1103280-28-9Relevant academic research and scientific papers
Solvent-mediated generation of cobalt-cluster-stabilised propargyl cations and radicals: Allyl migration versus peroxide formation
Kaldis, John H.,Brook, Michael A.,McGlinchey, Michael J.
, p. 10074 - 10084 (2008)
The protonation of [Co2(CO)6,[9-[(allyldimethylsilyl) ethynyl]-9H-fluoren-9-ol}] (4), with HBF4 in CH2Cl 2 led to migration of the allyl group from silicon to the cobalt-stabilised cationic site to furnish [Co2(CO) 6{9-allyl-9-[(dimethylfluorosilyl)ethynyl]-9H-fluorene}] (17). However, under the same conditions, [Co2(CO)6{9- [(benzyldimethylsilyl)ethynyl]-9H-fluoren-9-ol}] (5) underwent desilylation and rearrangement of the resulting terminal alkyne-dicobalt complex to give [Co 3(CO),(9H-fluorenylmethylcarbynyl)] (24); moreover, dimerisation of the (benzyldimethylsilyl)ethynyl-9H-fluorenyl moiety led to the propargyl-allene 26. In contrast, protonation of 5 in THF yielded [(Co2(CO) 6([(benzyldimethylsilyl)ethynyl-9H-fluorenyl])}2peroxide] (27) through a radical coupling process. Analogously, protonation of [Co 2-(CO)6{9-[(vinyldimethylsilyl)ethynyl]-9H-fluoren-9-ol}] (6) yields the corresponding peroxide 28. X-ray crystallographic data are reported for, among others, complexes 17, 24, 26, 27 and 28.
