic (one unpaired electron) complex [Mo{HB(3,5-Me₂C₃NH₂)₃}(NO)(NCMe)₂][PF₆]. The structure of this complex was determined crystallographically, and the six-coordinate geometry of the complex cation confirmed.     

The crystal and molecular structure of η5-cyclopentadienyliodomethyl(methylthio)carbene-(triphenylphosphine)iridium(III) iodide

The crystal and molecular structure of η⁵-cyclopentadienyliodomethyl(methylthio)carbene(triphenylphosphine)iridium(III) iodide [IrI{C(Me)SMe}(η⁵-C₅H₅)(PPh₃)]I has been determined from three dimensional X-ray data in order to clarify the contribution of the α-sulphur atom to the bonding in this carbenoid complex.The compound crystallizes in space group Pbc2₁ with four formula units in a cell of dimensions a 9.745(6), b 15.201(8), and c 17.364(10) Å. Least-squares refinement of the structure has led to the final discrepancy index R = 0.047 for the 1655 symmetry-independent observable reflections. The coordination geometry about the iridium atom is approximately tetrahedral; the coordination positions are occupied by the η⁵-C₅H₅ ring center, the phosphorus, the iodide I(1) and the carbon C(6) of the C(Me)SMe ligand (IrRc 1.89, IrP 2.280(7), Ir(1) 2.651(2) and IrC(6) 2.03(3) Å).The bonding of the C(Me)SMe group indicates that this complex must be formulated as a C(Me)SMe complex of iridium(III).     

Crystal structure of tris(triphenylphosphine) palladium

N. S. Kurnakov Institute of General and Inorganic Chemistry, Academy of Sciences of the USSR. Translated from Zhurnal Strukturnoi Khimii, Vol. 28, No. 4, pp. 103–106, July–August, 1987.     

Synthesis and crystal structure determination of Cl-substituted iridium(III) acetylacetonate

γ-Halogen-substituted iridium(III) acetylacetonates of general formula Ir(acacX)₃,where acacX = CH₃ -CO-CX-CO- CH₃,X =Br, I, were synthesized. The compounds are characterized by melting points and chemical analysis data for C, H, Br, and I. An X-ray diffraction analysis was performed for iridium(III) acetylacetonate and its y-substituted analogs, crystal data were obtained, and crystal structures were determined. The crystals are monoclinic;the structures are molecular. Crystal data: Ir(acac)3 _- IrO₆C₁₅H₂₁,a = 13.900(2), b = 16.440(3), c = 7.494(2) ?, γ =98.63(2)‡, V= 1693.2 ?³,space group P2₁/b,Z = 4, d_calc =1.92 g/cm³,sin θ/λ_max = 0.703, F_hkl = 2841, R = 0.044. Ir(acacBr)_3- IrBr₃O₆C₁₅H₁₈,a = 12.794(2), b = 15.753(2), c = 9.990(2) ? Β = 105.76(2)‡, V= 1937.6 ?³,space group P2₁/n,Z =4, d_calc =2.49 g/cm³, sinθ/λ_max = 0.702, F_hkl = 1748, R = 0.048. Ir(acacI)3- M₃O₆C₁₅H₁₈,a = 12.855(2), b = 10.136(2), c =16.338(3)?, Β = 104.6(2)‡, V=2059.8?³,space group P2₁/n, Z =4, d_calc = 2.79g/cm³, θ_max =25‡, F_hkl = 2817, R =0.032. The Ir..Ir distances were estimated to be > 7.49 ? for Ir(acac)3 and > 8.10 ? for Ir(acacBr)3 and Ir(acacl)₃.If the estimate is limited to 10 ?, the intermolecular coordination number (ICN) in the structures is 10. Translated fromZhurnal Struktumoi Khimii, Vol. 40, No. 2, pp. 331–339, March–April, 1999     

The preparation and characterization of TlClBrI complexes. X-ray crystal structure of chlorobromoiodo-bis-(triphenylphosphine oxide)thallium(III)

