Crystal Structures of Unusual Titanocene By-products from Attempted Dimerization of Terminal Alkynes

2000 ◽  
Vol 65 (8) ◽  
pp. 1248-1261 ◽  
Author(s):  
Róbert Gyepes ◽  
Ivana Císařová ◽  
Michal Horáček ◽  
Jiří Čejka ◽  
Lidmila Petrusová ◽  
...  
Keyword(s):  
Diffraction Analysis ◽  
Crystal Structures ◽  
Terminal Alkynes ◽  
X Ray Diffraction ◽  
X Ray ◽  
By Products

Structures of unusual organometallic products μ-[(1,2,3,3a,7a-η):(3a,4,5,6,7,7a-η)-4,7- bis(trimethylsilyl)indenyl]-di-μ-hydridobis(η5-cyclopentadienyl)titanium(TiIII/TiII) (9) and μ-[(3,4,5-η):(4,5,6-η)-(E,E)-2,2,7,7-tetramethylocta-3,5-diene}bis{bis(η5-methylcyclopentadienyl)titanium} (10a) were determined by X-ray diffraction analysis. Compounds 9 and 10a arose as by-products in very low yields in the Ti(C5H5)2(η2-Me3SiC≡CSiMe3)-HC≡CSiMe3 and Ti(C5H4Me)2(η2-Me3SiC≡CSiMe3)-HC≡CCMe3 systems, respectively, when exposed to sunlight. Mechanisms of their formation were tentatively discussed.

New Cu(II), Co(II), and Ni(II) complexes with thieno[2,3-b]pyridine and 2-methylthieno[2,3-b]pyridine as ligands: Synthesis and crystal structures

2009 ◽  
Vol 63 (3) ◽  
Author(s):  
Ján Halgaš ◽  
Viera Kolenová ◽  
Zuzana Števíková ◽  
Lucia Perašínová ◽  
Jozef Kožíšek
Keyword(s):  
Single Crystal ◽  
Diffraction Analysis ◽  
Crystal Structures ◽  
Elemental Analysis ◽  
Zinc Chloride ◽  
Coordination Compounds ◽  
Biological Activities ◽  
X Ray Diffraction ◽  
X Ray ◽  
Ft Ir

AbstractAlthough thienopyridines attract attention because of their biological activities, they have not been used as ligands in coordination compounds. Thieno[2,3-b]pyridine was prepared by known procedures; by reduction of 2-nitrothiophene, and reaction of the resulting 2-thienyl ammonium salt with malondialdehyde tetramethylacetal in the presence of zinc chloride. The same procedure was used for the preparation of a new derivative, 2-methylthieno[2,3-b]pyridine, starting from 2-methyl-5-nitrothiophene. The thienopyridines were used in the synthesis of coordination compounds. Chlorides, isothiocyanates, acetates, and chloroacetates of copper(II), nickel(II), or cobalt(II) were used as starting salts. The prepared complexes were characterized by elemental analysis and FT IR. Structures of the four complexes were determined by single-crystal X-ray diffraction analysis.

Synthesis and Crystal Structures of New 1,3-Disubstituted Imidazoline-2-thiones

2013 ◽  
Vol 68 (11) ◽  
pp. 1239-1252 ◽  
Author(s):  
Gerhard Laus ◽  
Volker Kahlenberg ◽  
Klaus Wurst ◽  
Thomas Müller ◽  
Holger Kopacka ◽  
...  
Keyword(s):  
Bond Length ◽  
Crystal Structures ◽  
1H Nmr ◽  
Significant Contribution ◽  
Resonance Structure ◽  
X Ray Diffraction ◽  
Reference Compound ◽  
X Ray ◽  
Hydrolysis Of ◽  
By Products

Two methods (MeOH/K2CO3, pyridine/Et3N) were assessed for the introduction of sulfur into the 2-position of 1,3-disubstituted quaternary imidazolium salts 1-9 (Cl, I, BF4, PF6, CH3OSO3 were used as anions) to yield nine 1,3-disubstituted imidazoline-2-thiones 10-18 (1, 10: R1 = CH3, R2 = CH3; 2, 11: R1 = OCH2Ph, R2 = CH3; 3, 12: R1 = OCH3, R2 = CH3; 4, 13: R1 = OCH3, R2 = OCH3; 5, 14: R1 = NH2, R2 = CH2Ph; 6, 15: R1 = NCHPh, R2 = CH3; 7, 16: R1 = NH2, R2 = CH3; 8, 17: R1 = NCHPh, R2 = NCHPh; 9, 18: R1 = NH2, R2 = OCH3). Compounds 11-18 represent N-alkyloxy and N-amino imidazoline-2-thiones, whereas 10 served as reference compound. The first method was advantageous for the conversion 1 → 10 due to faster reaction, whereas in the reaction 2 → 11 considerable amounts of by-products were formed. Pure thiones 11, 14, 16, 17, and 18 were obtained only by the second method. Both methods worked for the synthesis of the methoxy derivatives 12 and 13 from 3 and 4, and the benzylideneamino derivative 15 from 6. 1-Amino-3- methylimidazoline-2-thione (16) was also prepared by hydrolysis of the benzylideneamino derivative 15. Crystal structures of seven 1,3-disubstituted imidazoline-2-thiones were determined by singlecrystal X-ray diffraction. Intermolecular C-H···S contacts were identified and, additionally, N-H···S interactions in aminothiones 14 and 16. The 1H NMR shifts of 10 and 13 were satisfactorily correlated with the Kamlet-Abboud-Taft π* and b parameters in ten solvents. From the lack of correlation with the a parameter and from the C=S bond length (average 1.68 Å ) a significant contribution of a mesoionic imidazolium-2-thiolate resonance structure seems unlikely.

