Carbon disulfide with metal amides

The chemistry of zirconium and hafnium amides has been investigated further 101) using the general reactions of (1) metal amide with excess protic compound, (2) metal amide with a stoichiometric amount of protic compound, and (3) the reaction of a metal chloride with lithium dimethyl amide. The comyiounds jirepared are listed in Table V. They are all monomeric. Hafnium amides have not been described before, although there is a reference by Bradley (7fl) to the reaction of hafnium amide with carbon disulfide and metal carbonyls. 

CI3OP Noncombustible liquid. Fumes in moist air. Contact with water, steam, or alcohols produces hydrochloric acid, phosphoric acid, and phosphine gas, which is pyrophoric, with possible ignition or explosion (may be a delayed reaction). Contact with air produces corrosive fumes. Violent reaction with acetone and possibly other ketones carbon disulfide, 2,6-dimethylpyridine-A-oxide, dimethyl sulfoxide, ethers (especially when metal salts are present) ferrocene-l,l -dicarboxylie acid, pyridine, zinc powder or dust. Reacts, possibly violently, with acids, bases, amines, amides, inorganic hydroxides alkali metals, alkalis, combustible materials, dimethyl... 

DICHLOROTHIOCARBONYL (463-71-8) Reacts with water, decomposing to hydrochloric acid and sulfur dioxide, carbon disulfide, and carbon dioxide. Aqueous solution is incompatible with sulfuric acid, alkalis, ammonia, aliphatic amines, alkanolamines, alkylene oxides, amides, epichlorohydrin, organic anhydrides, isocyanates, vinyl acetate. Corrodes most metals in the presence of moisture. 

Examples of this behavior at late transition metal centers are also known, when the amide is stabilized, for example, by coordination to a ring. Thus, the dicarbonyl complex, [Re(CO)2(PPh3)2 S2CN(Me)CNSC2H2 ], has been prepared in low yield from the thermolysis of [Re(CO)2(PPh3)2(mat)] (mat = 2-methylaminothiazole) with excess carbon disulfide (Eq. 20) (194). 

Group 4 (IV B) dithiocarbamate chemistry is constrained to the 4-4 oxidation state. The first reported example was the eight-coordinate tetrakis(dithiocarba-mate) titanium complex, [Ti(S2CNBz2)4], prepared by Dermer and Femelius in 1934 (608), while the heavier zirconium and hafnium analogues were first prepared by Bradley and Gitlitz (193) from the reaction of metal amides, [M(NR2)4] (M = Ti, Zr, Hf), with 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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