The complexes TlClBrI·L₂ (L = C₅H₅NO, 2-, 3-, 4-CH₃C₅H₄NO, 4-ClC₅H₄NO, 4-CNC₅H₄NO, 4-NO₂C₅H₄NO, 4-CH₃OC₅H₄NO, HMPA and OPPh₃) have been prepared and characterized by elemental analysis. The solids behave as non-electrolytes in acetonitrile solution and are monomers in benzene. The structure of TlClBrI(OPPh₃)₂ has been determined by X-ray crystallography and refined to a conventional R factor of 0.05. This compound crystallizes in the monoclinic space group P2₁/c and a = 14.742(5), b = 14.418(3), c = 17.234(4) Å, β = 107.54(2)° and Z = 4. The structure consists of neutral monomeric complexes in which the thallium atom shows a five-fold coordination in the form of a distorted trigonal bipyramid, the halogen atoms being located in the equatorial plane. ¹H NMR and vibrational (IR and Raman) spectra of all of these complexes are discussed on the basis of this structure.     

In pursuit of the molybdenum(III) tris(thiolate) fragment: unusual structure of a dimolybdenum mu-nitrido complex

The new molybdenum nitrido-thiolate complex N triple bond Mo(SAd)3 (Ad = 1-adamantyl) was prepared by a ligand exchange route involving reaction of Ti(SAd)(OiPr)3 with Chisholm's nitrido-butoxide complex N triple bond Mo(OtBu)3. In an effort to abstract the nitrido nitrogen from N triple bond Mo(SAd)3, the compound was treated with Mo(N[tBu]Ph)3, a three-coordinate molybdenum(III) complex. This resulted in formation of the unusual and thermally unstable (mu-nitrido)dimolybdenum complex (AdS)3Mo(mu-N)Mo(N[tBu]Ph)3, which was isolated and characterized. An X-ray study revealed (AdS)3Mo(mu-N)Mo(N[tBu]Ph)3 to possess an unsymmetrical Mo-(mu-N)-Mo linkage, the Mo-thiolate fragment exhibiting a substantially longer bond to the bridging nitrogen atom. The structure of (AdS)3Mo-(mu-N)Mo(N[tBu]Ph)3 is noteworthy, displaying trigonal monopyramidal coordination at the (mu-N)-Mo-thiolate Mo center. Since N triple bond Mo(N[tBu]Ph)3 is a good leaving group, (AdS)3Mo(mu-N)Mo(N[tBu]Ph)3 should be a source of the reactive Mo(SAd)3 fragment. In all the studied reactions of the (mu-nitrido)dimolybdenum complex one of the observed products was N triple bond Mo(N[tBu]Ph)3. Two products containing the Mo(SAd)3 fragment were observed: (AdS)3Mo triple bond Mo(SAd)3 and [(ON)Mo(mu-SAd)(SAd)2]2. Upon treatment with pyridine, the tris(thio-1-adamantyl)-(nitrosyl)molybdenum dimer forms the pyridine adduct (AdS)3Mo(NO)(py), which is a monomer.     

The crystal structure of tris(triphenylphosphine)gold(I)-[dodecahydrido-6-thia-nido-decaborate(1—)]

The crystal structure of tris(triphenylphosphine)gold(I)[dodecahydrido-6-thia-nido-decaborate(1—)], [(C₆H₅)₃P]₃AuB₉H₁₂S, has been determined using X-ray techniques and counter data. The compound is a salt consisting of [(C₆H₅)₃P]₃Au⁺ cations and B₉H₁₂S^? anions. The cation is trigonal and nearly planar with AuP distances of 2.382(5) Å and PAuP anglés of 119.3(36)°. The B₉H₁₂S^? thiaborane anion is an open icosahedral fragment with the S atom in the 6 position, on the periphery of the decaborane polyhedron. The structure is the same as that found in solution for the isoelectronic B₁₀H₁₄^2? anion. Crystals are triclinic, space group P$\text{1}$, with a = 13.086(12), b = 19.635(32), c = 11.180(8) Å, α = 103.60(16), β = 72.10(9), and γ = 94.76(15)°. The structure was refined by least squares to a conventional R of 0.077.     

