SPECTROSCOPIC STUDIES OF ORGANOPHOSPHORUS COMPOUNDS: PART I. THE CONSTITUTION OF ALKYLPHOSPHINE – CARBON DISULFIDE ADDUCTS

1965 ◽  
Vol 43 (3) ◽  
pp. 608-613 ◽  
Author(s):  
M. Arshad A. Beg ◽  
M. S. Siddiqui
Keyword(s):  
Carbon Disulfide ◽  
Infrared Spectra ◽  
Organophosphorus Compounds ◽  
Spectroscopic Studies ◽  
Phosphorus Compound ◽  
Acceptor Molecule ◽  
Phosphine Oxides

The constitution of the alkylphosphine – carbon disulfide adducts has been investigated by the study of their infrared spectra. Certain definite features of the spectra of the adducts are the shift of the P—C asymmetric vibrations to higher frequencies and the large shifts in the fundamentals of the acceptor molecule. These features are attributed to the formation of a quadruply connected phosphorus compound. From a comparison of the spectra of the carbon disulfide adducts with those of the corresponding phosphonium compounds, phosphine oxides and phosphines, evidence is provided for the structure of these compounds which has been suggested to be of the phosphonium type.

Vibrational Spectroscopic Studies of Organophosphorus Compounds: CICH2–PCI2, XCH2–P(=O)X2, and CICH2–P(=S)CI2

1968 ◽  
Vol 22 (5) ◽  
pp. 452-459 ◽  
Author(s):  
R. A. Nyquist
Keyword(s):  
Infrared Spectrum ◽  
Infrared Spectra ◽  
Room Temperature ◽  
Organophosphorus Compounds ◽  
Spectroscopic Studies ◽  
Significant Information ◽  
Rotational Isomers ◽  
Torsion Vibration ◽  
Different Temperatures ◽  
Infrared Data

Infrared data were obtained for chloromethylphosphorous dichloride, chloromethylphosphonic dichloride (also Raman data), and chloromethylthiophosphonic dichloride over the region 45–3800 cm−1. Infrared data were also obtained for bromomethylphosphonic dibromide in the region 300–3800 cm−1. Infrared spectra for these compounds were recorded at different temperatures, and show that the pentavalent compounds exist as rotational isomers at room temperature. A previous study of chloromethylphosphonic dichloride and chloromethylthiophosphonic dichloride has established that these two compounds exist as rotational isomers, but the present study gives additional significant information. The infrared spectrum for methylphosphonic dichloride in the region 45–600 cm−1 has been recorded for purpose of comparison with the ClCH2–P series. No spectral evidence was observed for the P—CH3 torsion vibration in methylphosphonic dichloride.

Structural and spectroscopic studies of transition metal nitrite complexes. VIII. Crystal structures and spectra of three pentanuclear species with stoichiometry [Ni5(N-substituted ethane-1,2-diamine)4(OH)2(NO2)8]

1981 ◽  
Vol 34 (10) ◽  
pp. 2139 ◽  
Author(s):  
AJ Finney ◽  
MA Hitchman ◽  
CL Raston ◽  
GL Rowbottom ◽  
AH White
Keyword(s):  
Transition Metal ◽  
Crystal Structures ◽  
General Formula ◽  
Infrared Spectra ◽  
Spectroscopic Studies ◽  
Molecular Structures ◽  
Structural Variations ◽  
Crystal And Molecular Structures

The preparation of a series of novel compounds of general formula [Ni5L4(NO2)8(OH)2] formed by ethane-1,2-diamine or one of five N-substituted ethane-1,2-diamines (L) is described. The crystal and molecular structures of the ethane-1,2-diamine, N,N'-diethylethane-1,2-diamine and N,N-dimethylethane-1,2-diamine complexes are reported. Each compound contains a planar, pentameric arrangement of nickel(II) ions, linked by bridging hydroxide and nitrite ligands. The details of the nitrite bridges differ among the complexes, causing differences in their electronic and infrared spectra. The structural variations are probably caused by the differing steric requirements of the amine substituents.

