1.3-Dimethyl-1,3-diaza-2-R-5,6-benzo-2λ3-phosphorinan-4-one (R = F, Me2N, 2-Methylpiperidino, MeC(: 0 )N H -) als Liganden in Übergangsmetallkomplexen; Synthese und Struktur von Dichloro-Platin(II)- und Tetracarbonyl-Metall(O)- Koordinationsverbindungen (Metall = Cr, Mo und W) / 1.3-Dimethyl-1,3-diaza-2-R-5,6-benzo-2λ3-phosphorinan-4-ones (R = F, Me2N, 2-Methylpiperidino, MeC(: 0 )NH-) as Ligands in Transition-Metal Complexes; Synthesis and Structure of Dichloro-Platinum(II)- and Tetracarbonyl-Metal(0) Coordination Compounds (Metal = Cr, Mo and W)

1994 ◽  
Vol 49 (1) ◽  
pp. 100-110 ◽  
Author(s):  
Hans-Jürgen Plinta ◽  
Ion Neda ◽  
Reinhard Schmutzler
Keyword(s):  
Coordination Compounds ◽  
Nmr Spectra ◽  
Coupling Constants ◽  
Trans Isomers ◽  
Phosphorus Ligands ◽  
Tungsten Complexes ◽  
Significant Temperature ◽  
Derivatives Of ◽  
Cis Isomer

Abstract 1,3-Dimethyl-1,3-diaza-2-fluoro-5,6-benzo-1,3,2-phosphorinane-4-one (1) reacted with (COD)PtCl2 (COD = 1,5-cyclooctadiene) or K2PtCl4 to give the cis-dichloro-platinum(II) complex (2). The reactions of 1 with the tetracarbonyl norbornadiene derivatives of Cr, Mo and W furnished the complexes 3 - 6 . In the case of the chromium and tungsten complexes the trans-isomers 3 and 6 were formed, due to a cis-trans-isomerization. Room temperature and low temperature 31P NMR spectra of a mixture of 5 and 6 show no significant temperature dependence of the cis-trans equilibrium. The reaction of 1 with the pentacarbonyl tetrahydrofuran derivative of W led to the product 7. The spirophosphoranes 8 and 9 were obtained in low yields. The analogous reactions of 10, 15 and 20 with (COD)PtCl2 and the tetracarbonyl norbornadiene derivatives of Cr and Mo furnished the coordination compounds 11-14, 16-18, 21 and 23. In the case of all chromium complexes only the trans-isomers 11,16 and 21 were formed, whereas in the case of molybdenum cis-trans-isomer mixtures 12 and 13, as well as 17 and 18 were obtained. An attempt to obtain the cis-isomer of the molybdenum complex 22 failed. In the case of platinum the expected cis-complexes 14 and 23 were formed, while the attempted synthesis of 19 was unsuccessful. All these results are interpreted in terms of both steric and electronic factors. The ligands 1, 10, 15 and 20 coordinate via phosphorus. The validity of the concept of hard and soft acids and bases (HSAB) was confirmed. The characterization of 2 - 7 , 11-14, 16-18, 21 and 23 rests, especially, on their 1H, 13C and 31P NMR spectra, and their mass and infrared spectra. 31P - 31P coupling constants 2J(PP) for the cis-coordinated complexes 4, 5 and 14 involving two equivalent phosphorus ligands are also reported.

Anwendung der 15N-NMR-Spektroskopie zur Charakterisierung reaktiver, koordinativ ungesättigter Zinn-, Bleiund Phosphor-Stickstoff-Verbindungen / Application of 15N-NMR Spectroscopy to the Characterization of Reactive, Coordinatively Unsaturated Tin-, Lead- and Phosphorus-Nitrogen Compounds

1987 ◽  
Vol 42 (12) ◽  
pp. 1515-1519 ◽  
Author(s):  
Carin Stader ◽  
Bernd Wrackmeyer
Keyword(s):  
Nmr Spectra ◽  
Pulse Sequence ◽  
Coupling Constants ◽  
Spin Coupling ◽  
15N Nmr ◽  
Nmr Data ◽  
15N Nmr Spectroscopy ◽  
Spin Coupling Constants ◽  
Spin Spin Coupling

