- Matrix isolation and theoretical study of the reaction of substituted phosphines with CrCl2O2
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The reactions between CrO2Cl2 and a series of substituted phosphines have been investigated using matrix isolation infrared spectroscopy. For all of the phosphines except PF3, twin jet co-deposition of the two reagents into argon matrices at 14 K initially led to the formation of weak bands due to the corresponding phosphine oxide. For all of the phosphines, subsequent irradiation with light of λ > 300 nm led to the growth of a number of intense new bands that have been assigned to the phosphine oxide complexed to CrCl2O, following an oxygen atom transfer reaction. Gas-phase, merged jet reactions prior to matrix deposition led to a significant yield of the uncomplexed phosphine oxide. Theoretical calculations at the B3LYP/6-311++g(d,2p) level were carried out in support of the experimental work, to support product band assignments and clarify the nature of the molecular complexes.
- Delson, Adam J.,Ault, Bruce S.
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p. 13786 - 13791
(2008/10/09)
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- The gas-phase on-line production of phosphoryl halides, POX3 and their identification by infrared spectroscopy
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A new route has been devised, leading to the production of POX3 molecules where X = F, Br and I by an on-line process using phosphoryl chloride, POCl3 as a starting material passed over heated sodium fluoride, NaF, potassium bromide, KBr and potassium iodide, KI at 535, 690 and 480°C, respectively. The products have been characterised by the infrared (IR) spectra of their vapours. The low resolution gas-phase Fourier transform infrared spectra reported for the first time show strong bands centered at 1416.6, 1312.9, 1297.9 and 1285 cm-1, assigned to ν1(a1), the O=P stretching fundamental of POF3, POCl3, POBr3 and POI3, respectively.
- Allaf, Abdul W.
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p. 921 - 926
(2007/10/03)
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- OXIDATION OF PHOSPHORUS(III) HALIDES BY RED PHOTOLYSIS OF OZONE COMPLEXES IN SOLID ARGON
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PCl3-O3 and PBr3-O3 complexes in solid argon photolyze to give phosphoryl halides with red visible radiation that has no effect on isolated ozone.These observations and similar results for PH3-O3 and P4-O3 complexes show that the complex markedly increases the cross section for red photodissociation of ozone and suggest that this increase is due to the complex effectively lowering the barrier to dissociation by providing a strongly exothermic dissociation-recombination process.
- Moores, Brian W.,Andrews, Lester
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p. 1902 - 1907
(2007/10/02)
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- MASS SPECTROMETRIC AND MATRIX INFRARED INVESTIGATIONS OF THE FORMATION OF GASEOUS POBr.
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By reaction of mixtures of PBr//3 and O//2 with silver at about 1100 K, gaseous POBr is formed; this has been shown by mass spectrometric and infrared matrix measurements. The calculated values for the heat of formation and entropy are: DELTA H degree //2//9//8 (POBr) equals 10. 8 kJ/mol, S degree //2//9//8 (POBr) equals 292. 9 J/K multiplied by (times) mol. Based on the following three vibrational frequencies (1253. 0, 407. 1, and 253. 7 cm** minus **1) and some isotropic shifts (**1**60/**1**8O), approximate force constants have been calculated.
- Binnewies,Lakenbrink,Schnoeckel
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