136892-75-6Relevant academic research and scientific papers
Reactivity of some "ladder" type complexes under conditions of metallation
Orlova,Nekrasov,Petrovskii,Ezernitskaya,Magdesieva,Milovanov,Butin
, p. 1785 - 1788 (2007/10/03)
The behavior of binuclear "ladder" type complexes FpL, where Fp = Cp(CO)2Fe, L = p-MeC6H4Cr(CO)3 (4), CH2C6H5Cr(CO)3 (5), and p-FpC6H4Cr(CO)
Mechanistic aspects of the reactions of bis(tricarbonylchromium) coordinated biphenyl dianions with electrophiles and their subsequent oxidation
Rieke, Reuben D.,Daruwala, Khushroo P.,Schulte, Louis D.,Pankas, Steven M.
, p. 284 - 297 (2008/10/08)
Reaction of the (η6:η6-biphenyl)bis(tricarbonylchromium) dianion (2) with a wide variety of primary electrophiles results exclusively in an ipso addition. NMR data point out the formation of the endo isomer upon protonation. While a definitive answer is not possible for primary alkyl electrophiles, indirect evidence suggests either a carbanionic type SN2 or a metal-assisted endo addition to the ipso position. Reaction with cyclopropylcarbinyl bromide as well as 6-bromo-1-hexene suggests an inner-sphere polar SN2 mechanism for most of the primary electrophiles. However, easily reduced halides such as allylic and benzylic or those halides which have steric hindrance toward SN2 processes may well proceed via an electron-transfer process or a combination of SN2 and electron-transfer processes. 1,2-Aryl migration has been found to be the predominant pathway in the oxidative cleavage of the alkylated (η6:η 6-4,4′-dimethylbiphenyl)bis(tri-carbonylchromium) dianion (6), thereby indicating a cationic intermediate in the mechanism of this step. Alkylation followed by iodine oxidation of 4,4′-disubstituted biphenyls provides a short convenient approach to 2-alkyl-5,4′-disubstituted biphenyls.
