Fragmentation, Catenation, and Direct Functionalisation of White Phosphorus by a Uranium(IV)-Silyl-Phosphino-Carbene Complex

2021 ◽  
Author(s):  
Josef Boronski ◽  
John Seed ◽  
Ashley Wooles ◽  
Stephen Liddle

Room temperature reaction of the uranium(IV)-carbene [U{C(SiMe3)(PPh2)}(BIPMTMS)(μ-Cl)Li(TMEDA)(μ-TMEDA)0.5]2 (1, BIPMTMS = C(PPh2NSiMe3)2) with white phosphorus (P4) produces the organo-P5 compound [P5{C(SiMe3)(PPh2)}2][Li(TMEDA)2] (2) and the uranium(IV)-methanediide [U{BIPMTMS}{Cl}{μ-Cl}2{Li(TMEDA)}] (3). This is an unprecedented...

1968 ◽  
Vol 23 (7) ◽  
pp. 911-915 ◽  
Author(s):  
M. Scheffler ◽  
H. Drawe ◽  
A. Henglein

Trimethylthiophosphite and red phosphorus are formed when solutions of white phosphorus in dimethyldisulfide are exposed to γ-radiation. The red phosphorus has a high content of CH3S groups. It is very reactive and can be converted into trimethylthiophosphite upon further irradiation in dimethyldisulfide suspension. Both the formation of red phosphorus from white phosphorus and the formation of trimethylthiophosphite from red phosphorus are chain processes. The radiation chemical yields are of the order of several 100 molecules/100 eV at room temperature.


1962 ◽  
Vol 17 (11) ◽  
pp. 703-711 ◽  
Author(s):  
D. Perner ◽  
A. Henglein

Red phosphorus, phosphorus trichloride, trichloromethylphosphorus dichloride, hexachloroethane and a polymer consisting of carbon and chlorine are formed when solutions of white phosphorus in carbon tetrachloride are exposed to γ-radiation. Red phosphorus is the main product at room temperature. However, its yield rapidly decreases at higher temperatures and the yields of the low molecular weight products strongly increases. Typical G-values:The formation of the products PCl3 and CCl3PCl2 occurs by a chain reaction between phosphorus and carbon tetrachloride. A mechanism is proposed in which free radicals from the radiolysis of carbon tetrachloride attach the dissolved white phosphorus. The propagation of the chain is caused by chlorine transfer from carbon tetrachloride to partly trichloroalkylated or chlorinated phosphorus chains or rings. The activation energy of this transfer is found to be equal to 8.2 kcal/mole. This reaction with carbon tetrachloride is favored at high temperature while the competing process of the combination of those intermediate phosphorus chains and rings to give red phosphorus prodominates at low temperature. The red phosphorus formed contains one CCl3 group per 7 atoms of phosphorus. It was possible to synthesize trichloromethylphosphorus dichloride, trichloromethylphosphorus tetrachloride and trichloromethylphosphorus dibromide by treating the red phosphorus with chlorine or bromine, respectively.The thermal reaction between phosphorus and carbon tetrachloride also leads to PCl3 and CCl3PCl2 (ratio 1:3). Small amounts of red phosphorus and C2Cl6 could be traced too. The activation energy of the thermal reaction amounts to 22.2 kcal/moles. The photo reaction (visible light) leads to the same products. However, red phosphorus still is the main product at 100°C.


2020 ◽  
Vol 75 (1-2) ◽  
pp. 233-237 ◽  
Author(s):  
Philipp Müscher-Polzin ◽  
Christian Näther ◽  
Wolfgang Bensch

AbstractThe room temperature reaction of Hg(NO3)2 · H2O, cyclam (cyclam = 1,4,8,11-tetraazacyclotetradecane) and K8{Nb6O19} · 16 H2O in a mixture of H2O and DMSO led to crystallization of the novel compound {[Hg(cyclam)]6Nb6O19}(NO3)4 · 14 H2O, which is the first mercury containing polyoxoniobate. The structure consists of a {Nb6O19}8− cluster core which is expanded by six [Hg(cyclam)]2+ complexes via Hg–μ2-O–Nb bond formation. The title compound contains a positively charged polyoxoniobate cluster. The crystal water molecules form small aggregates by O–H · · · O hydrogen bonding which are joined into larger aggregates by N–O · · · H–O hydrogen bonding integrating the nitrate anions.


