Alkoxide-functionalized cyclopentadienyl complexes of yttrium containing a two-carbon tether

2002 ◽  
Vol 80 (10) ◽  
pp. 1285-1292 ◽  
Author(s):  
Roland AL Gendron ◽  
David J Berg ◽  
Tosha Barclay
Keyword(s):  
Solid State ◽  
Key Words ◽  
Intramolecular Cyclization ◽  
Thermal Reaction ◽  
Chloride Complex ◽  
State Structure ◽  
Reduced Pressure ◽  
X Ray ◽  
X Ray Crystallography ◽  
Cyclopentadienyl Complexes

The ligand C5H4(CH2CH2CArF2OH) (3) (ArF = 3,5-C6H3(CF3)2) was prepared in two steps, from the iodo ester ICH2CH2CO2Me by way of the cyclopentadienyl ester C5H5CH2CH2CO2Me (2), in 55% overall yield. Thermal reaction of 3 with {Y[N(SiMe3)2]2(THF)2(µ-Cl)}2 afforded the neutral chloride complex {η5:η1-C5H4[CH2CH2C(O)(3,5-C6H3(CF3)2)2]}YCl{THF}n (5a: n = 2, 5b: n = 1). Metathesis reactions of 5 with 1 equiv of NaN(SiMe3)2, LiO-2,6-t-Bu2C6H3, and LiCH(SiMe3)2 afforded {η5:η1-C5H4[CH2CH2C(O)(3,5-C6H3(CF3)2)2]}Y{N(SiMe3)2}{THF}n (6), {η5:η1-C5H4[CH2CH2C(O)(3,5-C6H3(CF3)2)2]}Y{O-2,6-t-Bu2C6H3}{THF}n (7), and {η5:η1-C5H4[CH2CH2C(O)(3,5-C6H3(CF3)2)2]}Y{CH(SiMe3)2}{THF}n (8), respectively, (a: n = 2, b: n = 1). Exposure of the bis(THF) solvates to reduced pressure resulted in desolvation to the mono(THF) adducts for 5–8. The solid state structure of 6b was established by X-ray crystallography. In addition, formation of a spirocyclic ether (C4H6CH2CH2C(O)(3,5-C6H3(CF3)2)2 4), obtained by the intramolecular cyclization of ligand 3, was confirmed by X-ray crystallography. Key words: yttrium, organometallic, cyclopentadienyl, X-ray, alkoxide, chelate, alkyl, hybrid ligand, NMR, cyclization.

Synthesis and structural characterization of a magnesium phthalocyanine(3–) anion

2012 ◽  
Vol 16 (01) ◽  
pp. 154-162 ◽  
Author(s):  
Edwin W.Y. Wong ◽  
Daniel B. Leznoff
Keyword(s):  
Absorption Spectrum ◽  
Solid State ◽  
Single Crystal ◽  
Structural Characterization ◽  
Heterometallic Complex ◽  
State Structure ◽  
Solid State Structure ◽  
X Ray ◽  
X Ray Crystallography

The reduction of magnesium phthalocyanine (MgPc) with 2.2 equivalents of potassium graphite in 1,2-dimethoxyethane (DME) gives [K2(DME)4]PcMg(OH)(1) in 67% yield. Compound 1 was structurally characterized using single crystal X-ray crystallography and was found to be a monomeric, heterometallic complex consisting of a μ3-OH ligand that bridges a [MgIIPc3-]- anion to two potassium cations solvated by four DME molecules. An absorption spectrum of 1 confirms the Pc ligand is singly reduced and has a 3–charge. The solid-state structure of 1 does not indicate breaking of the aromaticity of the Pc ligand. Compound 1 is only the second Pc3- complex and the first reduced MgPc to be isolated and structurally characterized.

