Selektive Additionsreaktionen an bifunktionalen neutralen Phosphenium-Ion-Komplexen / Selective Addition Reactions of Bifunctional Neutral Phosphenium Ion Complexes

1991 ◽  
Vol 46 (12) ◽  
pp. 1650-1658 ◽  
Author(s):  
Heinrich Lang ◽  
Michael Leise ◽  
Wolfgang Imhof
Keyword(s):  
Triple Bond ◽  
Spectroscopic Data ◽  
Multiple Bond ◽  
Addition Reactions ◽  
X Ray ◽  
Higher Temperature ◽  
New Compounds ◽  
Selective Addition ◽  
C Nmr ◽  
Membered Heterocyclic Compound

The reaction of bifunctional neutral phosphenium ion complexes, containing a carbon-carbon triple bond next to a phosphorus-molybdenum multiple bond, with carbenes and to carbene isolobal organometallic fragments is discussed.So, the reaction of (R)(PhC=C)P=MoCp′(CO), (R = 2,4,6-′Bu3C6H2O; Cp′ = η5-C5H5: la; Cp′ = η5-C5Me5: 1b) with CH2,Ν2 (2) yields the three membered heterocyclic compound (3). 3 reacts with Co2(CO)8 to afford complex (5) in which the phenylethynyl building block is η2-side-on coordinated to a Co2(CO)6 fragment. Similar to the reaction of 1 with 2, 1 forms with Fe2(CO)9 (6), compound (7). In 7 the PMo double bond is coordinated in a η2 fashion to the 16-electron organometallic fragment Fe(CO)4. Using an excess of 6 and a higher temperature, the phosphorus-alkynyl-carbon σ-bond is cleaved, and cluster MoCp*Fe3(CO)8η3-PR)(C≡CPh) (8) is formed.The reaction of 1 with Cr(CO)5(THF) yields 10, a complex, in which the PhC≡C ligand is η2-coordinated to Cp′(CO)2Mo, and the Cr(CO)5 group forms a dative bond with the phosphorus atom.All new compounds have been characterized by analytical as well as by spectroscopic data (IR, 1H, 31P, 13C NMR, MS), compound 10 by an X-ray analysis.

Synthese, Struktur und Reaktivität von 2-Amino- und 2-Imino-2,3-dihydro-1H-1,3,2-diazaborolen / Synthesis, Structure and Reactivity of 2-Amino- and 2-Imino-2,3-dihydro-1H-1,3,2-diazaboroles

1999 ◽  
Vol 54 (3) ◽  
pp. 363-371 ◽  
Author(s):  
Lothar Weber ◽  
Eckhard Dobbert ◽  
Andreas Rausch ◽  
Hans-Georg Stammler ◽  
Beate Neumann
Keyword(s):  
Diffraction Analysis ◽  
Spectroscopic Data ◽  
Ethylene Diamine ◽  
Gaseous Ammonia ◽  
X Ray Diffraction ◽  
X Ray ◽  
Elemental Analyses ◽  
New Compounds ◽  
C Nmr

The 2-halo-2,3-dihydro-1H-1,3,2-diazaboroles (1a′: R = tBu, X = Br; 1b: R = 2,6-Me2C6H3; X = I) were converted into the 2-amino-2,3-dihydro-1H-1,3,2- diazaboroles (2a: R = tBu; 2b: 2,6-Me2C6H3) by treatment with dry gaseous ammonia. Similarly reaction of 1a′ with 2,6-dimethylaniline or tBuNH2 afforded the corresponding derivates (3; R1 = 2,6-Me2C6H3; 4; R1 = tBu). The treatment of 1a′ with the ethylene diamine adduct of lithium acetylide led to the formation of (5). Lithiation of 2 a and subsequent silylation gave 6 (R1 = SiMe3), which was transformed to the diborolylamine (7) upon exposure to 1a′. Borolylketimine (8 ) and borolylcarbodiimide (9) resulted from 1a′ and Ph2C=NSiMe3 or Me3SiN=C=NSiMe3, respectively. All the new compounds were characterized by elemental analyses as well as spectroscopic data (IR, 1H, 11B, 13C NMR, MS). Heterocycle 5 was also subjected to an X-ray diffraction analysis.

