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Simple metathetical replacement reactions have been utilised to synthesise some triaryl phosphite complexes MX,[P(OR),], ( M = Ru or 0 s ; X = CI, Br, or I ) from the corresponding triphenylphosphine derivatives MX2(PPh,), ( x = 3 or 4). Carbonyl and nitrosyl derivatives MX,(CO) [P(OR),],, MX,(CO),[P(OR),],, and MX,(NO)[P(OR),],have also been prepared. The complexes RuHX(PPh,), (X = CI or Br) have been shown to undergo metathetical exchange to form triaryl phosphite complexes which react further, with elimination of a molecule of hydrogen, to yield organo-ruthenium (11) species. Structures containing a o-bond between the central ruthenium atom and an ortho-carbon atom of one of the aryl rings are proposed for these latter derivatives and supporting spectroscopic evidence is discussed.