Matrix-IR spectroscopic investigations of the thermolysis and photolysis of diazoamides

Matrix photolysis of N,N-dialkyldiazoacetamides 1a-d at 7-10 K results in either the formation of C-H insertion products (in case of N,N-dimethyl and N,N-diethyl diazoamides) or almost exclusive Wolff rearrangement to ketenes (in the case of the cyclic diazoamides N-(diazoacetyl)azetidine and N-(diazoacetyl)pyrrolidine). This can be ascribed to higher activation barriers for the approach of the singlet carbene p orbital in 5 (or of the diazo carbon in an excited state of 1) to the stronger and "tied back" nature of the C-H bonds in the cyclic substituents. In contrast, flash vacuum thermolysis (FVT) of diazoamides 1a-d, in which reactions of excited states are excluded, gives rise to clean C-H insertion with only minor Wolff rearrangement to ketenes

Tax Return as a Political Statement

The accuracy of a tax return is usually interpreted as an outcome of the tax evasion decision by an individual. However, in non-democratic regimes with predatory blackmail tax systems it is possible that large sums voluntarily reported by influential politicians or businessmen may be used as political statements. By openly acknowledging one's personal income an individual can signal the strength of one's position, or, on the contrary, the submissiveness to the political leadership. In this paper we explore the idea of the tax return as a political statement and test it using a unique dataset of the tax returns filed by the Russian regional governors and the members of their families for the year 2009. Our results conjecture that Russian governors may deliberately file their tax return as a political statement to signal their strength vis-à-vis the central government