Several Novel Ru(VI) and Ru(IV) Complexes Derived from [RuO<SUB>4</SUB>bipy] and [RuO<SUB>3</SUB>phen]<SUB>2</SUB>O
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Five novel neutral complexes of ruthenium(VI) and ruthenium(IV) with 2,2′-bipyridine and 1,10-phenanthroline, [RuO<SUB>2</SUB>(OH)<SUB>2</SUB>bipy]·3H<SUB>2</SUB>O, [Ru(OH)<SUB>3</SUB>phen]<SUB>2</SUB>O, [RuO<SUB>2</SUB>bipy<SUB>2</SUB>]·3H<SUB>2</SUB>O, [RuO<SUB>2</SUB>bipy·phen]·3H<SUB>2</SUB>O and [RuO<SUB>2</SUB>phen<SUB>2</SUB>], were prepared and characterized by a study of their infrared, visible and ultraviolet absorption spectra, and by polarographic measurements. [RuO<SUB>2</SUB>(OH)<SUB>2</SUB>bipy] and [Ru(OH)<SUB>3</SUB>phen]<SUB>2</SUB>O were obtained by the reduction of previously-reported complexes, [RuO<SUB>4</SUB>bipy] and [RuO<SUB>3</SUB>phen]<SUB>2</SUB>O respectively, with methanol, and [RuO<SUB>2</SUB>bipy<SUB>2</SUB>], [RuO<SUB>2</SUB>bipy·phen] and [RuO<SUB>2</SUB>phen<SUB>2</SUB>], by the reactions of [RuO<SUB>4</SUB>bipy] and [RuO<SUB>3</SUB>phen]<SUB>2</SUB>O in methanol with 2,2′-bipyridine and 1,10-phenanthroline respectively. [RuO<SUB>2</SUB>bipy·phen] and [RuO<SUB>2</SUB>phen<SUB>2</SUB>] were also obtained in methanol by the substitution reactions of [RuO<SUB>2</SUB>bipy<SUB>2</SUB>] and [RuO<SUB>2</SUB>bipy·phen] with 1,10-phenanthroline respectively. The five complexes were all diamagnetic. [RuO<SUB>2</SUB>(OH)<SUB>2</SUB>bipy] was assumed to be a "ruthenyl" complex with two oxide ions coordinated at the <I>trans</I> positions, like such well-known <I>trans</I>-dioxoruthenyl analogues as Cs<SUB>2</SUB>[RuO<SUB>2</SUB>Cl<SUB>4</SUB>] and [RuO<SUB>2</SUB>(OH)<SUB>2</SUB>(NH<SUB>3</SUB>)<SUB>2</SUB>], and [Ru(OH)<SUB>3</SUB>phen]<SUB>2</SUB>O was assumed to be a binuclear complex with an oxygen-bridge between ruthenium atoms. [RuO<SUB>2</SUB>bipy<SUB>2</SUB>], [RuO<SUB>2</SUB>bipy·phen], and [RuO<SUB>2</SUB>phen<SUB>2</SUB>] were assumed to be mononuclear complexes with two oxide ions coordinated at the <I>trans</I> positions, and their oxidation numbers were found polarographically, to be 4.
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