Chloroplatinic acid-Stannous chloride

Carbouylation of terminai okfins. Terminal olehns can be carbonylated to linear esters in high yield by use of a chloroplatinic acid-stannous chloride couple at 90° and... 

CARBENOID REACTIONS Methylene chloride-n-Butyllithium. CARBONYLATION Chloroplatinic acid-Stannous chloride. 

Oiloro-2-phenylquinazoline, 86-87,153 Chloroplatinic acid, 139, 393 Chloroplatinic acid-Stannous chloride, 87 N-Chloropolymaleimide, 87 ct-Chloropropanal, 80... 

Tetrachloropalladate(II) ion catalyzes the interconversion of 1- and 2-butenes in aqueous solutions containing chloride and hydronium ions. Sodium tetrachloropalladate(II) catalyzes the conversion of allylbenzene to propenyl-benzene in acetic acid solutions. Tetrakis(ethylene))Lt,/x -dichlororhodium(l) catalyzes butene isomerization in methanolic hydrogen chloride solutions . Cyclooctadienes isomerize in benzene-methanol solutions of dichlorobis-(triphenylphosphine)platinum(11) and stannous chloride. Chloroplatinic acid-stannous chloride catalyzes the isomerization of pentenes. Coordination complexes of zero-valent nickel with tris(2-biphenylyl)phosphite or triphenyl-phosphine catalyze the isomerization of cis-1,2-divinylcyclobutane to a mixture of c/5,m-l, 5-cyclooctadiene and 4-vinylcyclohexene . Detailed discussions of reaction kinetics and mechanisms appear in the papers cited. 

For the hydrogenation of ethylene and acetylene with chloroplatinic acid and stannous chloride as catalyst, a number of steps have been outlined which are characteristic of the mechanism 305). These steps are (1) competitive formation of a rr-ethyleneplatinum and a hydroplatinum complex (2) formation of the hydro-rr-ethyleneplatinum complex (3) rearrangement by insertion to form an ethylplatinum complex and (4) attack of the protonic hydrogen on the metal-carbon bond to form ethane and the catalyst. The reduction of acetylene to ethane proceeds via the intermediate formation of ethylene. 

As a final example of hydrogenation, a mixture of stannous chloride and chloroplatinic acid catalyzes the hydrogenation of ethylene almost quantitatively. It is interesting to note that the ease of hydrogenation parallels the ability of the olefin to complex with platinum. The higher olefins that do not readily complex with platinum also are found to be more difficult to hydrogenate. 

---