Preparation and X-Ray Crystal Structures of Tetrahydrofuran-Complexed Rare Earth Chlorides — a Structurally Rich Series

1998 ◽  
Vol 51 (1) ◽  
pp. 75 ◽  
Author(s):  
Glen B. Deacon ◽  
Tiecheng Feng ◽  
Peter C. Junk ◽  
Brian W. Skelton ◽  
Alexander N. Sobolev ◽  
...  
Keyword(s):  
Oxygen Atom ◽  
Crystal Structures ◽  
Ion Pairs ◽  
Far Infrared ◽  
Prolonged Treatment ◽  
Direct Reaction ◽  
Metal Powders ◽  
Metal Chlorides ◽  
X Ray ◽  
Linear Chains

Anhydrous lanthanoid metal chlorides LnCl3(thf)n (Ln = La, Ce, Nd, Sm, n = 2; Ln = Tb, Ho, n = 2·5; Ln = Dy, Tm, n= 2·7; Ln = Gd, Yb, Lu, n = 3; Ln = Er, n = 3·5) have been prepared in excellent yield by the direct reaction of the lanthanoid metal powders with hexachloroethane in tetrahydrofuran (thf), and (Ln = Eu, n = 0·8; Ln = La, n = 1·7; Ln = Pr, n = 2; Ln = Gd, n = 2·5; Ln = Er, n = 3) in good yield except for EuCl3(thf)0·8 from bulk metal. [YbCl3(thf)2]2 was prepared by prolonged treatment of solid YbCl3(thf)3 with pentane. The X-ray crystal structures of [LnC3(thf)2] (Ln = La, Ce or Pr), [LnCl3(thf)3.5] (Ln = Gd or Er), [YbCl3(thf)3] and [LaCl3(thf)(H2O)] have been determined. For [LaCl3(thf)2], a square antiprismatic single-stranded polymer, ... La(-Cl)3(thf)3La(-Cl)3(thf)2 ..., is the first eight-coordinate LnCl3(thf)n complex. The metal is surrounded by two sets of three bridging chlorines and cis thf oxygens. [LnCl3(thf)2] (Ln = Ce, Pr) have seven-coordinate structures with doubly chloride-bridged linear chains, ... LnCl(µ-Cl)3(thf)2LnCl(µ-Cl)2(thf)2 ... where the lanthanoid atom exists in a pentagonal bipyramidal environment, the pentagonal bipyramidal plane being defined by four chloride atoms and one oxygen atom of the thf ligand, and the axial positions being occupied by a chloride and a thf oxygen atom. [LnCl3(thf)3.5] (Ln = Gd, Er) crystallize as discrete ion pairs, [LnCl2(thf)5]+ [LnCl4(thf)2]¯. The lanthanoid atom in the cation displays pentagonal bipyramidal geometry with two apical chloride atoms and five equatorial thf ligands while the anion has quasi-regular octahedral stereochemistry with trans thf ligands. [LaCl3(thf)(H2O)] displays an eight-coordinate two-dimensional polymeric array with six bridging chlorides per lanthanum atom. Far-infrared spectra have been recorded for a number of products and used as a basis for structural proposals, particularly for products with fractional thf.

Organolanthanoids. XXI Synthesis of Bis- and Tris-(diphenylphosphinocyclopenta- dienyl)lanthanoid Compounds and the X-Ray Crystal Structures of [Ln(C5H4PPh2)3(OPPh3)]·(thf)1

1997 ◽  
Vol 50 (10) ◽  
pp. 959 ◽  
Author(s):  
Glen B. Deacon ◽  
Craig M. Forsyth ◽  
Bryan M. Gatehouse ◽  
Anna Philosof ◽  
Brian W. Skelton ◽  
...  
Keyword(s):  
Oxygen Atom ◽  
Single Crystal ◽  
Crystal Structures ◽  
Room Temperature ◽  
Central Metal ◽  
Metal Oxidation ◽  
X Ray

