Sutin

Marcus R A and Sutin N 1985 Eiectron transfers in chemistry and bioiogy Biochim. Biophys. Acta 811 265-322... 

Theory of electron transfer reactions insights and hindsights. N. Sutin. Prog. Inorg. Chem., 1983, 30, 441-498 (148). 

Free energies, barriers and reactivity patterns in oxidation-reduction reactions. N. Sutin. Acc. Chem. Res., 1968,1, 225-231 (39). 

The Szilard-Chambers Reactions in Solids Carman Harhotlle and Norman Sutin... 

Studies of metal alkyls and aryls deal largely with arsenic, germanium and antimony, although some work has also been done on tellurium, mercury, thallium, bismuth and lead. The major contributions can be neatly divided into four periods early studies by Maddock, Sutin and H 1155).56).57) studies by the Polish >- >- and the Strasbourg >- 2).79) groups, work by Riedel and and most recently a series... 

An isotope effect seen in Sb03 by Maddock and Sutin was studied by Hall and Sutin , whose results are shown in Table 3. Again, phenyl radicals were cited as the likely means of reforming the bonds. It was pointed out that owing to the occurrence of isomeric transitions in both of these antimony isotopes, differences in the conversion coefficients could lead to the isotopic differences. 

Fig. 1. Annealing curves (45 °C) for several products in neutron irradiated triphenylarsine. Note particularly the initial rise and subsequent fall of diphenylarsine derivatives (Redrawn from Maddock and Sutin )...

Not many organometallic systems have been subjected to extensive thermal annealing studies— the most thorough work has been done on the phenylarsenic compounds. The earliest such study was that of Maddock and Sutin on triphenylarsine. The results are in part given in Fig. 1, from which it was concluded that the reformation progresses in the stepwise fashion ... 

Harbottle, G., Sutin, N. The Szilard-Chalmers Reaction in Solids. Advan. Inorg. Chem. Radiochem. /, 267—314 (1959). 

Study of the recoil chemistry of organometallic compounds for its own sake, began really in 1955 with the publication of a study (56) by Mad-dock and Sutin on neutron activation of triphenylarsene. Since this time, most of the published work has been focussed on those radioactive atoms which did not permanently escape their ligands. Thus, in one way or another, they end up in molecular form. It is with these that this review is largely concerned. 

Maddock and Sutin (56) observed the formation of numerous oxygenated products in neutron-irradiated AsPhj which, they argued, must have come from reaction of AsPh radicals with oxygen or water during the separation. The annealing effect of heating at 45° led to increased yields of AsPhj, while AsPhj products first increased and then decreased. This was interpreted as showing the involvement of phenyl radicals in a series of consecutive reactions ... 

The early work of Sutin and Dodson (85) on neutron-irradiated ferrocene exemplifies the results and problems of recoil chemistry. After dissolving their samples in hexane and extracting with aqueous solutions they isolated, after further purification, radioactive FeCp2 and a species which emerged as ionic iron(III). Adsorbed on the walls of the glass vessels remained another species soluble in acetone which accounted for up to 50-60% of the radioactive iron. This species has not yet been identified. The FeCp2 activity accounted for some 10-12% of the Fe, which increased on standing several weeks at room temperature or 2-3 days at 110° C, as is shown in Table III. 

Data from Sutin and Dodson (85) and Hillman and Weiss (37). 

Previously many excellent reviews on these and related topics have appeared in the literature. Among these are articles by Sutin", Stranks and Wilkins, Halpern , Vlcek, Amphlett and Zwolinski et ai . 

Sutin et al have made a detailed study of the chloride-catalysed paths in deuterated water media, the exchange occurring more slowly in this solvent than in water. Accurate values of, in both water and heavy water, were obtained by spectrophotometry and enabled more precise rate parameters to be calculated. For aqueous media, values are 22.8 l.mole sec fork (n = 0.50 Af and 20 °C),... 

Sutin et al have recently re-examined the pathways of exchange involving chloride and have evaluated the rate coefficients as k- = 57.6 and k = 159 1. mole . sec at 25 °C and n = 3.0 M. These workers have pointed out that step with coefficient k can occur in two ways... 

---