Nature of Hydrogen Bond in 1,2-Bis(vic-Dioximo-N,N') Nickel(II) Compounds

Voter, R. C.; Banks, Charles V.; Fassel, Velmer A.; Kehres, P. W.

doi:10.1021/ac60060a003

Cited by 23 publications

(6 citation statements)

References 24 publications

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“…A comparison of the Nujol spectra of a-p-chloro-and a-9-nitrobenzaldoximes and their corresponding 0-and N-methyl ethers and sodium salts indicated that a band near 1300, cm.-1 could possibly be ascribed to an 0-H bending mode. Evidence favoring such an assignment stems from t h e work of Voter et al (18). T h e Nujol spectra of 1,2-cyclohexanedionedioxime and 1,2-cycloheptaneclionedioxime presented by these investigators show that deuteration of these compounds caused the disappearance of, among others, an intense band around 1300, cnl-l.…”

Section: Resultsmentioning

confidence: 97%

Infrared Study of the N—oh Group in Alpha and Beta Oximes

Palm¹,

Werbin²

1954

Can. J. Chem.

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The 0-H bending and N-0 stretching vibrations were studied in four pairs of isomeric oximes. A band a t 1265 cn1.-', characteristic of the solution spectra of the a oximes, is identified with the 0-H bending mode. Tentative assignments for the N-0 stretching vibration both in solid and solution spectra are advanced.The p isomers show a distinct shift of the band associated with the N-0 mode from about 950 cm.-' in the solid to about 930 cm.-l i n solution.The results of a recent investigation (13) of the infrared spectra of five pairs of isomeric oximes demonstrated that the most pronounced difference between the geometric isomers was the position of the band associated with the 0-H stretching vibration which occurred near 3250 cm.-I in the a and near 3115 cm.-I in the P oximes. Although the isomers could not be distinguished from one another on the basis of their frequencies in the 1300 cm.-1 and 900 cm.-I regions, tentatively attributed to the 0-H deformation and N-0 stretching modes, more detailed examination of these absorption bands seemed desirable in order to verify these assignments. This was attempted in the present study by examining the spectra of eight isomeric oximes a s Nujol mulls and in benzene and chloroforn~ solutions. The spectra of several N-and 0-methyl ethers as well as the sodium salts of some of the oximes were also obtained in order t o complenlent this work. E X P E R I M E N T A LThe preparation of the oximes has been described previously (13). T h e method of Goldschmidt and Kjellin (8) The sodium salts of a-benzaldoxime, a-p-nitro-, and a-p-cl~lorobenzaldoximes were prepared in the following manner. Slightly less than one millimole of sodium methoxide in methanol was added t o one nlillimok of the oxime. After standing for one to two minutes, the oxime salt was precipitated with copious amounts of anhydrous ether and filtered. T h e salt was washed several times with ether to remove unreacted oxime and was dried over phosphorous pentoxide. T h e infrared spectra de~nonstrated that the unreacted oximes had been completely removed from the salts. N o attempt was made to obtain analytically pure salts since they were used 'Manzrscript received M a y 17, 1954. Contribution jrom the

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Section: Resultsmentioning

confidence: 97%

Infrared Study of the N—oh Group in Alpha and Beta Oximes

Palm¹,

Werbin²

1954

Can. J. Chem.

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“…Although the infrared spectra of several oximes that are of value as analytical reagents have been reported (10,23), a review of the literature indicates that no serious attempts have been made to compare the infrared spectra of the a and p oximes. The 7000 cm.-I region (first overtone of the OH stretching frequency) of dilute carbon tetrachloride solutions of a and P benzilmonoximes (16) were found to be identical while a benzoinoxime acetate showed two weak bands that did not appear jn the P form (24).…”

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confidence: 99%

The Infrared Spectra of Alpha and Beta Oximes

Palm¹,

Werbin²

1953

Can. J. Chem.