1990 ◽  
Vol 67 (6) ◽  
pp. 3184-3187 ◽  
Author(s):  
P. S. Asoka Kumar ◽  
Shailaja Mahumuni ◽  
Pramada Kulkarni ◽  
I. S. Mulla ◽  
M. Chandrachood ◽  
...  

2013 ◽  
Vol 37 (1) ◽  
pp. 39-45 ◽  
Author(s):  
Sanja Ćulubrk ◽  
Vesna Lojpur ◽  
Željka Antić ◽  
Miroslav D. Dramićanin

Abstract Europium-doped yttrium oxide nanoparticles with different doping concentrations were prepared by self-propagation room temperature reaction method. This simple synthesis method provides particles in the range of 12nm to 50 nm, depending on the temperature of calcination. In all cases, the nanopowders showed intense red emission upon excitation with ultraviolet radiation. Structural and optical characterization showed that the nanoparticles obtained after calcination at 1100°C have smaller unit cell volume and microstrain and longer emission lifetimes compared to the nanoparticles obtained after calcination at 600°C and 800°C. The maximal emission intensity was found for the sample doped with 5at% of Eu3+.


1969 ◽  
Vol 47 (17) ◽  
pp. 3099-3106 ◽  
Author(s):  
M. J. Baldwin ◽  
R. K. Brown

Acid-catalyzed elimination of methanol from 2,4-dimethoxytetrahydropyran (1) produces 2-methoxy-5,6-dihydro-2H-pyran (3) rather than the expected olefin 4-methoxy-3,4-dihydro-2H-pyran (2).The reaction of 1,3-dibromo-5,5-dimethylhydantoin with 3 in ether – methanol gives a 2:1 mixture of the isomers 3β-bromo-2α,4α-dimethoxytetrahydropyran (5a) and 3α-bromo-2α,4β-dimethoxytetrahydropyran (5b) respectively. A rationale is given to explain the preponderance of 5a over 5b and the highly selective attack of the bromine of the hydantoin and the methanol on C-3 and C-4 respectively of the double bond of 3. Reduction of 5ab with zinc in ethanol provides only compound 3.The room temperature reaction of 1 in a mixture of water and 1,2-dimethoxyethane containing Amberlite IR-120, produces 2-hydroxy-4-methoxytetrahydropyran (6) as an equilibrium mixture of cis and trans isomers in the ratio 1:1. This gave a value of 0.9 kcal/mole for the anomeric effect in 6. Pyrolysis of the derivative, 2-acetoxy-4-methoxytetrahydropyran failed to produce the olefin 2 and resulted only in extensive decomposition.


1999 ◽  
Vol 77 (4) ◽  
pp. 434-438 ◽  
Author(s):  
Steven J Rettig ◽  
Alan Storr ◽  
James Trotter

The room-temperature reaction of Me3Ga with benzimidazole 2-carboxylic acid in xylene solvent has yielded a novel crystalline hexameric gallium compound with "MeGa" moieties bridged by the doubly depronotated ligand precursor. Crystals of [MeGa(4,5-benzimidazolato-2-carboxylato)]6·(C6H6)·(m-Me2C6H4)2 are monoclinic, a = 18.091(2), b = 17.094(2), c = 13.2215(5) Å, Z = 2, space group C2/m. The structure was solved by direct methods and refined by full-matrix least-squares procedures to R (F, I [Formula: see text] 3σ(I)) = 0.064 (Rw (F2, all data) = 0.134). The hexameric Ga complex contains a six-membered ring of Ga atoms, bridged by the benzimidazolate ligands with the benzo rings projecting alternately above and below the Ga plane, thus forming a ball-shaped molecule. The complex could have ideal D3d symmetry, but it contains an encapsulated molecule of benzene, which distorts the regularity of the Ga6 hexagon, and reduces the symmetry of the complex to the crystallographically observed C2h. The coordination geometry at each of the two independent GaO2N2C centres approximates a trigonal bipyramid, with a N2C trigonal plane, and the O atoms above and below; average dimensions are Ga-O = 2.176(2), Ga-N = 1.973(3), Ga-C = 1.927(5) Å, O-Ga-O = 165°. The unit cell also contains four m-xylene solvent molecules (outside the molecular cage).Key words: gallium, crystal structure, benzene intercalate, benzimidazolecarboxylic acid.


ChemInform ◽  
2006 ◽  
Vol 37 (31) ◽  
Author(s):  
Xiong Ding ◽  
Xianhai Lv ◽  
Bin Hui ◽  
Zhijuan Chen ◽  
Minliang Xiao ◽  
...  

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