The Pd(I)-Pd(I) dimer [Pd2(mu-PBu2t)(mu-PHBu2t)(PHBu2t)2](CF3SO3) (1(CF3SO3)) reacts with excess isoprene, giving [Pd2(mu-PBu2t)(mueta4-CH2=CHC(CH3)=CH2)(PHBu2t)2](CF3SO3) (2(CF3SO3)). Ethylene reacts with complex 1, giving [Pd2(mu-PBu2t){mueta2-O2S(O)CF3}(PEtBu2t)2 (3), which arises from insertion of the olefin into the two secondary phosphine P-H bonds. Complexes 2 and 3 were characterized via X-ray diffraction and multinuclear, multidimensional NMR spectroscopy. Relevant crystallographic parameters are as follows: for 2, space group Pbca, a = 17.321(4) angstrom, b = 22.115(3) angstrom, c = 21.531(9) angstrom, V = 8205(4) angstrom3, Z = 8; for 3, space group Cmc2(1), a = 15.435(3) angstrom, b = 18.142(9) angstrom, c = 14.833(4) angstrom, V = 4154(2) angstrom3, Z = 4.
Reaction of Phosphide-Bridged Palladium(I) Dimers Containing Secondary Phosphines with Ethylene and Isoprene. Coordination vs Insertion
LEONI, PIERO;PASQUALI, MARCO;
1993-01-01
Abstract
The Pd(I)-Pd(I) dimer [Pd2(mu-PBu2t)(mu-PHBu2t)(PHBu2t)2](CF3SO3) (1(CF3SO3)) reacts with excess isoprene, giving [Pd2(mu-PBu2t)(mueta4-CH2=CHC(CH3)=CH2)(PHBu2t)2](CF3SO3) (2(CF3SO3)). Ethylene reacts with complex 1, giving [Pd2(mu-PBu2t){mueta2-O2S(O)CF3}(PEtBu2t)2 (3), which arises from insertion of the olefin into the two secondary phosphine P-H bonds. Complexes 2 and 3 were characterized via X-ray diffraction and multinuclear, multidimensional NMR spectroscopy. Relevant crystallographic parameters are as follows: for 2, space group Pbca, a = 17.321(4) angstrom, b = 22.115(3) angstrom, c = 21.531(9) angstrom, V = 8205(4) angstrom3, Z = 8; for 3, space group Cmc2(1), a = 15.435(3) angstrom, b = 18.142(9) angstrom, c = 14.833(4) angstrom, V = 4154(2) angstrom3, Z = 4.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