Darstellung und 51V-NMR-spektroskopische Untersuchungen von η5-Cyclopentadienyl-tert-butylimidovanadium(III)-Komplexen mit σ-Donator, π-Akzeptor-Liganden / Synthesis and 51V NMR Spectroscopic Studies of η5 -Cyclopentadienyl-tert-butylimidovanadium( III) Complexes with σ -Donor, π -Acceptor Ligands

2003 ◽  
Vol 58 (10) ◽  
pp. 975-989 ◽  
Author(s):  
Martin Billen ◽  
Gabriele Hornung ◽  
Fritz Preuss
Keyword(s):  
Carbon Monoxide ◽  
Carbon Disulfide ◽  
Spectroscopic Studies ◽  
Reductive Dehalogenation ◽  
Spectroscopic Methods ◽  
Spin Configuration ◽  
51V Nmr

The imidovanadium(III) complexes [tBuN=VCp(PR3)2], [tBuN=VCp{P(OR)3}2] and [tBuN= VCp(CO)2] have been prepared starting from tBuN=VCpCl2 by reductive dehalogenation with magnesium. The reaction of [tBuN=VCp(PMe3)2] (2a) with carbon monoxide, alkynes, alkenes, tert-butylphosphaalkyne, nitriles, ketones and carbon disulfide furnished the complexes [tBuN=VCp(PMe3) (L)], while the vanadium(V) compound tBuN=VCp(O2C2Ph2) is formed with benzil. All vanadium(III) complexes obtained are diamagnetic (d2, low-spin configuration) and have been characterized by spectroscopic methods (MS; 1H, 13C, 31P, 51V NMR).

Spectroscopic Studies with N-Chloroarylsulphonamides: IR and 1H, 13C and 23Na Nmr Spectra of Sodium Salts of N-Chloro-Mono- and Di-Substituted-Benzenesulphonamides, 4-X-C6H4SO2NANCl (X = H; CH3; C2H5; F; Cl; Br; I or NO2) and i-X, j-YC6H3SO2NANCl (i-X, j-Y = 2,3-(CH3)2; 2,4-(CH3)2; 2,5-(CH3)2; 2-CH3, 4-Cl; 2-CH3, 5-Cl; 3-CH3, 4-Cl; 2,4-Cl2 or 3,4-Cl2)

2003 ◽  
Vol 58 (1) ◽  
pp. 51-56 ◽  
Author(s):  
◽  
J. D. D’Souza ◽  
B. H. Arun Kumar
Keyword(s):  
Solid State ◽  
Chemical Shift ◽  
Infrared Spectra ◽  
Phenyl Ring ◽  
Nmr Spectra ◽  
Chemical Shifts ◽  
Spectroscopic Studies ◽  
Sodium Salts ◽  
Experimental Chemical Shift ◽  
23Na Nmr

In an effort to introduce N-chloroarylsulphonamides of different oxydising strengths, sixteen sodium salts of N-chloro-mono- and di-substituted benzenesulphonamides of the configuration, 4- X-C6H4SO2NaNCl (where X = H; CH3; C2H5; F; Cl; Br; I or NO2) and i-X, j-YC6H3SO2NaNCl (where i-X, j-Y = 2,3-(CH3)2; 2,4-(CH3)2; 2,5-(CH3)2; 2-CH3,4-Cl; 2-CH3,5-Cl; 3-CH3,4-Cl; 2,4- Cl2 or 3,4-Cl2) are prepared, characterized through their infrared spectra in the solid state and NMR spectra in solution. The υN-Cl frequencies vary in the range 950 - 927 cm−1. Effects of substitution in the benzene ring in terms of electron donating and electron withdrawing groups have been considered, and conclusions drawn. The chemical shifts of aromatic protons and carbon-13 in all the N-chloroarylsulphonamides have been calculated by adding substituent contributions to the shift of benzene. Considering the approximation employed the agreement between the calculated and experimental chemical shift values for different protons or carbon-13 is quite good. Effects of phenyl ring substitution on chemical shift values of both 1H and 13C are also graphically represented in terms of line diagrams.

Catalyst- and Solvent-Free Addition of the P–H Species to Alkenes and Alkynes: A Green Methodology for C–P Bond Formation

Synthesis ◽  
2017 ◽  
Vol 49 (21) ◽  
pp. 4783-4807 ◽  
Author(s):  
Boris Trofimov ◽  
Nina Gusarova ◽  
Nataliya Chernysheva
Keyword(s):  
Organophosphorus Compounds ◽  
Bond Formation ◽  
Solvent Free ◽  
Secondary Phosphine ◽  
Phosphine Oxides ◽  
Secondary Phosphine Chalcogenides ◽  
Vinyl Sulfides ◽  
Radical Initiators ◽  
Phosphine Chalcogenides ◽  
Secondary Phosphines

