Henry Rzepa's Blog Chemistry with a twist

March 19, 2017

Pyrophoric metals + the mechanism of thermal decomposition of magnesium oxalate.

A pyrophoric metal is one that burns spontaneously in oxygen; I came across this phenomenon as a teenager doing experiments at home. Pyrophoric iron for example is prepared by heating anhydrous iron (II) oxalate in a sealed test tube (i.e. to 600° or higher). When the tube is broken open and the contents released, a shower of sparks forms. Not all metals do this; early group metals such as calcium undergo a different reaction releasing carbon monoxide and forming calcium carbonate and not the metal itself. Here as a prelude to the pyrophoric reaction proper, I take a look at this alternative mechanism using calculations.


December 30, 2009

Ménage à deux: Non-classical SC bonds.

A previous post posed the question; during the transformation of one molecule to another, what is the maximum number of electron pairs that can simultaneously move either to or from any one atom-pair bond as part of the reaction? A rather artificial example (atom-swapping between three nitrosonium cations) was used to illustrate the concept, in which three electron pairs would all move from a triple bond to a region not previously containing any electrons to form new triple bonds and destroy the old. Here is a slightly more realistic example of the phenomenon, illustrated by the (narcisistic) reaction below of a bis(sulfur trifluoride) carbene. Close relatives of this molecule are actually known, with either one SF3 of the units replaced by a CF3 group or a SF5 replacing the SF3 (DOI: 10.1021/ja00290a038 ).


Powered by WordPress