Phosphorus Nuclear Magnetic Resonance Spectroscopy

Abstract

It is well known from laboratory experiments that in the recombination process by three-body collisions, N2 and NO are formed to a large extent as electronically excited species. Especially in the case of NO it seems from our experimentation that the formation of electronically excited species is by far the most abundant process. It seems to be only reasonable to expect that electronically excited oxygen should be formed to a large extent by three-body recombination [2]. The Herzberg bands are actually emitted very weakly as is known from laboratory experiments with 0-atom-02 mixtures at about 1 mm. pressure. The atmospheric oxygen bands are somewhat more intense. The observed intensity of these bands is many decades weaker than the.light emission from the recombination processes of active nitrogen or from the NO formation under analogous conditions. It must be realized, however, that in the case of N2 and NO there are electronically excited states from which allowed transitions emitting light can occur, whereas in the case of the 0 2 the electronically excited species can only make forbidden or strongly forbidden transitions. Therefore the activated 0 2 species may become de-activated before light emission. We have some indication for this. In the night sky radiation, the Herzberg bands are most likely due to the process: O + O + M + 0 2 ( 3 2 3 + M and Received M a y 2, 1961 [A 164/3 IE] [43] G . ManneNa and P. Harteck, J. chem. Physics, in press. Nuclear magnetic resonance of the 31P nucleus IS suitable for the structural elucidation of phosphorus compounds, also for analytical and kinetic studies. In this paper, an attempt has been made towards the presentation of a comprehensive review of all 31P resonances so for determined.Nuclear magnetic resonance spectroscopy has recently become a technique of great importance to the chemist. The main emphasis has rightly been placed on proton resonance, but it has been found that the 31P nucleus gives rise to very useful resonance spectra. This subject was reviewed by Finegoldtl] in 1958, and a short account is also to be found in the book written by Pople, Bernstein, and Schneider [2a].

Synthetic, sterochemical, and electronic studies of organophosphorous ligands and their transition metal complexes

“…Me , 2-chloro-N-methyl-l,3,2-azaoxaphospholane (20) This compound was prepared by the reaction of phosphorus trichloride with a stoichiometric amount of the appropriate amino-alcohol. agreed well with that previously reported (44) and is given in Table 16. The and data support the proposed structure and are given in Tables 18 and 20, respectively. , 2-chloro-l,3,2-dioxaphosphorinane 24, maso-2-ch1oro-4,6-dimethyl-l,3,2-dioxaphosphorinane (25) The preparation of this compound requires the initial synthesis and purification of the meso form of 2,4-pentanediol followed by its reaction with phosphorus trichloride.…”

“…Preparations C1P(0CH2CH3)2, chlorodiethylphosphite (12) This compound was prepared and purified from the redistribution reaction of phosphorus trichloride and triethylphosphite by the modification of a procedure previously described (41,42), The modified procedure used is described in detail below. shifts of these pure compounds corresponded with those reported in the literature (43,44). and NMR data are in agreement with what would be expected based upon the structure and are reported in Tables 16 and 18, respectively.…”

“…yield = 62% (45)). The and nmr data were consistent with that previously reported (44) and are given in Tables 16 and 20, respectively.…”

“…yield = 69% (52)). The and data agreed well with those previously reported (54,44) and are given in Tables 16 and 20, respectively. Tables 16, 18, and 20, respectively, , 2-chloro-l,3,2-dioxaisophosphindolane (19) This compound was prepared using the previously reported procedures (57,58) involving the reaction of pyrocatechol with a stoichiometric quantity of phosphorus trichloride in diethyl ether.…”

“…The and spectra were consistent with those previously reported (50) and are given in Tables 16 and 20, respectively. , 2-chloro-l,3,2-dioxaphospholane (16) This compound was prepared by the method reported by Cason et al (51) from the reaction of dry ethylene glycol with phosphorus trichloride and purified prior to use by vacuum distillation (bp^^Qj = 41-43°C). The and nmr data corresponded with those previously reported (44) and…”