scholarly journals Chloroantimonate(III), IV. Darstellung und Kristallstruktur von 2,2′-Bipyridinium-pentachloroantimonat (C10H8N2H2)SbCl5 und der metastabilen Modifikation von 4,4′ -Bipyridinium-pentachloroantimonat (C10H8N2H2)SbCl5 / Chloroantimonates(III), IV. Preparation and Crystal Structures of 2,2′-Bipyridinium Pentachloroantimonate (C10H8N2H2)SbCl5 and of the Metastable Modification of 4,4′-Bipyridinium Pentachloroantimonate (C10H8N2H2)SbCl5

1983 ◽  
Vol 38 (12) ◽  
pp. 1615-1621 ◽  
Author(s):  
Annegret Lipka
Keyword(s):  
Single Crystal ◽  
Diffraction Analysis ◽  
Crystal Structures ◽  
Bond Order ◽  
X Ray Diffraction ◽  
X Ray ◽  
Bond Lengths ◽  
Distorted Octahedral ◽  
Intermolecular Contacts

2,2′-Bipyridinium pentachloroantimonate (III) and the metastable modification of 4,4′-bipyridinium pentachloroantimonate(III) were synthezised and investigated by single crystal X-ray diffraction analysis. The structures consist of 2,2′-bipyridinium and 4,4′-bipyridinium cations, respectively, and of pentachloroantimonate anions. With regard to bonding and short intermolecular contacts the coordination of the Sb atoms is distorted octahedral in both structures. Bond lengths of equivalent Sb-Cl bonds differ strongly within the structure of the 2,2′-bipyridinium salt (239.9 pm to 312.1 pm) and are not distinguishable from short intermolecular contacts (305.4 pm and 321.8 pm). In the structure of the 4,4′-bipyridinium salt, bond distances vary only from 240.9 pm to 267.8 pm and are clearly below intermolecular contacts at 318.2 pm. In spite of the different distances the total bond order for each Sb atom is 3. In the structure of the 2,2′-bipyridinium salt the anions build tetramers, whereas in the structure of the 4,4′-bipyridinium salt the anions form chains

Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalyse von cis-(n-Bu4N)2[ReBr4(NCS)2 ], cis-(n-Bu4N)2[ReBr4(NCSe)2] und cis-(n-Bu4N)2[ReBr4(NCS)(NCSe)] / Crystal Structures, Vibrational Spectra and Normal Coordinate Analyses of cis-(n-Bu4N)2[ReBr4(NCS)2], cis-(n-Bu4N)2[ReBr4(NCSe)2,] and cis -(n -Bu4N)2[ReBr4(NCS)(NCSe)]

2000 ◽  
Vol 55 (2) ◽  
pp. 178-184 ◽  
Author(s):  
L. Homolya ◽  
W. Preetz
Keyword(s):  
Low Temperature ◽  
Diffraction Analysis ◽  
Crystal Structures ◽  
Vibrational Spectra ◽  
X Ray Diffraction ◽  
Normal Coordinate ◽  
Triclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Ir And Raman

The crystal structures of cis-(n-Bu4N)2[ReBr4(NCS)2] (1) (triclinic, space group P1̄, a = 11.475(6), b = 20.096(16), c = 22.144(11) Å, α = 110.56(6), β = 92.97(5), γ = 99.77(7)°, Z = 4), cis-(n-Bu4N)2[ReBr4(NCS)2] (2) (triclinic, space group P1̄, a = 11.527(3), b = 20.237(7), c = 22.07(2) Å, α = 110.05(4), β = 93.86(6), γ = 99.49(4)°, Z = 4) and cis-{n- Bu4N)2[ReBr4(NCS)(NCSe)] (3) (triclinic, space group P1̄, a = 11.488(2), b = 20.164(6), c = 22.158(5) Å, α = 110.44(2), β = 93.34(2), γ = 99.626(18)°. Z = 4) have been determined by single crystal X-ray diffraction analysis. Based on these molecular parameters the low temperature (10 K) IR and Raman spectra of the (n-Bu4N) salts have been assigned by normal coordinate analysis. The valence force constants are fd(ReN) = 1.70 (1), 1.70 (2) and 1.72 (3), fd(ReBr) = 1.36 (1), 1.30 (2) and 1.36 mdyn/Å (3).

