203931-05-9Relevant articles and documents
Reactions of cationic palladium(II) methyl and vinyl complexes with alkynes
Lapointe, Anne M.,Brookhart, Maurice
, p. 1530 - 1537 (2008/10/08)
[(phen)Pd(CH3)(OEt2)]+[BAr′ 4]- (phen = 1,10 phenanthroline, Ar′ = 3,5-(CF3)2C6H3) reacts with RC=CR′ to form the η2-alkyne complexes [(phen)Pd(CH3)(η2-RC≡CR′] +[BAr′4]- (5a, R = R′ = SiMe3; 5b R=C6H5, R′ = H). In contrast, the reaction of the diimine complexes [(ArN=C(R)C(R)=NAr)Pd(CH3)(NCCH3)] +[BAr′4]- (1-3) (Ar = 2,6-(CH3)2C6H3, 2,6-(i-Pr)2C6H3; R = H, CH3, 1/2BIAN) with HC=CR′ (R′ = H, f-Bu) yielded the alkyne insertion products [(ArN=C(R)C(R)=NAr)Pd(CH=C(R)CH3)(NCCH3)] +[BAr(Equivalent to sign)4]- (3) while the reaction of 1-hexyne with 1a yielded a mixture of the 2,1- and 1,2-insertion products [(N-N)Pd-(C(C4H9)=CHCH3)(NCCH 3)]+[BAr′4]- and [(N-N)Pd(CH=C(C4H9)(CH3)(NCCH 3)]+[BAr′4]-, respectively The vinyl complexes [(N-N)Pd(CH=CRCH3)(NCCH3)]+[BAr′ 4]- react with acetylene to form the η1-dienyl complexes [(N-N)Pd(CH=CHCH=CRCH3)(NCCH3)] +[BAr′4]-, which then react with acetylene and rearrange to form the novel 5-ethyhdene-2-cyclopenten-1-yl complexes [(N-N)Pd(η3-C(CH3)(R)C5H5)] +[X]-. (R = H, t-Bu; X = BAr′4, O3SCF3) (8).