Redox transmetallation ofTl(C5H4PPh2)with an excess of Sm in refluxing thf (thf = tetrahydrofuran) or Eu indme (dme = 1,2-dimethoxyethane) at room temperature gave thelanthanoid(II) compounds[Sm(C5H4PPh2)2](1) and[Eu(C5H4PPh2)2(dme)](2). Crystallization of (1) or[Yb(C5H4PPh2)2(dme)]with OPPh3 in dme yielded[Sm(C5H4PPh2)2(OPPh3)2](3) and[Yb(C5H4PPh2)2(OPPh3)2](4). Room-temperature transmetallation ofTl(C5H4PPh2)with Nd gave the lanthanoid(III) compound[Nd(C5H4PPh2)3(thf)](5), but analogous reactions with La, Pr, Er, Gd and Y in refluxing thfgenerally gave intractable oils, although in one instance impure[La(C5H4PPh2)3(thf)]·(thf)0 · 5,namely(6)·(thf)0 · 5, wasisolated. This complex was also obtained at room temperature by usingLaI3-activated La metal. Oxidation of (1) with 1 equiv.ofTl(C5H4PPh2)in toluene yielded solvent-freeSm(C5H4PPh2)3(7). Addition of OPPh3 to these systems allowed theisolation of[Ln(C5H4PPh2)3(OPPh3)]·(thf)x(x = 0-1 · 5; Ln = La (8), Pr (9),Nd (10), Sm (11), Er (12), Y (13)). Single-crystal X-ray structuredetermination of(10)·(thf)1 · 5,(11)·(thf)1 · 5 and(12)·(thf)1 · 5revealed formally 10-coordinate complexes with an O-bondedOPPh3, threeη5-C5H4PPh2ligands and lattice thf. The centroids of the C5 ringsand the oxygen atom surround the central metal in a distorted tetrahedralarray.

Synthesis, characterization and reactivity of trans-dihydroxy platinum(IV) porphyrins

2016 ◽  
Vol 20 (07) ◽  
pp. 785-792 ◽  
Author(s):  
Yingying Ning ◽  
Yi Yu ◽  
Yi-Wei Liu ◽  
Jing Zhang ◽  
Hao-Ling Sun ◽  
...  
Keyword(s):  
Oxygen Atom ◽  
Single Crystal ◽  
Crystal Structures ◽  
Oxidation State ◽  
Photoelectron Spectroscopy ◽  
Catalytic Reactions ◽  
X Ray ◽  
Single Crystal Structures

Synthesis of two trans-dihydroxy platinum(IV) porphyrins (TPP, tetraphenylporphyrin and F[Formula: see text]TPP, tetrakispentafluorophenylporphyrin) by dimethyl dioxirane (DMD) oxidation of their Pt[Formula: see text] porphyrin precursors have been described. The oxidation state of Pt cation in such complexes was assessed by X-ray photoelectron spectroscopy and shown to be [Formula: see text]4. More importantly, proton was found to promote the formation and stabilization of the trans-dihydroxy platinum(IV) porphyrins, as revealed by UV-vis spectroscopic results and single crystal structures. In addition, these trans-dihydroxy Pt[Formula: see text] porphyrins were much easier to be reduced than their Pt(II) counterparts and capable to transfer oxygen atom to triphenylphosphine and thioanisol, which is important for further application of Pt(IV) complexes in catalytic reactions.

