77525-84-9Relevant academic research and scientific papers
Picosecond radical kinetics. Rate constants for ring openings of 2-aryl-substituted cyclopropylcarbinyl radicals
Newcomb,Choi,Toy
, p. 1123 - 1135 (2007/10/03)
The kinetics of ring openings of a series of eight (trans-2-arylcyclopropyl)methyl radicals (1) were studied by indirect kinetic methods using Barton's PTOC esters as radical precursors and reaction with PhSeH as the competition reaction. The substituents were CF3, F, Me, and OMe located on both the para and meta positions of the aromatic ring. Syntheses of the radical precursors and the products of the radical reactions are described. Kinetics were determined between -43 and 25°C in four cases (CF3 and OMe substituents) and at 0 and 25°C in the other four cases. The rate constants at 25°C ranged from 1.0 x 1011 s-1 (p-CH3) to 4.1 x 1011 s-1 (p-CF3). The relatively large acceleration of the p-CF3 group, ca. 2.5 times as fast as the parent system with Ar = Ph, correlates well with Adam's ΔD substituent parameters but not with other radical substituent parameters. These calibrated radical rearrangements provide a new set of ultrafast reactions that can be applied in mechanistic probe studies.
Synthesis and spectral characterization of a series of iron and ruthenium benzylidene complexes, Cp(CO)(L)M=CH(C6H4R)+ (M = Fe, Ru; L = CO, PPh3; R = p-H, p-F, p-CH3, p-OCH3). Barriers to a
Brookhart,Studabaker, William B.,Humphrey, M. Beth,Husk, G. Ronald
, p. 132 - 140 (2008/10/08)
The α-ether complexes Cp(CO)2Fe-CH(OCH3)C6H4R (7a, R = H; 7b, R = p-F; 7c, R = p-CH3; 7d, R = p-OCH3; 7e, R = m-OCH3; 7f, R = p-CF3), Cp(CO)2Ru-CH(OCH3