AbstractThe basic INEPT pulse sequence proved most useful for recording 15N NMR spectra at natural abundance of bis(amino)stannvlenes (1). -plumbylenes (2) and of imino-amino-λ2-phosphanes (3), where the nitrogen atoms carry bulky substituents like Me3Si-, t-Bu-, 2.4.4-trimethyl-2- pentyl-groups (t-Oct-groups) or are part of the 2.2.6.6-tetramethylpiperidinyl group. The sensitiv­ity of this technique is proved by the observation of 117/119Sn or 207Pb satellites owing to spin-spin coupling constants 1J(117/119Sn15N) and 1J(117/119Pb15N), respectively. NMR data of bis[bis(trimethylsilyl)methyl]tin (4) are reported in order to corroborate the arguments for the interpretation of the δ(15N) and 1J(119Sn15N) data. The 15N NMR data of the λ2-phosphanes (3) indicate a bonding situation similar to that in triazenes.

scholarly journals Synthesis and Characterization of Zinc(II)-Complexes with S-Alkyl Derivatives of Thiosalicylic Acid

2018 ◽  
Vol 19 (2) ◽  
pp. 113-117 ◽  
Author(s):  
Milos V. Nikolic ◽  
Marina Z. Mijajlovic ◽  
Dusan Lj. Tomovic ◽  
Andriana M. Bukonjic ◽  
Verica V. Jevtic ◽  
...  
Keyword(s):  
Nmr Spectra ◽  
Ethanol Solution ◽  
Alkyl Halides ◽  
Synthesis And Characterization ◽  
Direct Reaction ◽  
Thiosalicylic Acid ◽  
Alkyl Derivatives ◽  
Derivatives Of ◽  
C Nmr

Abstract New zinc(II)-complexes with S-alkyl derivatives of thiosalicylic acid (alkyl = benzyl-(L1), methyl-(L2), ethyl-(L3), propyl-(L4), butyl-(L5)) have been synthesized and characterized by elemental microanalysis, IR spectroscopy, and 1H and 13C NMR spectroscopy. The S-alkyl derivatives of thiosalicylic acid were prepared by alkylation of thiosalicylic acid by adding alkyl halides to an alkaline water-ethanol solution, while the corresponding zinc(II)-complexes were obtained via the direct reaction of ZnCl2 with S-alkyl derivatives of thiosalicylic acid in water. Based on the microanalysis results and the IR and NMR spectra of the S-alkyl derivatives of thiosalicylic acid and the corresponding zinc(II)-complexes, we concluded that the ligands are bidentately coordinated to the zinc(II)-ion.

Synthesis and study of Pt(II)–nitrile complexes. Multinuclear NMR spectra and crystal structures of compounds of the types [Pt(R-CN)Cl3]− and cis and trans-Pt(R-CN)2Cl2

1996 ◽  
Vol 74 (2) ◽  
pp. 144-152 ◽  
Author(s):  
Fernande D. Rochon ◽  
Robert Melanson ◽  
Eryk Thouin ◽  
Corinne Bensimon ◽  
André L. Beauchamp
Keyword(s):  
Crystal Structure ◽  
Crystal Structures ◽  
Trans Isomer ◽  
Nmr Spectra ◽  
Alkyl Chain ◽  
Coupling Constants ◽  
Trans Isomers ◽  
Multinuclear Nmr ◽  
Cis And Trans ◽  
Bond Trans

