ORGANOMETALLIC LEWIS-ACIDS .48. NEW PRECURSORS TO ORGANOMETALLIC CATIONIC LEWIS-ACIDS WITH 2 ACCESSIBLE COORDINATION SITES - (OC)4RE(OET2)FBF3 AND (OC)2(PPH3)2RU(FBF3)2

The allyl transfer reaction between Re(CO)5- and [eta3-allyl)PdCl]2 co mplexes leads to (allyl)rhenium complexes (eta3-H2CCR1CR2R3)Re(CO), (1 : R1, R2, R3 = H; 2: R2, R3 = H, R1 = Me; 3: R1, R2 = H, R 3 = Me; 4: R1 = H, R2, R3 = Me). The 2-methylallyl complex 2 has been characteriz ed by low-temperature X-ray diffraction. Protonation of 1 with HBF4.OE t2 in CH2Cl2 gives the complex (OC)4Re(OEt2)FBF3 (5), which is a precu rsor for the 14 e- System ''(OC)4Re+''. THF and H2O replace the diethy l ether in 5 to give [(OC)4Re(solvent)2]BF4 (6, 7). The reaction of (O C)2(PPh3)2RuCl2 with AgBF4 yields the complex (OC)2(PPh3)2Ru(FBF3)2 (8 ), which can be considered as a precursor for the 14 e- cation ''(OC)2 (PPh3)2Ru2+'' and reacts with H2O to give [(OC)2(PPh3)2Ru(F)(H2O)]BF4 (9). Complexes 5-9 are characterized by IR, H-1-, C-13-, P-31- and F-1 9-NMR spectroscopy.