Reaction with halogen-containing

Peroxides oxidize N,N-DPDD to Wurster s red, a semiquinone diimine derivative [4]. Similarly Wurster s red is also produced from N,N-DPDD by reaction with halogen-containing substances in the presence of sodium ethylate and UV light and by reaction with the chlorinated triazines produced by reaction with chlorine [7]. 

Peroxides oxidize TPDD to Wurster s blue, a product with a semiquinone diimine structure [1]. Similarly Wurster s blue is also produced from TPDD by reaction with halogen-containing substances produced by the reaction of aromatic amines and triazines with chlorine gas. 

Shokol, V.A. and Kozhushko, B.N., Phosphorohalidites and phospho-ropseudohalidites in the Arbuzov reaction with halogen-containing compounds, Russ. Chem. Rev., 54, 98, 1983. 

The study of alkali atom reactions with halogen-containing molecules comprises much of the history of reactive scattering in molecular beams. The broad features of the reaction dynamics and their relation to the electronic structure of the potential energy surface are well understood.2 The reaction is initiated by an electron jump transition in which the valence electron of the alkali atom M is transferred to the halogen-containing molecule RX. Subsequent interaction of the alkali ion and the molecule anion, in the exit valley of the potential surface, leads to an alkali halide product molecule MX. 

Some reactions considered as nucleophilic additions to silenes may in actuality proceed by radical mechanisms, such as the addition of Br2 and possibly even SiCT 113,292, as well as reactions with halogen-containing solvents. There has also been a report of an addition of the elements of acetonitrile to a silene under high-temperature conditions, and this too may involve radical processes292. 

This catalytic cycle, generating acetyl iodide from methyl iodide, has been demonstrated by carbonylation of anhydrous methyl iodide at 80°C and CO partial pressure of 3 atm using [(C6H5)4As][Rh(CO)2X2] as catalysts. After several hours reaction, acetyl iodide can be identified by NMR and infrared techniques. However, under anhydrous conditions some catalyst deactivation occurs, apparently by halogen abstraction from the acetyl iodide, giving rhodium species such as frans-[Rh(CO)2I4] and [Rh(CO)I4] . Such dehalogenation reactions are common with d8 and d10 species, particularly in reactions with species containing weak... 

ESR of, 16 117 IR spectrum of, 16 117 NMR spectrum of, 16 117 peroxide derivatives of, 16 125-127, see also specific compounds preparation of, 16 115-118 properties of, 16 115-118 Raman spectra of, 16 117 reactions of, 16 118-125 with carbonyls and carbonates, 16 124 with complex anions, 16 125 with halogen-containing compounds, 16 121-123... 

Neutral formyl complexes which contain ligating CO often decompose by decarbonylation however, several exceptions exist. For instance, the osmium formyl hydride Os(H)(CO)2(PPh3)2(CHO) evolves H2(54). Although the data are preliminary, the cationic iridium formyl hydride 49 [Eq. (14)] may also decompose by H2 evolution (67). These reactions have some precedent in earlier studies by Norton (87), who obtained evidence for rapid alkane elimination from osmium acyl hydride intermediates Os(H)(CO)3(L)(COR) [L = PPh3, P(C2H5)3], Additional neutral formyls which do not give detectable metal hydride decomposition products have been noted (57, 65) however, in certain cases this can be attributed to the instability of the anticipated hydride under the reaction conditions (H2 loss or reaction with halogenated solvents). 

Formation of the electrophilic halogen species leads to the potential for rapid reaction with compounds containing strongly activating groups, such as activated aryl compounds. Particularly, substances containing aromatic ring structures that have... 

This situation has been widely discussed [592a-c] and has not been finally resolved [592d]. At the same time, there is experimental data (reactions with halogens) in favor of the existence of dithiol structures of type 318b containing M — S bonds (M = Ni, Pd, Pt) with metal oxidation number +4 [592e,f]. 

Both the hexa- and dodecaallylation reactions are readily controllable. On the other hand, the reactions with excess benzyl bromide [42] or p-alkoxybenzyl bromide [43, 44] give only the hexabenzylated or hexaalkoxybenzylated complexes as the ultimate reaction products. Cleavage of the methyl group from the p-methoxybenzyl derivatives synthesized in this way yielded hexaphenolate stars, which could be combined with halogen-containing Fe-sandwich electrophilic compounds such as chlorocarbonylferrocene or [FeCp(7S-C6H5Cl)][PF6] (Scheme 9) [43, 44]. 

Energy disposal in the reactions of electronically excited inert gas atoms with halogen-containing molecules has been studied by observing the ultraviolet or visible emission spectra of the inert gas halide exciplex products under flow or molecular beam conditions. The experimental information consists of branching ratios for the formation of different electronic states of the inert gas halide, vibrational population distributions (obtained by computer simulation of the bound-free spectrum) and the degree of polarisation of the chemiluminescence emission. The metastable inert gases have ionisation potentials that are very similar... 

For aluminum pigments the temperature is less restrictive. In this case their chemical reactivity needs to be considered, particularly with halogen-containing polymers. In extreme cases, if halogen is released, a strong reaction can be anticipated (Wuerz synthesis [15]). 

Studies of reactive scattering have been almost entirely restricted until recently to the reactions of alkali atoms with halogen-containing compounds. 

---