Complexes of the type [Pt(R-CN)Cl3]− were synthesized and studied by 1H, 13C, and 195Pt NMR spectroscopies. The 2J(195Pt-13C) coupling constants are about 240 Hz. The signals due to the cyano carbon atoms of the coordinated ligands were observed at higher fields than those of the free ligands. The shielding on the cyano carbon increases as the alkyl chain lengthens and also when the branching increases. The 195Pt signals of all the complexes were observed around −2000 ppm. The crystal structures of (NMe4)[Pt(C3H7-CN)Cl3] (1) and (NMe4)[Pt(p-HO-C6H4-CN)Cl3] (2) were determined. Compound 1 is monoclinic, P21/c, a = 8.384(5), b = 15.336(19), c = 11.759(9) Å, β = 99.52(6)°, Z = 4, R = 0.054, and wR = 0.051. Crystal 2 is tetragonal with a = 16.222(6), c = 12.052(5) Å, Z = 8, R = 0.059, and wR = 0.044. The Pt—CL bond trans to the nitrile ligand is shorter than normal (2.276(3) Å for 1 and 2.264(7) Å for 2) while the two other bonds are normal (2.293(4), 2.287(3) Å for 1 and 2.320(7), 2.275(8) Å for 2). The Pt—N bonds are 1.97(1) Å (1) and 1.92(2) Å (2) and the segments Pt-N≡C-C are linear. Disubstituted compounds were also synthesized and studied by multinuclear NMR. The 195Pt signals of the cis isomers were observed at lower fields than those of the trans isomers (Δ ≈ 65 ppm), while the 13C signals of the cyano carbons of the trans isomers were observed at lower fields than those of the cis compounds (Δ ≈ 0.6 ppm). The cis complexes isomerize to the trans compounds upon heating. The crystal structures of cis-(3) and trans-Pt(C2H5-CN)2Cl2 (4) and also of cis-Pt(p-HO-C6H4-CN)2Cl2 (5) were determined. Crystal 3 is monoclinic, P21/c, a = 7.506(5), b = 9.539(5), c = 14.823(7) Å, β = 92.31(4)°, Z = 4, R = 0.050, and wR = 0.042. The trans isomer 4 is monoclinic with the Pt atom on an inversion centre, P21/c, a = 5.149(4), b = 9.394(8), c = 10.944(10) Å, β = 97.84(7)°, Z = 4, R = 0.017 and wR = 0.020. Finally, compound 5 is triclinic, P-1, a = 7.464(3), b = 10.712(6), c = 12.291(5) Å, α = 75.63(4)°, β = 75.63(4)°, γ = 80.32(4)°, Z = 2, R = 0.045, and wR = 0.056. The Pt—Cl bond distances for the cis isomers are 2.269(5), 2.270(4) Å for 3 and 2.274(2), 2.279(3) Å for 5 while they are 2.289(3) Å for the trans isomer (4). The Pt—N bonds are 1.962(14), 1.988(11) Å (3), 1.972(7), 1.976(7) Å (5) and 1.969(5) Å for 4. Key words: platinum, nitrile, NMR, isomerization, crystal structure.

Coordination compounds of indium. Part 44. The oxidation of indium(I) halides by tetrahalogeno-ortho-quinones

1988 ◽  
Vol 66 (11) ◽  
pp. 2935-2940 ◽  
Author(s):  
Theodore A. Annan ◽  
Dennis G. Tuck
Keyword(s):  
Coordination Compounds ◽  
Nmr Spectra ◽  
Dynamic Behaviour ◽  
Addition Product ◽  
Donor Ligands ◽  
Chelate Complexes ◽  
H Nmr ◽  
Anionic Complexes ◽  
Derivatives Of ◽  
C Nmr

The reaction of indium(I) halides (InX; X = Cl, Br, I) with tetrahalogeno-ortho-quinones (Y4C6O2; Y = Cl, Br) gives the oxidative addition product Y4C6O2InX, These compounds have been isolated as adducts with neutral bidentate donor ligands (N,N,N′,N′-tetramethylethanediamine (tmen), 1,10-phenanthroline) or as salts of the anionic complexes [Y4C6O2InCl2]− or [Y4C6O2In(Cl)Br]−. The number of coordinated tmen molecules, and hence the structure, depends on the method of preparation. Infrared, 1H NMR, and 13C NMR spectroscopy all confirm that these products are all substituted-catecholato derivatives of indium(III), and the structure of these various neutral or anionic derivatives is discussed. The temperature dependence of the 13C NMR spectra shows that the dynamic behaviour of these compounds (in d6-dmso) is similar to that observed in previous studies of indium(III) chelate complexes.

Synthese von Silicium-Phosphor-Ringen - Struktur eines cis-2.2.4.4-Tetrakis(silylamino)-1.3-diphospha-2.4-disilacyclobutans / Synthesis of Silicon-Phosphorus-Rings - Structure of a cis-2,2,4,4-Tetrakis(silylamino)-1,3-diphospha-2,4-disilacyclobutane

1983 ◽  
Vol 38 (12) ◽  
pp. 1557-1562 ◽  
Author(s):  
Uwe Klingebiel ◽  
Norbert Vater ◽  
William Clegg ◽  
Martin Haase ◽  
George M. Sheldrick
Keyword(s):  
Crystal Structure ◽  
Nmr Spectra ◽  
Room Temperature ◽  
Molar Ratio ◽  
Trans Isomers ◽  
Cis And Trans Isomers ◽  
Cis And Trans ◽  
By Products ◽  
Cis Isomer