Synthesis and crystal structure of tris(ethylenediamine)cobalt(III) bis(tetrachloroaurate(III)) chloride

The binary complex salt [Co(N₂C₂H₈)₃][AuCl₄]₂Cl has been synthesized. Its crystal structure has been determined. Crystal data for C₆H₂₄N₆Cl₉AuCo: a = 20.8976(14) Å, b = 14.4773(9) Å, c = 7.9944(5) Å; β = 110.809(2)°; V = 2260.9(3) ų, space group C2/c, Z = 4, d _calc = 2.798 g/cm³. The plane square environment of the gold atom of the complex anion is completed to a tetragonal pyramid by the chlorine atom of the neighboring complex anion (Au…Cl 3.538 Å). The structure is layered. Layers of complex cations and complex anions alternate along the X axis.     

Highly efficient phosphorescent iridium (III) diazine complexes for OLEDs: Different photophysical property between iridium (III) pyrazine complex and iridium (III) pyrimidine complex

The synthesis and luminescence of four new iridium (III) diazine complexes (1-4) were investigated. HOMO and LUMO energy levels of the complexes were estimated according to the electrochemical performance and the UV-Vis absorption spectra, showing the pyrimidine complexes have a larger increase for the LUMO than the HOMO orbital in comparison with the pyrazine complexes. Several high-efficiency yellow and green OLEDs based on phosphorescent iridium (III) diazine complexes were obtained. The devices emitting yellow light based on 1 with turn-on voltage of 4.1 V exhibited an external quantum efficiency of 13.2% (power efficiency 20.3 lm/W), a maximum current efficiency of 37.3 cd/A. The electroluminescent performance for the green iridium pyrimidine complex of 3 is comparable to that of the iridium pyridine complex (PPY)₂Ir(acac) (PPY = 2-phenylpyridine), which is among the best reported.     

A cyclometallated iridium(III) dimethylphenylphosphine complex

[Ir(cod)Cl]₂ (cod = 1,5-cyclooctadiene) reacts with PMe₂Ph in CH₃CN to give the red cation [Ir(PMe₂Ph)₄]⁺. This complex in CH₃CN reacts with H₂ to give cis-[IrH₂(PMe₂Ph)₄]⁺, but on reflux for 6 h in the absence of H₂, it gives the first example of a cyclometallated PMe₂Ph complex fac-[IrH(PMe₂C₆H₄)(PMe₂Ph)₃]⁺, as shown by PMR spectroscopy and preliminary X-ray crystallographic data.     

A bright tetranuclear iridium(III) complex

A cyclic tetranuclear cyclometallated iridium(III) complex using cyanide anions as bridging ligands and displaying a tetrahedrally distorted square geometry has been obtained with high yield; photo- and electrochemical characterizations show that most interesting properties of mononuclear cyclometallated iridium complexes are retained in the tetranuclear assembly.     

An iridium(III) complex that exhibits dual mechanism nonlinear absorption

The photophysical properties of the complex (L)Ir(ppy)(2)(+), where ppy = 2-phenylpyridine and L = 4,4'-(2,2'-bipyridine-5,5'-diylbis(ethyne-2,1-diyl))bis(N,N-dihexylaniline), have been investigated under one- and two-photon excitation conditions. In THF solution, the complex exhibits broad ground-state absorption with lambda(max) approximately 500 nm and weak photoluminescence with lambda(max) approximately 730 nm. Excitation of (L)Ir(ppy)(2)(+) at 355 nm produces a long-lived excited state (tau approximately 1 mus) that features a strong excited-state absorption in the near-infrared (lambda(max) approximately 875 nm, Deltaepsilon approximately 6.1 x 10(4) M(-1) cm(-1)). Photoluminescence and transient absorption studies of (L)Ir(ppy)(2)(+) carried out using 5 ns, 1064 nm pulsed excitation demonstrate that the same long-lived and strongly absorbing excited state can be efficiently produced by two-photon absorption. Solutions of the complex in THF display nonlinear absorption of 5 ns, 1064 nm pulses in a process that is believed to involve a combination of two-photon absorption and reverse saturable absorption.