Reaction of isocyanides with [(PPh3)2Pt(η3-CH2CCPh)]+ and the formation of the indenyl complex trans-[(PPh3)2Pt(η1-1H-inden-2-yl) (CNC(CH3)3)]+

The reaction of [(PPh3)(2)Pt(eta(3)-CH2CCPh)]X (X = CF3SO3-, BF4-, PF6-) with CNR (R = C(CH3)(3), CH2Ph) yields a mixture of the eta(1)-propargyl and -allenyl complexes trans-[(PPh3)(2)Pt(eta(1)-CH2C drop CPh)(CNR)](+) and trans-[(PPh3)(2)Pt(eta(1)-CPh=C=CH2)(CNR)](+) respectively, in about a 6/1 proportion. Isolation of the pure propargyl complex was possible in several eases (R = C(CH3)(3), X = CF3SO3-; R = CH2Ph, X = BF4-, PF6-). In solution the cationic complex trans-[(PPh3)(2)Pt(eta(1)-CH2C drop CPh)(CNC(CH3)(3))](+) rearranges to an indenyl complex which was isolated as the triflate salt trans-[(PPh3)(2)Pt(eta(1)-1H-inden-2-yl)(CNC(CH3)(3))]CF3SO3 (4). In contrast trans-[(PPh3)(2)Pt(eta(1)-CH2C drop CPh)(CNCH2Ph)](+) does not undergo this rearrangement under similar conditions. The structure of 4.2THF has been determined by X-ray diffraction techniques.