Fluorosilylphosphanes of the type R2SiFPHR′ (R = CHMe2, CMe3, NMeSiMe3; R′ = H, C6H5; 1-4) are obtained in the reaction of difluorosilanes with lithiated phosphanes in a molar ratio 1:1. Diphosphasilanes (5, 6) and a difluorosilylphosphane (7) are isolated as by-products. 1-4 react with n-C4H9Li to give cyclic silylphosphanes, LiF, and C4H10 (8-11). Dilithiated 5 reacts with F2PN(CMe3)SiMe3 to form of a four-membered SiP3-ring 12. The 31P NMR spectra of 9 and 11 show signal coalescence for the cis-and trans-isomers at room temperature. The crystal structure of the cis-isomer of 11 has been determined. The substituted ring 13 is prepared in the reaction of lithiated 9 and Me2SiF2

Coordination compounds of methyl gallium hydrides

1969 ◽  
Vol 47 (4) ◽  
pp. 673-679 ◽  
Author(s):  
A. Storr ◽  
V. G. Wiebe
Keyword(s):  
Coordination Compounds ◽  
Proton Magnetic Resonance ◽  
Proton Magnetic Resonance Spectroscopy ◽  
Resonance Spectroscopy ◽  
Relative Stabilities ◽  
New Class ◽  
Gallium Hydride ◽  
Derivatives Of ◽  
Gallium Compounds

Although the organo hydride derivatives of boron and aluminium are well characterized, little work has been reported on the corresponding gallium systems. The present study was initiated to determine the relative stabilities of organo gallium hydride derivatives as compared to the stabilities of the corresponding compounds of boron and aluminium. Various preparative routes in this new class of gallium compounds have been investigated. These include the use of organo mercury and organo lithium reagents in reactions with gallium hydride compounds and their halogen substituted derivatives, and also equlibration reactions between gallium hydride and organo gallium compounds. Both infrared and proton magnetic resonance spectroscopy techniques have been used extensively in following the progress of these reactions and in the characterization of the products.

scholarly journals Synthese und spektroskopische Charakterisierung mehrfach silylierter Ethene / Synthesis and Spectroscopic Characterization of Di- and Trisilylethenes

1987 ◽  
Vol 42 (12) ◽  
pp. 1543-1548 ◽  
Author(s):  
H. Schmidbaur ◽  
J. Ebenhöch
Keyword(s):  
Nmr Spectra ◽  
Spectroscopic Characterization ◽  
Coupling Constants ◽  
Methyl Groups ◽  
Coupling Constant ◽  
Catalytic Hydrosilylation

AbstractDi- and trisilylethenes have been prepared by catalytic hydrosilylation of trimethylsilyl-, bis-(trimethylsilyl)- and bis(trichlorosilyl)ethyne and converted into the hydrogenated derivatives by LiAlH4-reduction. The stereochemistry of the products and the effects of substitution of methyl vs. chlorine ligands on the NMR coupling constants J(29Si/1H) have been investigated by analysis of selectively (Me)-decoupled 29Si NMR spectra. From the results it has been concluded, that the catalytic hydrosilylation of silylated ethynes proceeds in a stereospecific syn fashion yielding trans adducts. Substitution of methyl by chlorine at one or two Si-atoms in tris(trimethylsilyl)ethene leads to an increase of the coupling constant J(29Si/1H vinyl) with the chlorinated Si-atoms and reduces the values for those Si-atoms, where the methyl groups are retained.

Derivatives of 5α-androstan-3α- and 3β-ol with acrylonitrile side chain

1991 ◽  
Vol 56 (12) ◽  
pp. 2906-2916 ◽  
Author(s):  
Vladimír Pouzar ◽  
Hana Chodounská ◽  
Ivan Černý ◽  
Pavel Drašar
Keyword(s):  
Double Bond ◽  
Nmr Spectra ◽  
Sodium Hydride ◽  
Coupling Constants ◽  
Side Chain ◽  
H Nmr ◽  
Derivatives Of

Aldehydes II - III were reacted with diethyl cyanomethylphosphonate and sodium hydride in 1,2-dimethoxyethane to give the respective pairs of unsaturated nitriles IVa and Va, VIa and VIIa, and VIIIa and IXa differing in configuration at the 20(21)-double bond. The pure isomers were obtained by chromatography on alumina, and the configuration at the double bond in them has been established on the basis of the coupling constants J(20, 21) in their 1H NMR spectra. Nitriles IVa - VIIa and IXa were converted via the corresponding hydroxy derivatives into hemisuccinates IVd - VIId and IXd, and into β-D-glucosides IVe - VIIe and IXe.

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