Zur Umsetzung von Tri(phenylethinyl)arsan und -stiban mit Octacarbonyldicobalt; Kristallstruktur von (Ph– C≡ C)As[(η2-C≡ C – Ph)Co2(CO)6]2 / Reaction of Tri(phenylethynyl)arsane and -stibane with Octacarbonyldicobalt; Crystal Structure of (Ph–C≡C)As[η2-C≡C–Ph)Co2(CO)6]2

1990 ◽  
Vol 45 (11) ◽  
pp. 1529-1536 ◽  
Author(s):  
Heinrich Lang ◽  
Laszlo Zsolnai
Keyword(s):  
Crystal Structure ◽  
Spectroscopic Data ◽  
X Ray ◽  
Sterically Hindered ◽  
New Compounds ◽  
C Nmr

The synthesis of tri(phenylethynyl)arsane (1) and -stibane (7) is discussed. Octacarbonyldicobalt reacts selectively with 1 or 7 to yield the η2-side-on co-ordinated phenylethynyl complexes (Ph–C=C)nE[(η2-C≡C–Ph)Co2(CO)6]3-n (E = As: n = 2: 3, n = 1: 4, n = 0: 5; E = Sb: n = 2: 8; n = 1: 9; n = 0: 10), which contain sterically hindered carbon-cobalt tetrahedrane cluster units. 3 gives upon heating {(Ph–C≡C)2As[(η2-C=C–Ph)Co2(CO)5]}2 (6) a compound containing a six-membered Co2As2C2 ring.All new compounds have been characterized by analytical and spectroscopic data (IR, 1H, 13C NMR), and (Ph –C≡C)As[(η2-C≡C–Ph)Co2(CO)6]2 (4) by X-ray analysis.

Synthese und Kristallstrukturen einiger Tetramethylstibonium-Hydrogendicarboxylate / Synthesis and Crystal Structures of Some Tetramethylstibonium Hydrogendicarboxylates

1982 ◽  
Vol 37 (11) ◽  
pp. 1393-1401 ◽  
Author(s):  
Beatrix Milewski-Mahrla ◽  
Hubert Schmidbaur
Keyword(s):  
Hydrogen Bonds ◽  
Crystal Structures ◽  
Spectroscopic Data ◽  
Molar Ratio ◽  
Ionic Structure ◽  
X Ray Diffraction ◽  
X Ray ◽  
Carboxylate Oxygen ◽  
Donor Acceptor ◽  
New Compounds

Reactions of pentamethylantimony (CH3)5Sb with carboxylic acids in the molar ratio 1:2 afford one equivalent of methane and essentially quantitative yields of crystalline tetramothylstibonium hydrogendicarboxylates. Six new compounds of this series have been synthesized using benzoic, o-phthalic, salicylic, 4-ethoxy-salicylic, oxalic, and malic acid, and characterized by analytical and spectroscopic data. An ionic structure with strong hydrogen bonds in the anionic components is proposed.The crystal structures of the hydrogen-dibenzoato (1), hydrogen-ortho-plithalato (2) and 4-ethoxy-hydrogen-salicylate (3) were determined by single crystal X-ray diffraction. The compounds can be described as having ionic lattices with some donor-acceptor inter­actions between the stibonium centers and the carboxylate oxygen atoms. The anions are characterized by strong hydrogen bonds O...H...O. Thus, the (CH3)4Sb-tetrahedron in 1 is distorted by two benzoate oxygon atoms (at 304(2) and 340(2) pin). The cation in 2 is largely undistorted and the anion has a hydrogenphthalate hydrogen bond of d(O...H...O) = 232 pm. The cation-anion contact in 3 is as short as d(Sb-O) = 289 pm rendering the Sb atom pentacoordinate.

Bis[dicarbonyl(cyclopentadienyl)ruthenium(I)] Komplexe / Bis[dicarbonyl(cyclopentadienyl)ruthenium(I)] Complexes

2002 ◽  
Vol 57 (9) ◽  
pp. 1017-1026 ◽  
Author(s):  
Herbert Schumann ◽  
Susanne Stenz ◽  
Frank Girgsdies ◽  
Stefan H. Mühle
Keyword(s):  
Single Crystal ◽  
Nmr Spectra ◽  
X Ray ◽  
Tert Butyl ◽  
New Compounds ◽  
C Nmr

Ru3(CO)12 reacts with 1-tert-butyl-2,4-cyclopentadiene (1), 1-trimethylsilyl-2,4-cyclopentadiene (2), 1-tert-butyl-3-methyl-2,4-cyclopentadiene (3), 1,3-di(tert-butyl)-2,4-cyclopentadiene (4), 1-iso-propyl-2,3,4,5-tetramethyl-2,4-cyclopentadiene (5), 1-tert-butyl-2,3,4,5-tetramethyl- 2,4-cyclopentadiene (6), 1-phenyl-2,3,4,5-tetramethyl-2,4-cyclopentadiene (7), 2,5- diphenyl-2,4-cyclopentadiene (8), or 2,3,4,5-tetraphenyl-2,4-cyclopentadiene (9) with formation of the corresponding bis[dicarbonyl(cyclopentadienyl) ruthenium(I)] complexes [RuCp# (CO)2]2 1a to 9a. The 1H and 13C NMR spectra of the new compounds 3a and 5a to 9a as well as the single crystal X-ray structures of 1a, 4a, 5a, 7a, 8a, and 9a are reported and discussed

