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D ep a rtm en t o f Inorganic C h em istry, C ath olic U niversity, T oern ooiveld, N ijm egen (The N etherlands) (R eceived O ctober 2 5th , 1 9 7 3) Summary Solutions o f RhCl(PCy3)2 react w ith 0 2, N 2, C2H4, CO and H2 to give trans-RhClA(PCy3)2 (A = 0 2, N 2, C2H4 and CO, Cy = cy clo h ex y l) and RhClH2(PCy3)2 ; the spontaneous form ation o f the rather air-stable RhCl(PCy3)2N 2 is ascribed to a com bination o f the steric requirem ents and electronic properties o f th e phosphine ligand.