209963-71-3Relevant articles and documents
Catalytic arene H/D exchange with novel rhodium and iridium complexes
Rhinehart, Jennifer L.,Manbeck, Kimberly A.,Buzak, Sara K.,Lippa, Geoffrey M.,Brennessel, William W.,Goldberg, Karen I.,Jones, William D.
experimental part, p. 1943 - 1952 (2012/04/23)
Three novel pendant acetate complexes, [Rh(bdmpza)Cl3] -M+, [Rh(bdmpza)Cl2(py)], and [Ir(bdmpza)Cl3]-M+ (bdmpza = bis(3,5-dimethylpyrazol-1-yl) acetate, M+ = Li+, Na +), were synthesized. Abstraction of halide from these complexes with silver salts yielded species capable of C-H activation of arenes. The catalytic H/D exchange reaction between benzene and trifluoroacetic acid-d was optimized, and these conditions were used to evaluate H/D exchange in other arenes. Branched alkyl substituents in alkyl aromatics showed an affinity toward deuterium exchange in the β-alkyl position only. DFT calculations were performed to determine the mechanism of H/D exchange.
Mode attack of atomic carbon on benzene rings
Armstrong, Brian M.
, p. 6007 - 6011 (2007/10/03)
Reaction of are generated carbon atoms with tert-butylbenzene, 4, gives 3-methyl-3-phenyl-1-butene, 5, and 1,1-dimethylindane, 6. Labeling studies and isotope effects demonstrate that 5 results from an insertion into a methyl C-H bond followed by 1,2 hydrogen shift while 6 arises from initial ortho C-H insertion followed by intramolecular insertion into a methyl C-H bend. When fluoroboric acid is added to the 77 K matrix of 4 + C, tert-butyltropylium fluoroborate, 18, is formed. Labeling studies indicate that 18 results from initial insertion of C into meta and para C-H bonds of 4 followed by ring expansion to cycloheptatetraenes which are subsequently protonated. The reaction of C with benzene gives similar results, indicating that initial C-H insertion is the preferred mode of attack of atomic carbon on benzene rings.
