Abstract
Photolysis of the cyclotriphosphato complex (PPN)[Ru(P3O9)(η6-C6H6)] (2) with bpy (2,2′-bipyridyl) in alcohols generated a violet solution of (PPN)[Ru(P3O9)(bpy)(ROH)] (3) with a labile alcohol ligand. Complexes 3 were readily oxidized during recrystallization to give the Ru(III) alkoxo complexes (PPN)[Ru(OR)(P3O9)(bpy)] (4). Treatment of 3 with internal alkynes led to selective formation of η2-alkyne complexes (PPN)[Ru(P3O9)(bpy)(η2-RC≡CR′)] (7), which did not undergo vinylidene rearrangement under heating and photoirradiation conditions in contrast to its dppe analogues. On the other hand, diphenylacetylene complex 7c (R = R′ = Ph) gave the α-ketocarbene complex (PPN)[Ru(P3O9)(bpy)(═CPhCOPh)] (8) on reaction with m-CPBA. This observation provides a very rare example for the direct and controlled oxidation of a coordinated alkyne ligand. Reactions of 3 with the terminal alkynes in alcohols and in DMF afforded the alkoxycarbene complexes (PPN)[Ru(P3O9)(bpy){═C(OR)CH2CR′}] (9) and the carbonyl complex (PPN...
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