Monoalkylthallium(III) derivatives: preparation and X-ray crystal structure of cyclopropylbis(isobutyrato)thallium(III)

Cyclopropylbis(isobutyrato)thallium(III) has been synthesised and its crystal structure determined. The compound crystallises in the orthorhombic space group Pna2₁, with a 7.316, b 12.079, c 16.19 Å. Linear polymers are present in which thallium is seven-coordinate. Two types of carboxylate ligands are present; one weakly chelating and the other both chelating and bridging.This structure allows clarification of infrared spectroscopic data, presented for mono- and diorganothallium(III) carboxylates, in the solid state in solution.     

The structure of di-μ-pentafluorobenzoatobis[bis(pentafluorophenyl)(triphenylphosphine oxide)thallium(iii)]

An X-ray crystallographic study has shown that the complex (C₆H₅)₂TlO₂CC₆F₅(OPPh₃) has a dimeric structure with unsymmetrical pentafluorobenzoate bridging (TlO 2.531 and 2.789 Å) but an exact crystallographic centre of symmetry. The pentafluorobenzoate groups are also unsymmetrically chelated to thallium (TlO 2.389 and 2.531 Å.), which overall has irregular six coordination.     

A novel synthesis and crystal data for thallium(III) oxide bromide

Thallium(III) oxide bromide, TlOBr, has been prepared from thallium(I) carbonate and liquid bromine. It crystallizes in an orthorhombic unit cell with, a = 4.147(1) Å, b = 3.760(1) Å, c = 8,706(3) Å, Z = 2, space group Pmmn, and is isomorphous to InOBr (FeOCl type).     

Characterization and X-ray crystal structure of butanoylsalophencobalt(III)

The synthesis and characterization of the pentacoordinated butanoylsalophencobalt(III) compound, including X-ray analysis, are described. The chemical shift in the ¹³C-n.m.r. of the carbonyl carbon was determined by means of an HMBC experiment. Collision induced dissociation (CID) and high resolution mass spectrometry were used to establish the fragmentation pattern of the CoC₂₄H₂₁N₂O₃ compound. X-ray diffraction analysis shows the presence of two conformations for the acylsalophen ligand system in the same monocrystal, as well as two different OH–C hydrogen bonds with unusual interactions.     

The preparation and X-ray crystal and molecular structure of (α,1,2-η-6-methylbenzyl) bis(triphenylphosphine)rhodium(I)

Reaction of [RhCl(PPh₃)₃] with [o-MeC₆H₄CH₂MgBr] affords high yields of the non-fluxional complex, [Rh(CH₂C₆H₄Me)(PPh₃)₂] which has been shown crystallographically to contain a 1-3-η-benzyl group bound through the phenyl carbon atom that is not substituted with the methyl group. Crystals of this compound are triclinic, space group P$\text{1}$, with a = 10.561(6). b = 17.705(3), c = 10.934(4) Å, α = 80.69(3), β = 116.86(4), γ = 102.30(4)° and Z = 2. The structure was solved via the heavy-atom method and refined to R = 0.032 using 5379 diffractometer data with I > 1.56(I). Attempts to prepare π-bonded xylylene complexes from this compound by reaction with base have been unsuccessful, but protonation followed by recrystallisation from acetone gives [Rh{(CH₃)₂CO}₂(PPh₃)₂]BF₄.     

Crystal and molecular structures of two europium(III) nitrate complexes with triphenylphosphine oxide

The X-ray structures of the complexes Eu(NO₃)(Ph₃PO)₃(acetone)₂ (A) (Ph₃PO = triphenylphosphine oxide) and Eu(NO₃)₃(Ph₃PO)₂(ethanol) (B) have been solved by the heavy-atom method, by using the three-dimensional Patterson-Fourier synthesis. The crystals are both monoclinic and belong to the space group P2₁/n, with Z = 4. The cell dimensions are: a = 27.825(4) Å, b = 19.422(4) Å, c = 11.238(2) Å, β = 94.9(3)° for A; and a = 22.193(4) Å, b = 10.866(2) Å, c = 17.101(3) Å, β = 105.6(3)° for B. In both complexes the europium(III) ion is ennea-coordinated to three chelate nitrate groups and three oxygens of the Ph₃PO ligands for A and two of the Ph₃PO and one of the ethanol for B. The acetone molecules of A are outside the coordination sphere of the metal and disordered.     

