The 2c-2e- P-P bonded dimers [(CH)2(NR)2P]2 dissociate in solution to give the persistent new 7pi radicals [(CH)2(NR)2P]*, which are isoelectronic with the well known S/N thiazolyl radicals.
The quantification of Lewis acidity is accomplished by a deuterated quinolizidine probe utilizing 2H NMR spectroscopy. The chemical shifts of the 2H NMR signals for aluminum, boron, titanium, and zinc halides are reported. The rate constants for Lewis acid catalyzed reactions were determined by utilizing UV/Vis spectroscopy for Diels–Alder and Povarov reactions under pseudo‐first‐order conditions. The magnitude of the 2H NMR chemical shifts correlates with the rate constants of the organic transformations for many Lewis acids investigated in the same order, whereas some deviations are identified.
Transition metal-mediated dehydrocoupling is a developing synthetic tool for the preparation of an extensive range of main group element-element bonded species, with broad applications to molecular and polymeric materials. Recent results have stressed the relationship between this class of transition metal reagents and their entirely main group counterparts. But what are the similarities and differences between transition metal and main group systems?
Reaction of the redox-active base Sn(NMe(2))(2)/(n)BuLi with o-phenylene diamine leads to oxidative dehydrocoupling and rearrangement into the triazolyl anion.
The room-temperature reactions of stannocene, Cp*(2)Sn, with a range of primary phosphines, RPH(2), result in diphosphanes [RP(H)P(H)R]. The reactions involving Cp*(2)SnCl(2), however, result in catalytic dehydrocoupling; the first example of main group metal catalysed dehydrocoupling to be identified.
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