The reactions of the monodentate organometallic phosphines [MI2(CO)3{MeC(CH2PPh2)3-P,P′}] (M = Mo, W) with π-allyl molybdenum(II) complexes and iron(O) and iron(II) carbonyl complexes

Equimolar quantities of [MoX(CO)(2)(NCMe)(2)(eta(3)-C3H4R)] (X = CI, R = H or Me; X = Br, R = H) and [MI2(CO)(3)-{MeC(CH2PPh2)(3)-P,P'}] (M = Mo or W) react in CH2Cl2 at room temperature to eventually give the tetrametallic complexes, [{Mo([mu-X)(CO)(2)(L-Mo or L-W)(eta(3)-C3H4R)}(2)] {L-Mo = [MoI2(CO)(3){MeC(CH2PPh2)(3)-P,P'}]; L-W=[WI2(CO)(3){MeC(CH2PPh2)(3)-P,P' }]} (1-6) in good yield. Reaction of [MoX(CO)(2)(NCMe)(2)(eta(3)-C3H4R)] (X = Cl, R = H or Me; X = Br, R = H) with 2 equiv. of L-Mo or L-W affords the trimetallic complexes [Mo(CO)(2)(L-Mo or L-W)(2)(eta(3)-C3H4R)] (7-12). Treatment of [Fe-2(CO)(9)] with 2 equiv. of L-Mo or L-W in CH2Cl2 at room temperature yields the bimetallic complexes, [Fe(CO)(4)(L-Mo or L-W)] (13 and 14). Equimolar amounts of [FeI(CO)(2)(Cp or Cp')] (CP = C5H5; CP' = C5H4Me) and L-Mo or L-W react in warm CH2Cl2 to give the cationic bimetallic complexes, [Fe(CO)(2)(L-Mo or L-W)(Cp or Cp')]l (15-18). The cationic nature of these complexes was established by reacting equimolar amounts of [Fe(CO)(2)(LCp)-Cp-w]I with Na[BPh4] in CH2Cl2 to give the anion-exchanged product, [Fe(CO)(2)(LCp)-Cp-W][BPh4] (19). (C) 2002 Elsevier Science Ltd. All rights reserved.