Synthesis,characterization and crystal structure of triphenylphosphine copper(I) methylpyruvate thiosemicarbazones

This paper reports the synthesis of a series of methylpyruvate thiosemicarbazone derivatives containing, on the terminal nitrogen, substituents of different nature and size and namely, ethyl, phenyl and methylphenyl. These ligands were reacted with bis(triphenylphosphine)copper(I) nitrate and acetate to produce the respective complexes: [Cu(PPh₃)₂(Et-Hmpt)]₂(NO₃)₂ (1), [Cu(PPh₃)₂(Ph-Hmpt)]NO₃ (2), [Cu(PPh₃)₂(MePh-Hmpt)]NO₃ (3), [Cu₂(O₂CCH₃)(Et-pt)(PPh₃)₂] · H₂O (4), [Cu(Ph-mpt)(PPh₃)] (5) and [Cu₂(MePh-mpt)₂(PPh₃)₂] (6). All of them were characterized by elemental analysis, IR, ¹H NMR, EPR spectroscopy and, for compounds 1, 2, 4, and 6, by X-ray crystallography. The characterization revealed that the coordinating behaviour of the ligands is influenced by a series of factors, predominant among which is the hard soft nature of the atoms involved in the interactions with the metal centre. The complexes obtained from the nitrate copper(I) salt are formed by cationic molecules with a nitrate as a counterion, while those derived from the acetate salt present deprotonated ligands and a few unexpected features. In particular, one of the compounds (4) is a mixed valence dinuclear complex with an acetate oxygen and the thiosemicarbazone sulfur acting as bridging between the two Cu(I) and Cu(II) ions. Another one (6) presents instead a Cu(I)–Cu(I) sulfur bridged binuclear cluster.     

Luminescent and triboluminescent properties of europium(III) hexafluoroacetylacetonate and trifluoroacetate complexes with triphenylphosphine oxide

Crystalline and strongly luminescent complexes of europium hexafluoroacetylacetonate and trifluoroacetate with triphenylphosphine oxide of Eu(HFAA)₃ · 2TPPO and [Eu(TFA)₃ · 2TPPO(H₂O)]₂ composition are synthesized that demonstrating triboluminescent properties. It is established that the measured photoluminescence and triboluminescence spectra of these noncentrosymmetric complex compounds are identical, due to the characteristic f-f-luminescence of the europium(III) ion.     

Novel ternary cobalt(II) and nickel(II) complexes of N-phthaloylglycinate. Synthesis, characterization and X-ray crystal structure

A new series of N-phthaloylglycineate (N-phthgly) ternary complexes of cobalt(II) and nickel(II) with imidazole (imi), N-methylimidazole (mimi) and 2,2′-bipyridyl (bipy) have been synthesized and characterized by elementary analyses, IR spectroscopy, thermogravimetric analysis. X-ray crystal structure analyses of the three complexes of [Co(mimi)₂(N-phthgly)₂] (1), [Co(bipy)(OH₂)₄](N-phthgly)₂ (2) and [Ni(imi)₂(N-phthgly)₂(OHCH₃)₂] (3) were also carried out. In complex (1), the Co(II) exists in a distorted tetrahedral enviroment, where two nitrogen atoms of two methylimidazole molecules and two oxygen atoms of the carboxylate group of two N-phthaloylglycinate molecules are coordinated. On the other hand, in complex (2) the cobalt atom coordinates a 2,2′-bipyridine molecule and four water oxygen atoms forming a distorted octahedral conformation. A molecule of N-phthaloylglycinate is connected by van der waals contact and H-bonds. For complex (3), the nickel atom is surrounded by four oxygens (two oxygens of two different N-phthaloylglycinate molecules and two of methanol ligand) in the basal plane of octahedron along with two imidazole nitrogen atoms at the apical positions. Strong intramolecular H-bond exists between the uncoordinated carboxylic oxygen of the N-phthaloylglycinate ligand and the O–H of the methanol group.     