Synthesis and characterization of the binuclear diamido titanium chalcogenides [(Ar)NCH2CH2CH2N(Ar)]2Ti(µ-E)2 (E = Se, Te)

2002 ◽  
Vol 80 (11) ◽  
pp. 1524-1529 ◽  
Author(s):  
Tianle Zhang ◽  
Warren E Piers ◽  
Masood Parvez
Keyword(s):  
Solid State ◽  
Key Words ◽  
Synthesis And Characterization ◽  
Catalyst Precursor ◽  
Tellurium Atom ◽  
Titanium Complex ◽  
X Ray ◽  
X Ray Crystallography ◽  
Atom Source

Reaction of McConville's chelating amido titanium complex [(Ar)NCH2CH2CH2N(Ar)]Ti(CH3)2 (Ar = 2,6-i-Pr2C6H3) with either elemental Se or the tellurium atom source Te=PBu3 resulted in the formation of bis-µ-chalcogenido dimers [(Ar)NCH2CH2CH2N(Ar)]2Ti(µ-E)2 (E = Se, 2; Te, 3) with concommitant loss of EMe2. The dimers 2 and 3 were characterized spectroscopically and via X-ray crystallography. The two compounds are isostructural in the solid state. The tellurido dimer 3 may also be synthesized by reduction of the diamido dichloride [(Ar)NCH2CH2CH2N(Ar)]2TiCl2 with Na–Hg amalgam followed by treatment with Te=PBu3. This dimer is unreactive toward further Te=PBu3 or stannanes such as HSnBu3. Unlike decamethyltitanocene derivatives, the diamido complex is not an effective catalyst precursor for the heterohydrodecoupling of Te=PBu3 and HSnBu3.Key words: diamido titanium complexes, selenides, tellurides.

The two solid-state conformations of nefopam methiodide, a quaternary ammonium salt of the analgesic drug

1990 ◽  
Vol 68 (7) ◽  
pp. 1128-1134 ◽  
Author(s):  
Robert Glaser ◽  
André Michel ◽  
Marc Drouin
Keyword(s):  
Solid State ◽  
Ammonium Salt ◽  
Quaternary Ammonium ◽  
Quaternary Ammonium Salt ◽  
State Structure ◽  
X Ray Diffraction ◽  
Analgesic Drug ◽  
X Ray ◽  
Positional Disorder ◽  
X Ray Crystallography

The solid-state structure of nefopam methiodide, a quaternary ammonium salt of nefopam hydrochloride (a non-narcotic analgesic drug), has been determined by single crystal X-ray diffraction analysis. Nefopam methiodide gives crystals belonging to the monoclinic P21/c space group and, at 298 K, a = 10.001(1), b = 9.928(1), c = 17.598(1) Å, β = 94.41(1)°, V = 1742.2(2) Å3, Z = 4, R(F) = 0.086, and Rw(F) = 0.108. Due to disorder, the boat (flattened chair) and twist-chair (flattened chair) conformations of the 2,5-benzoxazocine eight-membered ring were both observed in the crystal with 55:45 occupancy, respectively. Positional disorder was also observed for the iodide counterion, which showed occupancies of 81:9.5:9.5. Keywords: nefopam, analgesic, X-ray crystallography, conformation.

Cyclic Alkyl(aryl)boranes for 1,1-Carboboration of Monoalkynyltin Compounds

2013 ◽  
Vol 68 (5-6) ◽  
pp. 493-502 ◽  
Author(s):  
Bernd Wrackmeyer ◽  
Peter Thoma ◽  
Wolfgang Milius
Keyword(s):  
Solid State ◽  
High Selectivity ◽  
Ring Expansion ◽  
Membered Ring ◽  
Reaction Products ◽  
State Structure ◽  
Alkyl Aryl ◽  
X Ray ◽  
X Ray Crystallography ◽  
Nmr Techniques

Two cyclic alkyl(aryl)boranes, a 1-bora-indane derivative 1, and a tricyclic derivative 4, containing the boron atom in a six-membered ring, were structurally characterized by NMR techniques in solution. The solid-state structure of the 1-bora-indane 1 was determined by X-ray crystallography. The reactivity of these cyclic alkyl(aryl)boranes towards monoalkynyltin compounds, Me3Sn-C≡C-Me and Me3Sn-C C-Fc (Fc=ferrocenyl), was studied using multinuclear magnetic resonance methods (1H, 11B, 13C, 119Sn NMR). Novel alkenylboranes were formed by 1,1-carboboration reactions. This process involves an expansion of both five- and six-membered rings. Insertion into the respective B-C(aryl) bond was preferred with high selectivity. In the case of the six-membered ring in 4, the ring expansion to seven-membered rings proved to be readily reversible, and the thermodynamically stable reaction products were formed by ring contraction and concomitant transfer of the exocyclic B-nPr group

