The Photochemistry of Ru(CO)4(PPh3).

It is well known that Ru(CO)4(PPh3) and Ru(CO)3(PPh3)2 are catalyst precursors for processes such as hydrogenation and isomerisation of olefins.

In an attempt to understand the catalytic cycles involved, photochemistry has been used to generate key intermediates.

Photolysis of a dichloromethane solution of Ru(CO)4(PPh3) under an atmosphere of ethene yields the novel complex Ru(CO)3(PPh3)(C2H4).

Addition of acetonitrile to an irradiated dichloromethane solution of Ru(CO)4(PPh3) leads to the generation of the novel mononuclear complex Ru(CO)3(PPh3)(MeCN).

This reacts readily with a further equivalent of phosphine, PR3, to form either the bis-phosphine complex Ru(CO)3(PPh3)2 if R = Ph or else the mixed phosphine compound Ru(CO)3(PPh3)((PR3).

As a result of these studies there is scope for detailed study of the electronic and steric effects of different phosphines on the catalytic activity of Ru(CO)3(PR3)(PR'3) complexes.

Back Forward