The trans-influence in polyenyl—metal complexes; The crystal and molecular structure of hydrido-(η-pentamethylcyclopentadienyl)bis(triphenylphosphine)-rhodium(III) hexafluorophosphate

The structure of [Rh(η-C₅Me₅)H(PPh₃)₂]PF₆ has been determined by ¹H NMR studies and a single-crystal X-ray analysis. The compound crystallises in the orthrhombic space group P2₁2₁2₁ with lattice constants a 12. 926(3), b 15.216-(3) and c = 20.957(4) Å, with Z = 4. The structure was determined using diffractometer data and by least-squares techniques to R = 0.0887 based on 2805 independent reflections with F₀?4o(F₀). The geometry about the metal atom may be inferred to be a “piano-stool” arrangement with the C₅Me₅ ring representing the seat and the PPh₃ and H ligands the legs, although the hydrogen atom was not directly located in the crystallographic analysis. The observed distortions in the C₅Me₅ ring may be attributed to the large trans-influence of the hydrido ligand.     

The crystal structure of tris(acetonitrile)nitrosylbis(triphenylphosphine)iridium(III) dihexafluorophosphate. An unusual iridium nitrosyl hexacoordinate complex

Summary The structure of [Ir(NCMe)₃(NO)(PPh₃)₂][PF₆]₂ has been ] determined by x-ray methods. Crystals are orthorhombic, space groupPca 2₁ , witha = 21.753(14),b = 11.678(10),c = 18.474(12) Å and Z = 4. The structure has been solved from diffractometer data and refined by full-matrix leastsquares to R = 0.076 for 2776 observed reflections. The cation is a hexacoordinate and not a pentacoordinate species as expected. The extra acetonitrile molecule,trans to the nitrosyl ligand, is much more weakly bound to the metal atom [Ir-N 2.360(26) against 1.965(20) and 1.912(14) Å for the other two acetonitriles]. The nitrosyl is bent [Ir-N-O 111(1)° Å] and acts as the formally one-electron donor NO^–.     

Synthesis and crystal structure of (18-crown-6)(perchlorato-O)(triphenylphosphine oxide)potassium

A new complex, (18-crown-6)(perchlorato-O)(triphenylphosphine oxide)potassium, was synthesized and its structure was studied by X-ray diffraction. The crystals are trigonal: a = 14.419,c = 13.895 Å, Z = 3, space group R3m; the structure was solved by the direct method and refined by the anisotropic full-matrix least-squares method, R = 0.079 on 1930 independent reflections, CAD-4 automated diffractometer, λMoK _α . The structure contains a highly symmetric host-guest complex molecule [K(ClO₄)(18-crown-6)(Ph₃PO)] in position 3m (with three Ph rings of the Ph₃PO ligand and all the O atoms of a crown ligand lying in three m planes). The coordination polyhedron of the K⁺ cation is a distorted hexagonal bipyramid with six O atom of the 18-crown-6 ligand in a base and the O atom of the Ph₃PO ligand and disordered O atom of the ClO ₄ ^? ligand in the axial vertices.     