B(C6F5)3-guided cyclotrimerization-rearrangement of phenylacetylene. Evidence of the (C6F5)3B−–C(H)=C+Ph intermediate in a 1,1-carboboration reaction

2016 ◽  
Vol 71 (10) ◽  
pp. 1029-1041
Author(s):  
Wanli Nie ◽  
Guofeng Sun ◽  
Chong Tian ◽  
Maxim V. Borzov
Keyword(s):  
Nmr Spectroscopy ◽  
Diffraction Analysis ◽  
Crystal Structures ◽  
Variable Temperature ◽  
Spectroscopy Study ◽  
X Ray Diffraction ◽  
X Ray ◽  
Spectral Evidence ◽  
A Minor ◽  
Zwitterionic Intermediate

AbstractIn presence of 2,2,6,6-tetramethylpiperidinium ([TMPH]+) chlorotris(pentafluorophenyl)borate ([TMPH]+[ClB(C6F5)3]−, 3), phenylacetylene undergoes an unusual cyclotrimerization-rearrangement leading to tris(pentafluorophenyl)(3,4,5-triphenylphenyl)borate anion (1) as a minor product which can be isolated and purified in a form of salts [1·(TMPH)n·Cl(n–1)] (n=3 or 5). A variable temperature and concentration NMR spectroscopy study of 3 in CDCl3 unambiguously demonstrated its ability to liberate free B(C6F5)3, which initiates cyclotrimerization and guides rearrangements towards formation of the tetraarylborate anion 1. For the previously studied “spectator” reaction between phenylacetylene and B(C6F5)3 in CDCl3, 1H, 19F, and 11B NMR-spectral evidence of the (C6F5)3B−–C(H)=C+Ph zwitterionic intermediate of the 1,1-carboboration reaction has been demonstrated. The crystal structures of [1·(TMPH)3·Cl2], the salt 3, and a 1:1 adduct of 1,3,5-tris(4-fluorophenyl)benzene and 2,4,6-tris(pentafluorophenyl)-1,3,5,2,4,6-trioxatriborinane (2) have been established by X-ray diffraction analysis.

Formation and Crystal Structures of 9-Methylanthracene Photodimer and Lepidopterene

2003 ◽  
Vol 2003 (7) ◽  
pp. 445-447
Author(s):  
Qing-Xiang Liu ◽  
Hai-Bin Song ◽  
Feng-Bo Xu ◽  
Qing-Shan Li ◽  
Xian-Shun Zeng ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Single Crystal ◽  
Diffraction Analysis ◽  
Crystal Structures ◽  
Single Crystal Structure ◽  
X Ray Diffraction ◽  
X Ray

The 9-methylanthracene photodimer (6) and lepidopterene (7) were prepared by a photo-dimerisation reaction of 1-(9-anthracenylmethyl)-3-ethylimidazolium iodide (1) or α, α'-di[1-(9-anthracenylmethyl) imidazolium]- p-xylene dibromide (2). Compound 6 is derived from the head-tail [4+4] cycloaddition of two molecular 9-methylanthracenes, and the butterfly-shaped compound 7 is formed via the 9-methyleneanthracene radical in a two steps precess. The single crystal structure of 6 was determined by X-ray diffraction analysis. The changes of luminescent intensities of compounds 1, 2 and 7 are reported.

Ethene-1,1,2,2-tetracarbonitrile and Methanol in the Methylating Reaction of Tertiary Amines to the Quaternary Ammonium Compounds of 1,1-Dicyano-2-methoxy-2-oxoethane-1-ide

Synlett ◽  
2018 ◽  
Vol 30 (02) ◽  
pp. 173-177
Author(s):  
Vladimir Р. Sheverdov ◽  
Vera Davydova ◽  
Oleg Nasakin ◽  
Maksim Mar’yasov ◽  
Olga Lodochnikova
Keyword(s):  
Diffraction Analysis ◽  
Crystal Structures ◽  
Quaternary Ammonium ◽  
Room Temperature ◽  
Quaternary Ammonium Compounds ◽  
Tertiary Amines ◽  
X Ray Diffraction ◽  
X Ray ◽  
Methanol Solutions ◽  
Ammonium Compounds