A New Bis-Tröger's Base: Synthesis, Spectroscopy, Crystal Structure and Isomerization

2006 ◽  
Vol 71 (9) ◽  
pp. 1278-1302 ◽  
Author(s):  
Martin Valík ◽  
Pavel Matějka ◽  
Eberhardt Herdtweck ◽  
Vladimír Král ◽  
Bohumil Dolensky
Keyword(s):  
Crystal Structure ◽  
Spectroscopic Data ◽  
The Other ◽  
X Ray Diffraction ◽  
One Pot ◽  
Molecular Tweezers ◽  
X Ray ◽  
Troger's Base ◽  
Ir And Raman ◽  
C Nmr

A new bis-Tröger's base was prepared from a tetraamine precursor as a mixture of two diastereoisomers. One of the isomers has a chair-like geometry, and the other possesses a boat-like geometry, embodying molecular tweezers. A one-pot preparation of bis-TB isomers and their interconversion under acid conditions was also studied. Structures of both isomers were confirmed by single-crystal X-ray diffraction. Extensive spectroscopic data, including 1H and 13C NMR, IR and Raman spectra of the isomers, are given.

scholarly journals New Synthetic Routes for 1-Benzyl-1,4,7,10-tetraazacyclododecane and 1,4,7,10-Tetraazacyclododecane-1-acetic Acid Ethyl Ester, Important Starting Materials for Metal-coded DOTA-Based Affinity Tags

2007 ◽  
Vol 62 (3) ◽  
pp. 397-406 ◽  
Author(s):  
Stephan W. Kohl ◽  
Katharina Kuse ◽  
Markus Hummert ◽  
Herbert Schumann ◽  
Clemens Mügge ◽  
...  
Keyword(s):  
Acetic Acid ◽  
Ethyl Ester ◽  
Nmr Spectra ◽  
Acid Ethyl Ester ◽  
Affinity Tags ◽  
X Ray ◽  
H Nmr ◽  
Synthetic Routes ◽  
New Compounds ◽  
C Nmr

Two improved routes to synthesize 1-benzyl-1,4,7,10-tetraazacyclododecane (6) and 1,4,7,10- tetraazacyclododecane-1-acetic acid ethyl ester (11) are described as well as the synthesis of 1-{2-[4-(maleimido-N-propylacetamidobutyl)amino]-2-oxoethyl}-1,4,7,10-tetraazacyclododecane- 4,7,10-triacetic acid (17) and its Y, Ho, Tm, and Lu complexes. The 1H and 13C NMR spectra of the new compounds as well as the single crystal X-ray structure analyses of the intermediates 4-benzyl-1,7-bis(p-toluenesulfonyl)diethylenetriamine (3) and 1,4,7-tris(p-toluenesulfonyl)diethylenetriamine (7) are reported and discussed. The rare earth complexes of 17 have been characterized by 1H NMR spectroscopy and MALDI-TOF mass spectrometry.

scholarly journals Solid State Structure and Absolute Configuration of Filifolinol Acetate

2011 ◽  
Vol 6 (6) ◽  
pp. 1934578X1100600
Author(s):  
Marcelo A. Muñoz ◽  
Alejandro Urzúa ◽  
Javier Echeverría ◽  
Brenda Modak ◽  
Pedro Joseph-Nathan
Keyword(s):  
Density Functional Theory ◽  
Solid State ◽  
Absolute Configuration ◽  
Spectroscopic Data ◽  
Density Functional ◽  
Vibrational Circular Dichroism ◽  
State Structure ◽  
Functional Theory ◽  
X Ray ◽  
C Nmr

Careful reevaluation of the 1H and 13C NMR spectroscopic data of filifolinol acetate (4) led to the reassignment of the C-10 and C-11 signals, as well as the gem-dimethyl signals. Single crystal X-ray analysis provided an independent structural confirmation of 4, and comparison of the experimental vibrational circular dichroism spectrum with calculations performed using density functional theory provided the absolute configuration of this 3H-spiro-1-benzofuran-2,1′-cyclohexane and related molecules.

scholarly journals Übergangsmetall-Carben-Komplexe, CXXXIV [1]. Synthese neuer Mono- und Biscarben-Komplexe der VI. Nebengruppe; Röntgenstruktur des ersten Bis[amino(alkoxy)carben]-Komplexes / Transition Metal Carbene Complexes, CXXXIV [1]. Synthesis of New Mono- and Bis-Carbene Complexes of Group VIb Elements; Structure of the First Bis[amino(alkoxy)carbene]-Complex