Organothallium compounds : XVII. Halogenobis(polyfluorophenyl)thallium(III) complexes

The preparations, stabilities and structures of the complexes R₂TlX and R₂ LTlX (R = C₆F₅, p-HC₆F₄, or o-HC₆F₄; X = Br or Cl; L = Ph₃PO, 2,2′-bipyridyl (bpy) or Ph₃P) have been examined or (R = C₆ F₅) reinvestigated. The derivatives R₂TlX are monomeric in acetone, from which the complex (p-HC₆F₄)₂ Me₂COTIBr has been isolated. In this solvent, the complexes R₂LTlX (L = Ph₃PO, bpy, or Ph₃P) undergo partial dissociation by loss of L. When L = bpy, there is also slight ionization into R₂LTl⁺ and R₂TlX^?₂. The acceptor properties of R₂TlX compounds towards uncharged ligands decrease R = C₆F₅ ? p-HC₆F₄ > o-HC₆F₄ > Ph. Dimeric behaviour is observed for R₂TIX compounds in benzene, whilst R₂LTlX (L = Ph₃PO or bpy) derivatives show slight but significant association. In the solid state, R₂TlX compounds are considered to be polymeric with five coordinate thallium, and R₂LTlX derivatives to be dimeric with five (L = Ph₃PO) or six (L = bpy) coordinate thallium by contrast with four coordinate dimeric and four or five coordinate monomeric structures previously proposed for the respective pentafluorophenyl derivatives. Halogen bridging is unsymmetrical for R = C₆F₅ or p-HC₆F₄, but may be more symmetrical for R = o-HC₆F₄ when L = Ph₃PO or bpy. Reported structural data for the complexes (C₆F₅)LTlX (L = Ph₃AsO, Ph₃P, Ph₃As, or 1,10-phenanthroline; X = Br or Cl) and (C₆F₅)₂TlCl^?₂ are reinterpreted and the proposed structures revised.     

The synthesis and X-ray structure of five co-ordinate imidodiphosphinate complexes of indium(III)

We report the synthesis and structural characterisation of three five co-ordinate indium(III) bis-chelate complexes of imidodiphosphinates with general formula InCl{N(PR₂X)₂}₂, (R=Ph or Prⁱ, X=S or Se), formed from the 1:2 reaction of indium(III) trichloride and the potassium or sodium salt of the ligand in methanol/THF. The complexes consist of discrete monomeric, molecules and show a trigonal–bipyramidal co-ordination pattern. These are the first examples of five co-ordinate complexes containing this type of ligand, in contrast to other indium(III) and main group element complexes of similar ligands in which only the six co-ordinate tris-chelates are known.     

Nitrato(triphenylphosphine) complexes of the platinum metals; Detection of triphenylphosphine oxide ligands

Reactions of some platinum group metal triphenylphosphine complexes with nitric acid afford nitrato(triphenylphosphine) derivatives in good yield; the complex “Rh(NO₃) (NO)₂(OPPh₃)₂” is positively identified as [Rh(NO₃)₂ (NO) (PPh₃)₂]     

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).     

The crystal and molecular structure oftrans-Di(methylsulphito)bis-(triphenylphosphine)platinum(II)

Summary The crystal and molecular structure oftrans-di(methylsulphito)bis(triphenylphosphine)platinum(II), Pt(SO₃Me)₂ (PPh₃)₂, derived from the reaction of Pt(PPh₃)₂ (O₂) with SO₂ in MeOH and in the presence of sodium tetraphenylborate(III), has been determined from diffractometer data. The complex crystallizes in the space group P ¯1- (C_i ¹) with one molecule in a unit cell of dimensionsa = 9.744(2) Å,b = 10.062(3) Å,c = 11.153(2) Å; = 68.59(2)°, = 82.69(2)° and = 62.25(2)°. Leastsquares refinement has led to a value of the conventional R index (on F) of 0.031 for the 3308 reflections having F²>3(F₀ ²). The complex is a typical square-planar platinum(II) complex with the platinum atom lying on a crystallographically imposed centre of symmetry. The important structural parameters are Pt-P 2.369(1) Å, Pt-S 2.308(1) Å, and the oxygen atoms complete an approximate tetrahedron about the sulphur atoms with S-O 1.448(5) Å and S-O(Me) 1.620(5) Å.