High-Resolution Nuclear Magnetic Resonance Spectra of the Pentafluorosulfur Group.

Merrill, Claude I.; Williamson, Stanley M.; Cady, George H.; Eggers, D. F.

doi:10.1021/ic50002a004

Cited by 41 publications

(11 citation statements)

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“…T h e same explanation has been proposed t o explain the apparent magnetic equivalence of the fluorine atoms in PF;, and other trigonal bipyramid molecules (14,15). I t should be noted, however, t h a t (18). Thus, it cannot be concluded with certainty t h a t there is a time-averaging of nonequivalent fluorines, although this seems very plausible.…”

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confidence: 68%

THE ¹⁹F N.M.R. SPECTRUM OF IF₇

Gillespie¹,

Quail²

1964

Can. J. Chem.

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I t is shown that the line shape calculated for the n.m.r. spectrum of a magnetic nucleus attached to a nucleus of spin 5/2 undergoing quadrupole relaxation agrees well with the observed spectrum of iodine heptafluoride. The iodine-fluorine coupling constant was found to be J I F = 2 100 C/S. The apparent magnetic equivalence of the fluorine atoms in IF7 is discussed.The I T nuclear magnetic resonance (n.m.r.) spectrum of IF7 a t room temperature is an extrenlely broad doublet (Fig. 1A). Our spectrum agrees closely with that reported previously (1-4). Muetterties and Packer (3) have suggested that the observed spectrum is a partially collapsed sextet arising from the coupling of seven spectroscopically equivalent fluorines to the iodine which is undergoing quadrupole relaxation. They did not, ho~vever, calculate the expected spectrum. Recently, Suzuki and Kubo (5) have given a general method for calculating multiplet line contours for the resonance of nuclei coupled to a high-spin nucleus which is undergoing quadrupole relaxation. Previous calculations of line shapes for nuclei coupled to nuclei having I = 1 (6, 7) and I = 3/2 (8) may be considered as limited applications of this illore general theory. I t has been pointed out that the theory involves some approximations (5, 6) but the agreement between calculated and experimental line shapes for I = 3/2 (8) indicates that the approximations do not lead t o any serious error. Suzuki and Kubo calculate spectral shapes as a function of a parameter a = (e2;~)2 --9 where e = the charge on an electron, eq = the electric field gradient a t the nucleus, eQ = the quadrupole moment of the nucleus, T , = the correlation time for molecular 'Present address:

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confidence: 68%

THE ¹⁹F N.M.R. SPECTRUM OF IF₇

Gillespie¹,

Quail²

1964

Can. J. Chem.

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“…The photosensitivity of fluorinated hypervalent sulfur‐containing compounds has been previously reported. Pentafluorosulfanyl halides undergo photochemically initiated addition reactions o alkenes and alkynes . These processes required room‐temperature gas phase or low‐temperature solution‐phase reaction conditions, that have limited exploitation of the unique photochemistry.…”

Section: Methodsmentioning

confidence: 99%

Photosensitive Hypervalent Fluorinated Sulfur Containing Polymers for Light Sensitive Applications

Bonetti

Murphy

Brainard

et al. 2020

Journal of Polymer Science

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Photochemical initiation of polymerization by visible or broadband ultraviolet irradiation of a mixture of 1,4‐(bis‐chlorotetrafluoro‐λ6‐sulfanyl) benzene and 1,4‐diethynyl benzene forms light responsive polymers. The novel polymers have a trans‐tetrafluoro‐λ6‐sulfanyl (tetrafluorosulfanyl, SF4) group backbone and are sensitive to electron beam (EB) and extreme ultraviolet (EUV) irradiation. Both EB lithography and EUV contrast experiments demonstrate the sensitivity of the polymer films to short wavelength irradiation.

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“…Early syntheses of fluorinated peroxides involved the coupling of oxy-radicals to form the peroxide bond. 1 In fact, the cophotolysis of the mixtures of peroxides SF 5 OOSF 5 /CF 3 OOCF 3 and SF 5 OOSF 5 /FS(O 2 )OO(O 2 )SF have been employed by Cady and coworkers to prepare SF 5 OOCF 3 and SF 5 OO(O 2 )SF. 1 The fluorinated peroxides allow study of the role that the electron-withdrawing effect of electronegative groups plays on their reactivity, energetics and conformation.…”

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confidence: 99%

“…1 In fact, the cophotolysis of the mixtures of peroxides SF 5 OOSF 5 /CF 3 OOCF 3 and SF 5 OOSF 5 /FS(O 2 )OO(O 2 )SF have been employed by Cady and coworkers to prepare SF 5 OOCF 3 and SF 5 OO(O 2 )SF. 1 The fluorinated peroxides allow study of the role that the electron-withdrawing effect of electronegative groups plays on their reactivity, energetics and conformation. Here we report the determination of the rate coefficient for the recombination of FC(O)O and FS(O 2 )O radicals to form the new peroxide FC(O)OO(O 2 )SF at 296 K. In addition, the rate coefficient for the reaction of FS(O 2 )O with CO has been determined for the first time.…”

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confidence: 99%