Solid-state structure of NH-pyrazolium hydrochlorides and hydrobromides by X-ray crystallography and CPMAS NMR

1997 ◽  
Vol 415 (1-2) ◽  
pp. 81-92 ◽  
Author(s):  
Concepción Foces-Foces ◽  
Lourdes Infantes ◽  
Rosa Marı́a Claramunt ◽  
Concepción López ◽  
Nadine Jagerovic ◽  
...  
Keyword(s):  
Solid State ◽  
State Structure ◽  
Solid State Structure ◽  
X Ray ◽  
X Ray Crystallography

Self-Assembly of a Charge-Neutral Molecular Square

2004 ◽  
Vol 57 (5) ◽  
pp. 409 ◽  
Author(s):  
Mohammad Akbar Ali ◽  
Paul V. Bernhardt ◽  
Chong Lee Kiem ◽  
Aminul Huq Mirza
Keyword(s):  
Molecular Weight ◽  
Solid State ◽  
Self Assembly ◽  
1H Nmr Spectroscopy ◽  
The Self ◽  
State Structure ◽  
X Ray ◽  
X Ray Crystallography ◽  
A Charge ◽  
Molecular Square

Complexation of cadmium(II) by the ditopic (bis-tridentate) thiocarbazone ligand 1,5-bis(6-methyl-2-pyridyl- methylene)thiocarbonohydrazide, H2L1, results in the self-assembly of a charge-neutral 2 × 2 molecular grid, [Cd4(L1)4], comprising four metals and four ligands in an interlocked cyclic array. The solid-state structure of this tetramer has been established by X-ray crystallography and in solution by 1H NMR spectroscopy. The presence of lower molecular weight oligomers was identified by both NMR and ESI-MS.

Vanadium and niobium diamidophosphine complexes and their reactivity

2003 ◽  
Vol 81 (12) ◽  
pp. 1431-1437 ◽  
Author(s):  
Michael P Shaver ◽  
Robert K Thomson ◽  
Brian O Patrick ◽  
Michael D Fryzuk
Keyword(s):  
Coordination Chemistry ◽  
Solid State ◽  
Molecular Nitrogen ◽  
Tridentate Ligand ◽  
State Structure ◽  
Butyl Lithium ◽  
Solid State Structure ◽  
X Ray ◽  
X Ray Crystallography ◽  
Unstable Complex

The tridentate ligand precursors R′P(CH2SiMe2NR′′)2 (R′R′′[NPN]: R′ = Cy, Ph; R′′ = Ph, Mes, Me) were prepared from metathesis reactions of a lithiated amine, chloro(chloromethyl)dimethylsilane, the appropriate 1° phosphine, and n-butyl lithium and were isolated as solvent adducts. Metathesis between CyPh[NPN]Li2(OEt2), 2, and VCl3(THF)3 afforded (CyPh[NPN]VCl)2, 7, whose solid-state structure was established by X-ray crystallography. Reduction attempts of the (R′R′′[NPN]VCl)2 species with KC8 incorporated molecular nitrogen but were complicated by imide formation and ligand decomposition. Metathesis of 2 with NbCl2Me3 afforded the highly unstable complex CyPh[NPN]NbMe3, 15. Attempts to hydrogenate this species were unsuccessful.Key words: vanadium, niobium, metathesis, coordination chemistry, reduction, hydrogenation.