Bis(allyl)ruthenium(iv)-initiated S - S and C - S Bond Cleavages in Tetraalkylthiuram Sulfides. Formation and X-ray Crystal Structures of Dithiocarbamato Complexes

2009 ◽  
Vol 62 (11) ◽  
pp. 1537 ◽  
Author(s):  
Chang Xu ◽  
Sumod A. Pullarkat ◽  
Lai Yoong Goh
Keyword(s):  
Crystal Structures ◽  
Quantitative Yield ◽  
Direct Reaction ◽  
X Ray ◽  
High Yields

The direct reaction of [{Ru(η3:η3-C10H16)(μ-Cl)Cl}2] (1) with tetraalkyldithiuram disulfides [R2NC(S)S-]2 (R = Me, iPr) and monosulfide [Me2NC(S)]2S led to the formation of orange solids of [Ru(η3:η3-C10H16)(η2-S2CNR2)Cl] (2a, R = Me; 2b, R =iPr) in high yields. Reaction of 1 with KPF6 and monosulfide [Me2NC(S)]2S resulted in [Ru(η3:η3-C10H16)(η2-S2CNMe2)(CH3CN)](PF6) (3). The treatment of 2a with KPF6 also yielded 3 in quantitative yield. Compounds 2–3 have been spectroscopically and crystallographically characterized.

Synthese und Kristallstrukturen der 1,3,4-λ5σ4-Diazaphosphole / Syntheses and Crystal Structures of the 1,3,4-λ5σ4-Diazaphospholes

1993 ◽  
Vol 48 (6) ◽  
pp. 730-736 ◽  
Author(s):  
Gudrun Stieglitz ◽  
Bernhard Neumüller ◽  
Kurt Dehnicke
Keyword(s):  
Nitrogen Atom ◽  
Oxygen Atom ◽  
Crystal Structures ◽  
Structure Determination ◽  
Lithium Atom ◽  
Ion Pair ◽  
Space Group ◽  
X Ray ◽  
Lithium Complex ◽  
Moisture Sensitive

has been prepared by the reaction of Li(DME)[P(t-Bu)2] with benzonitrile in 1,2-dimethoxyethan solution. The compound forms violet, moisture sensitive crystals, which were characterized by an X-ray structure determination [Space group P21/n, Z = 4, 3282 observed unique reflections, R = 0.082. Lattice dimensions at -40°C: a = 851.0(5), b = 1238.0(3), c = 3029.2(4) pm, β = 90.53(4)°]. The compound forms an ion pair, in which the lithium atom is coordinated by two oxygen atoms of a chelating DME molecule, by an oxygen atom of a nonchelating DME molecule, and by the nitrogen atom of the planar diazaphosphole ring in 1-position. The phenyl groups are nearly coplanar with the diazaphosphole ring. is the product of the reaction of the lithium complex with methanol. It forms colourless crystals [Space group Ρ21/n, Ζ = 4, 2015 observed unique reflections, R = 0.068. Lattice dimensions at -80°C: a = 1458.3(2), b = 824.8(1), c = 1716.9(2) pm, β = 105.37(9)°]. The molecules have planar 5 H-diazaphosphole rings.

Element–Element-Bindungen, IV. Molekül-und Kristallstruktur des Tetramethyldiphosphans und -diarsans /Element–Element Bonds, IV. Molecular and Crystal Structure of Tetramethyldiphosphane and -diarsane

1988 ◽  
Vol 43 (8) ◽  
pp. 952-958 ◽  
Author(s):  
Otto Mündt ◽  
Heinz Riffel ◽  
Gerd Becker ◽  
Arndt Simon
Keyword(s):  
Crystal Structure ◽  
Single Crystal ◽  
Crystal Structures ◽  
Molecular And Crystal Structure ◽  
X Ray Diffraction ◽  
X Ray ◽  
Linear Chains ◽  
Extended Interaction ◽  
Molecular And Crystal Structures

Abstract The molecular and crystal structures of the isotypic compounds tetramethyldiphosphane 1 and -diarsane 2 have been determined by single crystal X-ray diffraction (monoclinic; C2/m; Z = 2; 1/2: -155/-144 °C\a = 540.6(2)/555.8(2); b = 1131.0(6)/l 136.7(6); c -602.5(2)/612.8(2) pm;β = 97.31(3)/95.24(3)°;P-P 221.2(1)/As-As 242.9(1) pm). In accordance with the crystallographically imposed symmetry 2/m, the molecules adopt antiperiplanar conformation. Their crystal structures are closely related to those of the homologues tetramethyldistibane 3 [1] and -dibismuthane 4 [3]. As found for the latter compounds, the E -E units (E = P, As) are also aligned in linear chains, but the intermolecular E···E contacts (P···P 381/As···As 370 pm) do not allow any extended interaction between molecules, which otherwise would result in thermochromic effects.