Traditional methods for C–P bond formation via direct addition of P–H species to unsaturated compounds are usually implemented in the presence of base and metal catalysts or radical initiators in various organic solvents. During the last five years, a novel efficient and general catalyst/initiator- and solvent-free version of the hydrophosphination and hydrophosphinylation of multiple C–C bonds with H-phosphines and their chalcogenides has begun to develop and it is attracting growing attention. This approach corresponds to the recently emerged pot-, atom-, and step-economy (PASE) green paradigm. This review covers the literature on the synthesis of useful and in-demand organophosphorus compounds via catalyst- and solvent-free addition of P–H species to alkenes and alkynes.1 Introduction2 Addition of Secondary Phosphines to Alkenes3 Hydrophosphinylation of Alkenes with Secondary Phosphine Chalcogenides3.1 Oxidative Addition of Phosphine Oxides to Vinyl Sulfides3.2 Addition of Secondary Phosphine Sulfides and Phosphine Selenides to Alkenes3.3 Addition of Secondary Phosphine Sulfides and Phosphine Selenides to Divinyl Chalcogenides3.4 Hydrophosphinylation of Alkenes with Secondary Phosphine/Chalcogen Pair (Three-Component Reactions)4 Addition of Secondary Phosphines to Alkynes5 Addition of Secondary Phosphine Chalcogenides to Alkynes6 Conclusion

Organophosphorverbindungen mit tertiären Alkylsubstituenten. III*: Synthese und Reaktionen Di-1-adamantylsubstituierter Phosphorverbindungen; Kristallstruktur von Di-1-Adamantylphosphinsäurechlorid / Organophosphorus Compounds with Tertiary Alkyl Substituents. Ill: Synthesis and Reactions of Di-1-adam antyl-Substituted Phosphorus Compounds; Crystal Structure of Di-1-adam antylphosphinic Chloride

1994 ◽  
Vol 49 (6) ◽  
pp. 801-811 ◽  
Author(s):  
Jens R. Goerlich ◽  
Axel Fischer ◽  
Peter G. Jones ◽  
Reinhard Schmutzler
Keyword(s):  
Organophosphorus Compounds ◽  
Phosphorus Compounds ◽  
Secondary Phosphine ◽  
Phosphine Oxides ◽  
X Ray ◽  
Dry Air ◽  
Nmr Data ◽  
Standard Procedures ◽  
Hydrolysis Of ◽  
Tertiary Alkyl

The reaction of adamantane with PCl3/A1Cl3, followed by hydrolysis, gave (1-Ad)2P(:O)Cl 1, which was converted to (1-Ad)2P(:O)F 2 and (1-Ad)2P(:S)Cl 3 by standard procedures. The structure of 1 was confirmed by a single crystal X-ray structure determination; despite the bulky substituents the P-C bond lengths are normal (184.0(3), 185.0(3) pm). Whereas chlorine-fluorine exchange in 3 with AsF3 furnished (1-Ad)2P(:S)F 4, desulfuration of 3 with Ph3P to give (1-Ad)2PCl 5 failed. The secondary phosphine oxides R 1R2P(:O)H (R1, R2 = 1-Ad: 6; R1 = 1-Ad, R2 = tBu: 7; R1, R2 = tBu: 8) were synthesized by reaction of 1, 1-AdP(:O)Cl2 and tBuP(:0)Cl2 with tBuLi. 6 and 8 reacted readily with chloral to give the adducts R2P(:O)CH(OH)CCl3 (R = 1-Ad: 9; R = tBu: 10). Silylation of 6 with Me2NSiMe3 in the presence of dry air led to (1-Ad)2P(:O)OSiMe3 11, which was hydrolyzed to give (1-Ad)2P(:O)OH 12. (1-Ad)2POSiMe3 13 was obtained by the reaction of 6 with n-BuLi, followed by Me3SiCl. No reaction took place upon heating 6 with Mo(CO)6. (1-Ad)2PCl 5 was synthesized in low yield by the reaction of 6 with PCl3. The action of tetrachloro-obenzoquinone (TOB) upon 6 furnished (1-Ad)2P(:O)(o-OH)C6Cl4 15, whereas the tbutyl analogue of 15, 16, was synthesized by hydrolysis of the TOB-adduct of di-tbutylfluorophosphine. Analogous 1-adamantyl- and tbutyl-phosphorus compounds are compared with regard to their 31P NMR data

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