Structural diversity in thallium chemistry: structures of four chlorothallate(III) salts including a novel compound containing three geometrically different anions

1996 ◽  
Vol 74 (8) ◽  
pp. 1490-1502 ◽  
Author(s):  
Margaret Ann James ◽  
Jason A.C. Clyburne ◽  
Anthony Linden ◽  
Bruce D. James ◽  
John Liesegang ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
Solid State ◽  
Structural Diversity ◽  
State Structure ◽  
X Ray ◽  
Coordination Numbers ◽  
X Ray Crystallography ◽  
Hydrogen Bonding Networks ◽  
Alkyl Ammonium ◽  
High Coordination

Four new thallium-containing salts with different alkyl ammonium cations have been prepared and characterized by X-ray crystallography: 1: bis(p-toluidinium) pentachlorothallate(III), [CH3C6H4NH3]2 [TlCl5], M = 597.9, monoclinic, P21/c, a = 7.515(2), b = 21.376(6), c = 12.769(2) Å, β = 92.13(2)°, V = 2050(1) Å3, Z = 4, Dcalc = 1.937 Mg m−3, µ = 8.512 mm−1, T = 293(1) K, R = 0.046; 2: 1,5-pentanediammonium pentachlorothallate(III), [NH3(CH2)5NH3] [TlCl5], M = 485.83, orthorhombic, P212121, a = 13.226(2), b = 13.595(2), c = 7.628(2) Å, V = 1371.6(3) Å3, Z = 4, Dcalc = 2.352 Mg m−3, µ = 12.84 mm−1, T = 173(1) K, R = 0.025; 3: pentakis(2-adamantaneammoniumn) bistetrachlorothallate(III) hexachlorothallate(III), [C10H18N]5 [TlCl4]2[TlCl6], M = 1870.75, monoclinic, P21a = 16.466(5), b = 25.985(2), c = 7.724(3) Å, β = 90.14(3)°, V = 3305(2) Å3, Z = 2, Dcalc = 1.880 Mg m−3, µ = 7.978 mm−1, T = 173(1) K, R = 0.056; 4: bis(piperazinium) decachlorodithallate(III) trihydrate, [NH2C4H8NH2]2 [Tl2Cl10]•3H2O, M = 993.62, monoclinic, C2/c, a = 14.154(3), b = 15.445(3), c = 13.228(3) Å, β = 114.44(1)°, V = 2632.7(9) Å3, Z = 4, Dcalc = 2.506 Mg m−3, µ = 13.39 mm−1, T = 173(1) K, R = 0.026. For most of the salts examined, formation of [TlCl5]2− is possible; however, no isolated [TlCl5]2− anions were observed. In most cases, high coordination numbers at thallium were observed (CN = 6), and these can be achieved via formation of anionic chains or through dimerization, giving [Tl2Cl10]4−. Of particular interest is the solid state structure of salt 3 in which there are three geometrically different chlorothallate ions. Extensive hydrogen-bonding networks are observed in each structure. Key words: thallium, thallium(III) chlorides, chlorothallate, hydrogen bonding, alkyl ammonium cations.

Synthesis, characterization, and reactivity of the first hafnium alkyl complex stabilized by amidate ligands

2005 ◽  
Vol 83 (6-7) ◽  
pp. 1037-1042 ◽  
Author(s):  
Robert K Thomson ◽  
Brian O Patrick ◽  
Laurel L Schafer
Keyword(s):  
Coordination Chemistry ◽  
Solid State ◽  
Key Words ◽  
Low Temperatures ◽  
Variable Temperature ◽  
X Ray ◽  
X Ray Crystallography ◽  
Exchange Processes ◽  
Hydrolysis Of

A photo and thermally stable bis(amidate)–dibenzyl complex of Hf ([DMP(NO)Ph]2Hf(CH2Ph)2(THF) (2a) was formed as a monosolvated THF adduct in near quantitative yield from Hf(CH2Ph)4 and N-2,6-dimethylphenyl(phenyl)amide (1). Isomerization between the THF-bound product and the THF-free product can be observed visually by the conversion from a red-orange product at low temperatures to a pale yellow product at high temperatures. Solid-state crystallographic characterization of the orange product confirmed its constitution as a monosolvated species. Kinetic parameters for the exchange of the THF moiety were determined from variable-temperature NMR experiments. The product of the hydrolysis of the Hf dibenzyl species by water was characterized by X-ray crystallography, and was found to be a rare tetrametallic Hf oxo cluster species (3).Key words: hafnium, protonolysis, amidate, coordination chemistry, organometallic chemistry, exchange processes.

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