1984 ◽  
Vol 39 (5) ◽  
pp. 668-674 ◽  
Author(s):  
Ernst Otto Fischer ◽  
Rudolf Reitmeier ◽  
Klaus Ackermann
Keyword(s):  
Molecular Structure ◽  
Transition Metal ◽  
Spectroscopic Data ◽  
The Novel ◽  
Nucleophilic Agent ◽  
Reaction Conditions ◽  
Carbene Complexes ◽  
X Ray ◽  
X Ray Crystallography ◽  
New Compounds

The hexacarbonyl compounds of chromium, molybdenum and tungsten react with the highly nucleophilic agent Li NiPr2 and in a subsequent alkylation with (Et3O)BF4 to give the carbene complexes (CO)5M[C(N′Pr2)OEt] (1, 3, 4). In case of W(CO)6 and Mo(CO)6 the novel biscarbene complexes cis(CO)4M[C(NiPr2)OEt]2 (2, 5) are additionally obtained. Reaction conditions, properties and spectroscopic data of the new compounds are reported. The molecular structure of cis(CO)4W[C(NiPr2)OEt]2 (4) was determined by X-ray crystallography

Alkinol- und Alkindiol-substituierte Titanocen-Komplexe; Synthese, Reaktionsverhalten und Strukturmerkmale / Alkyne-ol and Alkyne-diol Substituted Titanocene Complexes; Synthesis, Reaction Behaviour and Structural Features

1995 ◽  
Vol 50 (6) ◽  
pp. 923-930 ◽  
Author(s):  
Heinrich Lang ◽  
Katrin Köhler ◽  
Mathias Herres ◽  
Christiane Emmerich
Keyword(s):  
Spectroscopic Data ◽  
Structural Features ◽  
Synthesis Reaction ◽  
Addition Compound ◽  
X Ray ◽  
C Nmr

The reaction of (η5-C5H4SiMe3)2TiCl2 (1) with HO(CH2)nC ≡ CR (2a: n = 1, R = H; 2b: n = 1, R = CH3; 2c: n = 1, R = CH2OH ; 3: n = 2, R = H; 4: n = 4, R = H) affords in toluene at 25 °C in the presence of NEt3 the monoalkyne-ol substituted titanocenes (η5-C5H4SiMe3)2Ti(Cl)[O(CH2)nC ≡ CR] (5a: n = 1. R = H; 5b: n = 1, R = CH3; 5c: n = 1, R = C H2OH; 6: n = 2, R = H; 7: n = 4. R = H ). Compound 5c reacts with one equivalent of 1 in the presence of NEt3 to yield (η5-C5H4SiMe3)2(Cl)Ti-OCH2C ≡ CCH2O -Ti(Cl)(η5-C5H4SiMe3)2 (8). In addition, compound 8 can be synthesized directly by treatment of (η5- C5H4SiMe3)2TiCl2 (1) with 0.5 equivalents of HOCH9C≡CCH2OH (2c) in the presence of NEt3. The reaction of (η5-C5H4SiMe3)2Ti(Cl)(OCH2C ≡ CCH3) (5b) with Co2(CO)8 (9) yields (η5-C5H4SiMe3)2Ti(Cl)[(η2-OCH2C ≡ CCH3)Co2(CO)6] (10). Treatment of 5b or 10 with HCl(aq) (11) leads to the formation of (η5-C5H4SiMe3)2TiCl2 (1) and HOCH2C ≡ CCH3 (2b) (reaction of 5b with 11) or (η5-C5H4SiMe3)2TiCl2 (1) and [(η2-HOCH2C ≡ CCH3)Co2(CO)6] (12) (reaction of 10 with 11). All compounds have been characterized by analytical and spectroscopic data (IR , 1H, 13C NMR, MS) and (η5-C5H4SiMe3)2Ti(Cl)(OCH2C ≡ CCH3) (5b) by X -ray analysis.

(3E)-5-Hydroxy-3-[5-(hydroxymethyl)furan-2-ylmethylene]-1-benzofuran-2(3H)-one

2007 ◽  
Vol 63 (11) ◽  
pp. o4354-o4354
Author(s):  
Hong-Yan Ma ◽  
Ji Shi ◽  
Chang-Hong Wang ◽  
Zheng-Tao Wang
Keyword(s):  
Hydrogen Bonds ◽  
Spectroscopic Data ◽  
Furan Ring ◽  
Crystallographic Analysis ◽  
Relative Configuration ◽  
X Ray ◽  
H Nmr ◽  
Compound C ◽  
A Chain ◽  
C Nmr

The title compound, C14H10O5, was isolated from Senecio cannabifolius Less var. integrifolius aqueous extract. The structure was elucidated on the basis of spectroscopic data, including MS, 1H NMR and 13C NMR, and the relative configuration was confirmed by X-ray crystallographic analysis. The benzofuran ring is almost coplanar with the furan ring [dihedral angle = 10.47 (15)°]. A chain is formed through supramolecular R 2 2(10) synthons and three-centre hydrogen bonds.

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