Treatment of (η 5 -C 5 H 5 ) 2 Rh 2 (CO){η 1 -Ph 2 P (CH 2 ) n PPh 2 }(μ-η 1 :η 1 -CF 3 C 2 CF 3 ) (I) with (η 5 -CH 3 C 5 H 4 )Mn(CO) 2 (thf) or Cr(CO) 5 (thf) gives the hetero-trinuclear products (η-C 5 H 5 ) 2 Rh 2 (CO)(μ-CF 3 C 2 CF 3 ) {μ:η 1 :η 1 -Ph 2 P(CH 2 ) n PPh 2 } (η-CH 3 C 5 H 4 )Mn(CO) 2 (II, n = 1-4) and (η 5 -C 5 H 5 ) 2 Rh 2 (CO)(μ-CF 3 C 2 CF 3 ) {μ:η 1 :η 1 -Ph 2 P(CH 2 ) n PPh 2 }Cr(CO) 5 (IV, n = 1-4) in good yields. In these products, the configuration of the CO and bisphosphine units on the Rh-Rh bond is trans. Related reactions between (η 5 :η 5 -C 5 H 4 CH 2 C 5 H 4 )Rh 2 (CO) {η 1 -Ph 2 P(CH 2 ) n PPh 2 } (μ-η 1 :η 1 -CF 3 C 2 CF 3 ) (V) and the same solvated manganese and chromium complexes give (η 5 :η 5 -C 5 H 4 CH 2 C 5 H 4 )Rh 2 (CO) (μ-CF 3 C 2 CF 3 ){μ:η 1 :η 1 -Ph 2 P(CH 2 ) n PPh 2 }(η-CH 3 C 5 H 4 )Mn(CO) 2 (VI, n = 1, 2 or 4) and (η 5 :η 5 -C 5 H 4 CH 2 C 5 H 4 )Rh 2 (CO) (μ-CF 3 C 2 CF 3 ){μ:η 1 :η 1 -Ph 2 P(CH 2 ) 3 PPh 2 } (CrCO) 5 (VIII). The complexes (VI) and (VIII) have a mutually cis arrangement of CO and the bisphosphine on the Rh-Rh bond. Attempts to induce the complexes (IV), (V), (VI), and (VIII) to form clusters by loss of CO and Rh-M bond formation were not successful. Treatment with trimethylamine oxide or sunlight irradiation generally resulted in loss of the hetero-metal and formation of the dirhodium phosphine oxide complexes (III, n = 2 or 4) and (VII, n = 2, 3).