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'The spectra of several isomeric osimes in the solid state were examined in the range 700-3600 cm-'. The associated O H stretching-frequency near 3250 cm.-1 in the a oximes is displaced towards lower frequency in the @ oximes. The region of the OH stretching mode of several oximes was also studied in benzene and chloroform solutions. T h e frequencies near 1300 cm.-l and 920 cm.-1 are tentatively assigned to the 014 deformation and the N-OH stretching modes, respectively. No consistent differences are observed betweel! the a and the 6 oximes with respect to these vibrations. The band a t approxi~nately 1640 CIII.-~ ascribed to the C = N vibration remains essentially unchanged in the spectra of the two isomeric forms.Although the infrared spectra of several oximes that are of value as analytical reagents have been reported (10, 23), a review of the literature indicates that no serious attempts have been made to compare the infrared spectra of the a and p oximes. The 7000 cm.-I region (first overtone of the OH stretching frequency) of dilute carbon tetrachloride solutions of a and P benzilmonoximes (16) were found to be identical while a benzoinoxime acetate showed two weak bands that did not appear jn the P form (24).The spectra of a and P oximes are not expected to be identical since the arrangement and bonding of the atoms in the n~olecule give rise to characteristic absorption bands. The present investigation was undertaken, therefore, in order to determine possible differences in the infrared spectra of the two isomeric forms. The data presented in this report on 15 oximes in the solid state, 10 of which are geometric isomers, demonstrate that one can distinguish between the a and 6 compounds on the basis of the position of the OH stretching frequency. E X P E R I M E N T A L Infvaved SpectvaThe spectra were recorded in the region 700-3600 cm.-' with a Perkin-Elmer Model 21 double-beam spectrometer. The crystalline con~pounds were dried over phosphorus pentoxide, ground to a fine powder to reduce the scattering effect, and measured between two salt plates as Nujol mulls. The solutions (about 0.02 &I) were examinecl in sodium chloride cells of 0.03 mm. tl~ick~less. The instrunlent was set a t a slit schedule of 4 and speed 3 for each run. Duplicate spectra of the same compound did not differ by more than 5 1 0 cm.-' a t 3000 cm.-' and f 5 cnl.-' a t 1500 cm-I.The following oximes were commercial samples and, with the exception of a-benzaldoxime which was used directly, were recrystallized until the melting 1 Il.fanz~script received Jzme 8, 1955.

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“…The OH bending vibration absorbs between 1000 and 1420 om-l in a variety of compounds (Bellamy 1958) : a band near 1300 om-l in a-p-nitro-and p-chlorobenzaldoximes is absent in the 0 and N methyl ethers (Palm and Werbin 1934) and deuteration of l,2-cyclohexadione dioxime suppresses a strong 1300 cm-l band (Voter et al 1951), which is therefore assigned to the OH deformation mode. The configurations of (I), (11), and (111) were characterized by the VOH band which indicated a general assignment of the 6 0~ vibration : a-isomers absorb above 1300 cm-l and p-isomers at a lower frequency.…”

Section: Resultsmentioning

confidence: 99%

The Infrared Spectra of Bispyridinium Oximes

Tregellas-Williams¹

1962

Aust. J. Chem.

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This paper describes the spectra of isomeric oximes of a number of pyridinium compounds having the general formula :The bispyridinium oximes decompose on melting and are extremely insoluble in all solvents except water, in which they dissolve readily. The absorption frequency of the OH stretching mode in the oxime group has been found by Palm and Werbin (1953) to be characteristic of the a-and P-configurations in the case of several aromatic oximes (e.g. benzaldoxime and p-nitrobenzaldoxime) : a-and @-forms are those in which the H and OH groups are respectively cis and trans to one another. Palm and Werbin (1954) also found no significant correlation between structure and the OH deformation mode, except in solution. The OH stretching frequency in the solid state has therefore been used to characterize the isomers : the OH deformation has also been studied and ranges assigned to each configuration. EgperimentalSpectra were recorded on a Perkin-Elmer model 112 double-pass spectrometer equipped with lithium fluoride and rock-salt prisms. In the short-wave region samples were examined in silver iodide disks to avoid bonded OH bands in alkali halide disks but potassium bromide disks were used with the rock-salt prism. Duplicates did not differ by more than j l . 5 em-l in the spectral regions covered.The oximes were prepared according to the method of Poziomek, Hackley, and Steinberg (1958).

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Nature of Hydrogen Bond in 1,2-Bis(vic-Dioximo-N,N') Nickel(II) Compounds

Cited by 23 publications

References 24 publications

Infrared Study of the N—oh Group in Alpha and Beta Oximes

Infrared Study of the N—oh Group in Alpha and Beta Oximes

The Infrared Spectra of Alpha and Beta Oximes

The Infrared Spectra of Bispyridinium Oximes

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