Nickel complexes carbon disulfide

The formation of complexes of l,2,3,4-thiatriazole-5-thiol has been well described in CHEC-II(1996) 1,2,3,4-thiatriazole-5-thiol can form complexes with various metals such as palladium, nickel, platinum, cobalt, zinc, etc. <1996CHEC-II(4)691>. These complexes can be prepared either by cycloaddition reactions of carbon disulfide with metal complexes of azide anion (Equation 20) or directly from the sodium salt of l,2,3,4-thiatriazole-5-thiol with metal salts. For instance, the palladium-thiatriazole complex 179 can be obtained as shown in Equation (20) or it may be formed from palladium(ll) nitrate, triphenylphosphine, and sodium thiatriazolate-5-thiolate. It should be noted that complexes of azide ion react with carbon disulfide much faster than sodium azide itself. 

Chlorohydridobis(tricyclohexylphosphine)nickel is a yellow-brown solid. It is thermally stable at ambient temperature but reacts with air. It is very soluble in benzene, tetrahydrofuran, and dichloromethane and is soluble in diethyl ether and petroleum ether. Carbon tetrachloride, carbon disulfide, and chloroform decompose the complex. The infrared spectrum shows a sharp v(Ni—H) band at 1916 cm-1 (KBr disk and Nujol mull). The high-field H nmr spectrum in benzene solution has a triplet (1 2 1) at t34.6 (TMS) with JpH 73.5 Hz. The splitting is caused by the coupling of the hydride proton with two equivalent 31P nuclei. This is consistent with a trans square-planar configuration. 

Although many transition-metal derivatives react with cyclopropenes by ring opening (See Section 2.C. and ref 107 for examples), 1,2-dimclhylcyclopropene was regenerated from the complex 8 by reaction with triphenylphosphane or carbon disulfide, and a number of related nickel ° and niobium complexes of cyclopropenes which retain the three-membered ring have been reported. ... 

Carbon disulfide reacts with a wide range of bases to produce ligands which readily coordinate to metals. New synthetic work including the formation of aryl xanthates, disulfide products, and oxidized metal dithiolates is reviewed. The sulfur addition and abstraction reactions are discussed, along with the photobleaching reaction of [Ni(n-butyldtc)a] Bridged mercaptide complexes of nickel triad elements are also described. 

Cyclohexyne nickel(O) complex 19, prepared by the reductive elimination of 1,2-dibromocyclohexene with sodium amalgam in the presence of Ni(C2H4)L2 (L2 = Cy2PCH2CH2PCy2), also reacts with carbon dioxide or carbon disulfide to give complexes 20 and 21, respectively (Eq.ll). ... 

The azido nickel complex 80 reacts with carbon disulfide at room temperature to give the [3+2] cycloadduct 81 . ... 

It is not clear when dithiocarbamates were first prepared, but certainly they have been known for at least 150 years, since as early as 1850 Debus reported the synthesis of dithiocarbamic acids (1). The first synthesis of a transition metal dithiocarbamate complex is also unclear, however, in a seminal paper in 1907, Delepine (2) reported on the synthesis of a range of aliphatic dithiocarbamates and also the salts of di-iTo-butyldithiocarbamate with transition metals including chromium, molybdenum, iron, manganese, cobalt, nickel, copper, zinc, platinum, cadmium, mercury, silver, and gold. He also noted that while dithiocarbamate salts of the alkali and alkali earth elements were water soluble, those of the transition metals and also the p-block metals and lanthanides were precipitated from water, to give salts soluble in ether and chloroform, and even in some cases, in benzene and carbon disulfide. 

All types of electrophiles have been used with 2-lithio-l,3-dithiane derivatives, including alkyl halides, sulfonates, sulfates, allylic alcohols, arene-metal complexes, epoxides, aziridines, carbonyl compounds, imines, Michael-acceptors, carbon dioxide, acyl chlorides, esters and lactones, amides, nitriles, isocyanates, disulfides and chlorotrialkylsilanes or stannanes. The final deprotection of the dithioacetal moiety can be carried out by means of different types of reagents in order to regenerate the carbonyl group by heavy metal coordination, alkylation and oxidation184 or it can be reduced to a methylene group with Raney-nickel, sodium or LiAIII4. 

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