Reaction between Yttrium Nitrate and 2,2':6',2"-Terpyridine (terpy) in MeCN: Preparation, Crystal Structures and Spectroscopic Characterization of [Y (NO3)3(terpy)(H2O )] and [Y(NO3)3(terpy)(H2O )] · terpy · 3 MeCN

2001 ◽  
Vol 56 (2) ◽  
pp. 122-128 ◽  
Author(s):  
Athanassios K. Boudalis ◽  
Vassilios Nastopoulos ◽  
Aris Terzis ◽  
Catherine P. Raptopoulou ◽  
Spyros P. Perlepes
Keyword(s):  
Oxygen Atom ◽  
Single Crystal ◽  
Crystal Structures ◽  
Spectroscopic Characterization ◽  
Yttrium Nitrate ◽  
X Ray ◽  
X Ray Crystallography ◽  
H Nmr ◽  
Tricapped Trigonal Prism

Abstract The reaction of Y(NO3)3 · 5H2O and 2,2':6',2"-terpyridine (terpy) in MeCN leads to [Y(N03 )3(terpy)(H2O )] (1) and [Y(N03 )3(terpy)(H2O )] terpy-3MeCN (2) in good yields depending on the isolation conditions. The structures of both complexes were determined by single-crystal X-ray crystallography. The YIII atom in 1 is 9-coordinate and ligation is provided by one terdentate terpy molecule, two chelating nitrates, one monodentate nitrate and one terminal H2O molecule; the coordination polyhedron about the metal may be viewed as a tricapped trigonal prism. The YIII atom in 2 is 10-coordinate and its coordination sphere consists of three nitrogen atoms from the terdentate terpy, six oxygen atoms from the three chelating nitrates (one of them being “anisobidentate”) and one oxygen atom from a terminal H2O molecule; the polyhedron about the metal may be viewed as a distorted sphenocorona. The interstitial terpy is strongly hydrogen-bonded to the O atom of the coordinated H2O molecule to form [Y(NO3 )3(terpy)(H20)] ··· terpy pairs. The new complexes were characterized by IR and 1H NMR spectroscopies. The YIII/NO3-/terpy chemistry is compared to the already well-developed LnIII/NO3-/terpy chemistry (Ln = lanthanide).

Synthesis of New Multiple Layered Dion-Jacobson Perovskites

2014 ◽  
Vol 1655 ◽  
Author(s):  
Léa Gustin ◽  
Jérôme Lefebvre ◽  
Clare Davis-Wheeler ◽  
Amy K. Pressley ◽  
John B. Wiley
Keyword(s):  
Solid State ◽  
Alkali Metals ◽  
Layered Compound ◽  
Direct Reaction ◽  
Exchange Reactions ◽  
Metal Chlorides ◽  
Ceramic Method ◽  
X Ray ◽  
New Compounds ◽  
Layered Perovskites

ABSTRACTNew multiple layered perovskites with general formula RbLaNaxNb2+xO7+3x, x = 1 and 2, were synthesized via a ceramic method. While the triple layered compound could be obtained by simple direct reaction, the quadruple layered one was synthesized using a two-step solid state approach. The compounds were characterized by X-ray powder diffraction; the newly obtained compounds appear to be isostructural with the previously reported RbCa2Nb3O10 and RbCa2NaNb4O13 for RbLaNaNb3O10 and RbLaNa2Nb4O13, respectively. Preliminary results show that the new compounds can undergo ion exchange reactions involving alkali metals and transition metal chlorides.

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