We discovered a new method to methylate tertiary amines such as urotropine, triethylamine, pyridine, 2-methylpyridine, 4-acetylpyridine, and isonicotinamide, up to quaternary ammonium compounds, with 1,1-dicyano-2-methoxy-2-oxoethane-1-ide being the counterion. Methyl-1,3,5,7-tetraazaadamantan-1-ium 1,1-dicyano-2-methoxy-2-oxoethane-1-ide, N,N-diethyl-N-methylethanaminium 1,1-dicyano-2-methoxy-2-oxoethane-1-ide, and substituted-methylpyridinium 1,1-dicyano-2-methoxy-2-oxoethane-1-ides were synthesized. Quaternary ammonium compounds of 1,1-dicyano-2-methoxy-2-oxothane-1-ide were synthesized within a single stage by stirring methanol solutions of tertiary amines with ethene-1,1,2,2-tetracarbonitrile (ETCN) at room temperature. In the reaction of ETCN with tertiary amines in methanol, processes occur that form the 1,1-dicyano-2-methoxy-2-oxoethane-1-ide fragment with simultaneous N-methylation. Crystal structures based on X-ray diffraction analysis of the obtained compounds were studied.

Darstellung, 11B-, 13C-NMR-und Schwingungsspektren von Aminom ethylhexahydro-closo-hexaborat(1-), [B6H6(CH2NH2)]- sowie Kristallstrukturen von Cs[B6H6(CH2NH2)] und K[B6H6(CH2NH2)] / Preparation, 11B, 13C NMR and Vibrational Spectra of Aminomethylhexahydro-closo-hexaborate(1-), [B6H6(CH2NH2)]-, and Crystal Structures of Cs[B6H6(CH2NH2)] and K[B6H6(CH2NH2)]

1994 ◽  
Vol 49 (9) ◽  
pp. 1267-1271 ◽  
Author(s):  
A. Franken ◽  
W. Preetz
Keyword(s):  
Single Crystal ◽  
Diffraction Analysis ◽  
Crystal Structures ◽  
13C Nmr ◽  
Vibrational Spectra ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Nmr Spectrum ◽  
X Ray ◽  
C Nmr

By reaction of [B6H6]2- with N-(chloromethyl)phthalimide in dichloromethane the intermediate phthalimidomethylhexahydro-closo-hexaborate(1-), [B6H6(CH2(NC8O2H4)]-, is formed which with an excess of hydrazine reacts to give am inomethylhexahydro-closo-hexaborate(1-). The crystal structures of Cs[Bf,H6(CH2NH2)] and K[B6H6(CH2NH2)] have been determined by single crystal X -ray diffraction analysis. They are monoclinic, space group C2/m with a = 11.123(6), b = 6.8441(11), c = 12.810(7) Å, β = 124.032(5)° for Cs[B6H6(CH2NH2)] and with a = 10.767(2), b = 6.6255(6), c = 12.2648(14) Å, β = 123.880(10")° for K [B6H6(CH2NH2)]. The 11B NMR spectrum is consistent with a monohetero substituted octahedral B6 cage with local C4v symmetry. In the 13C NMR spectrum of Cs[B6H6(CH2NH2)] a quartet at 32.7 ppm with 1J(C,B) 65 Hz is observed. The IR and Ram an spectra exhibit characteristic CH, NH, BH and B6 vibrations

Synthesis and Crystal Structures of Dinuclear Trichloro(tetramethylcyclopentadienyl)titanium Complexes

2006 ◽  
Vol 71 (2) ◽  
pp. 164-178 ◽  
Author(s):  
Lenka Lukešová ◽  
Róbert Gyepes ◽  
Vojtech Varga ◽  
Jiří Pinkas ◽  
Michal Horáček ◽  
...  
Keyword(s):  
Diffraction Analysis ◽  
Crystal Structures ◽  
X Ray Diffraction ◽  
Titanium Complexes ◽  
Sandwich Complexes ◽  
Common Procedure ◽  
X Ray ◽  
Half Sandwich

Dinuclear half-sandwich complexes [{TiCl3(η5-C5Me4)}2SiMe2] (2) and [{TiCl3(η5-C5Me4SiMe2CH2)}2] (4) were prepared by synproportionation of ansa-titanocene dichlorides [TiCl2{(η5-C5Me4)2SiMe2}] (1) and [TiCl2(η5-C5Me4SiMe2CH2)2] (3), respectively, with TiCl4. Compound 3 was synthesized from 1,2-bis(chlorodimethylsilyl)ethane, 1,2,3,4-tetramethylcyclopentadienyllithium, and [TiCl3(thf)3] by a common procedure. Crystal structures of 2, 3, and 4 were determined by X-ray diffraction analysis.

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