Hieracium dubium
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Abstract
Complexes [PtMe<sub>2</sub>(NN)], with NN = 2,2′-bipyridine
(bipy), 4,4′-di-<i>tert</i>-butyl-2,2′-bipyridine
(bu<sub>2</sub>bipy), di-2-pyridylamine (dpa), or di-2-pyridyl ketone
(dpk), react easily with phthaloyl peroxide to give a mixture of the
chelate complex [PtMe<sub>2</sub>{κ<sup>2</sup>-<i>O</i>,<i>O</i>′-1,2-(O<sub>2</sub>C)<sub>2</sub>C<sub>6</sub>H<sub>4</sub>}(NN)], which was structurally characterized
when NN = bu<sub>2</sub>bipy, and an oligomer or polymer [PtMe<sub>2</sub>{μ-κ<sup>2</sup>-<i>O</i>,<i>O</i>′-1,2-(O<sub>2</sub>C)<sub>2</sub>C<sub>6</sub>H<sub>4</sub>}(NN)]<sub><i>n</i></sub>. In the case with NN = dpa, no
phthalate chelate complex is formed. These complexes are easily hydrolyzed,
and the complexes <i>cis</i>-[PtMe<sub>2</sub>(OH){κ<sup>1</sup>-<i>O</i>-O<sub>2</sub>CC<sub>6</sub>H<sub>4</sub>-2-CO<sub>2</sub>H}(bipy)] and <i>trans</i>-[PtMe<sub>2</sub>{κ<sup>1</sup>-<i>O</i>-O<sub>2</sub>CC<sub>6</sub>H<sub>4</sub>-2-CO<sub>2</sub>H}(dpkOH)] have been structurally characterized.
It is argued that the oxidative addition of phthaloyl peroxide occurs
by a polar mechanism and that the hydrolysis is easy because there
is no special stability associated with the seven-membered platinum-phthalate
chelate ring
