from first principles PP-I-1

OY-II-1The Role of Monovalent Nickel in Metalcomplex CatalysisBocharova V.V., Kraikivskii P.B., Saraev V.V.Federal State Budget Institution of Higher Education "Irkutsk State University",st. Karl Marx, 1664003, Irkutsk, Russiaviktoriabocharova@mail.ruThe reaction of comproportionation with the formation of complexes of Ni(I) proceed in thejoint presence in the system of Ni(0) and Ni(II) as the cationic and electroneutral types ofstabilized olefin or organoelement ligands, that has been shown on the basis of analysis ofexperimental data. The spontaneous decay of hydride and organometallic complexes of Ni(II)also leads to the formation of complexes of Ni (I), it is set on the example of individualcomplexes of Ni(II). The experimental data presented in this report allow us to assert thatdespite the established notions, the equilibriumNi(II) Ni(0)2Ni(I)in nickel metal complex catalytic systems is almost completely shifted to the right and theformation of Ni(I) complexes is not out of the ordinary case.Complexes of Ni(I) formed in the catalytic systems have several unique properties thatprovide them the opportunity to participate directly in key reactions of various catalyticcycles. It is shown that one of the unique properties of cationic complexes of Ni(I) is thepossibility to stabilize only olefinic ligands in the solution.Complexes of Ni(I) can be easily incorporated into oxidative addition reaction of alkenes andalkynes to form complexes of Ni(III), the catalytic transformations of olefins and acetylenestake place with the formed complexes of Ni(III). The possibility of easy transformation ofcationic complexes of Ni(I) to the organometallic complexes of Ni(III) allowed for the firsttime to carry out the reaction of cyclodimerization of cyclooctadiene-1,5 with the formationof tetracyclic product wich had not been described before. For example, the atom-economicalcatalytic system Ni(COD) 2 /BF 3·OEt 2 was developed and showed high activity in the additivepolymerization of norbornene (1930(kg NB) (mol·Ni) -1 h -1 . The metallocyclic mechanism ofpolymerization of norbornene with complexes of Ni(I) and Ni(III) has also been suggested byus.This work was supported by the Federal Program "Scientific and scientific-pedagogicalpersonnel of innovative Russia" (contract number P732).88