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

Abstract Equimolar quantities of [MoX(CO) 2 (NCMe) 2 (η 3 -C 3 H 4 R)] (X=Cl, R=H or Me; X=Br, R=H) and [MI 2 (CO) 3 {MeC(CH 2 PPh 2 ) 3 - P , P ′}] (M=Mo or W) react in CH 2 Cl 2 at room temperature to eventually give the tetrametallic complexes, [{Mo(μ-X)(CO) 2 (L Mo or L W )(η 3 -C 3 H 4 R)} 2 ] {L Mo =[MoI 2 (CO) 3 {MeC(CH 2 PPh 2 ) 3 - P , P ′}]; L W =[WI 2 (CO) 3 {MeC(CH 2 PPh 2 ) 3 - P , P ′}]} ( 1 – 6 ) in good yield. Reaction of [MoX(CO) 2 (NCMe) 2 (η 3 -C 3 H 4 R)] (X=Cl, R=H or Me; X=Br, R=H) with 2 equiv. of L Mo or L W affords the trimetallic complexes [MoX(CO) 2 (L Mo or L W ) 2 (η 3 -C 3 H 4 R)] ( 7 – 12 ). Treatment of [Fe 2 (CO) 9 ] with 2 equiv. of L Mo or L W in CH 2 Cl 2 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=C 5 H 5 ; Cp′=C 5 H 4 Me) and L Mo or L W react in warm CH 2 Cl 2 to give the cationic bimetallic complexes, [Fe(CO) 2 (L Mo or L W )(Cp or Cp′)]I ( 15 – 18 ). The cationic nature of these complexes was established by reacting equimolar amounts of [Fe(CO) 2 L W Cp]I with Na[BPh 4 ] in CH 2 Cl 2 to give the anion-exchanged product, [Fe(CO) 2 L W Cp][BPh 4 ] ( 19 ).