New Ti complexes bearing phenoxy−imine ligands with pendant aryl−OMe donors have been developed for ethylene trimerization to produce 1-hexene. These Ti complexes combined with methylaluminoxane selectively trimerize ethylene to form 1-hexene with exceptionally high activity (e.g., 6.59 tons of 1-hexene/((g of Ti) h)) .

The rhodium cationic complex [[h5 +h 1 -{3-(NIM)Ind-P} n = 2 ]Rh(CO)Me]BF 4 (1) reacts with 1-phenylpropyne regioselectively and stereospecifically to afford the alkenyl complex [[h 5 +h 1 -{3-(NIM)Ind-P} n = 2 ]Rh{h 2 -ONC(CH 3 )-C(CH 3 )NCPh}]BF 4 (2).

We have shown concrete evidence for migration of an alkyl group in carbonyl insertion and deinsertion steps between the methyl carbonyl rhodium complex [{η 5 :η 1 -(Ind-P) n)3 }Rh(CO)Me]BF 4 (3) and the acetyl rhodium complex {η 5 :η 1 -(Ind-P) n)3 }RhI(COMe) (1) by crystallography as well as by 1 H NMR spectroscopy.

The first optically active cyclopentadienyl-phosphine bidentate ligands ([Cp-P]H ligands) in which a diphenylphosphino group and a cyclopentadienyl or an indenyl group are connected by an L-threitol derivative or an (S,S)-trans-1,2-dimethylenecyclo-pentane group have been prepared. The rhodium and ruthenium complexes of their anions have been prepared and characterized.

Several types of rhodium carbonyl complexes, {η5,η1-(Ind-P)n}RhCO [(Ind-P)n = C9H6(CH2)nPR2; n = 2-4; R = Ph or Cy (Cy = cyclohexyl)], have been prepared. The substitution of the carbonyl group of {η5,η1-(Ind-P)n=4}RhCO with nBu3P proceeded via a novel “lid-on-off” mechanism to afford {η5,η1-(Ind-P)n=4}Rh(nBu3P). However, the reaction of {η5,η1-(Ind-P)n}RhCO having an ethylene or a propylene spacer with nBu3P gave the addition products, {η3,η1-(Ind-P)n}Rh(CO)(nBu3P).