Continuous and batch microwave reactors were constructed for efficient, "green" synthesis with low-boiling solvents at high temperature in closed vessels. Capabilities for rapid heating and cooling, concurrent heating and cooling, and differential heating facilitated novel chemical reactions and processes. Commercial microwave systems based on these developments are available. Times required for conventional reactions typically are decreased by 2-3 orders of magnitude. Green processes also have resulted through use of less or no catalyst, readily recyclable solvents, or media and yields that are often higher than normal. Complementary interactive software for calculating optimal conditions was developed.

published as an Advance Article on the web 9th October 2001 Calix[4]resorcinarenes may be prepared in high yield and purity by direct reaction of resorcinol and benzaldehyde derivatives in the presence of a catalytic amount of solid acid and at ambient temperature under solvent-free conditions. This represents a viable alternative to traditional solution phase methodology. The solvent-free method measures up well with respect to energy usage, solvent wastes and associated hazards, reaction time and yield. In addition, the relevant benzaldehyde derivatives are prepared in polypropylene glycol, which is readily recycled.

A series of [K(ar) 2 ] + and [Rb(toluene) 3 ] + cations (ar ) benzene, toluene, o-xylene, or p-xylene) has been synthesized and crystallized in the presence of [M{N(SiMe 3 ) 2 } 3 ]anions (M ) Mg or Zn). In the solid state all form either extended supermolecular, dimeric or supramolecular, polymeric structures. Only [K(toluene) 2 ][Mg{N(SiMe 3 ) 2 } 3 ] was found to exist as both suprastructural isomers. Introducing cyclopentadienyl to the system gave a similar zincate with the unusual [K 2 Cp] + cation. The absence of any traditional Lewis bases facilitates short metal-to-arene contact distances and makes these species excellent candidates for the study of alkali metal cation-π interactions. It is shown that K-π interactions and to a lesser extent Rb-π interactions are heavily influenced by the number and nature of agostic methyl interactions, especially when the electron-donating ability of these is maximized by adoption of near-linear geometries. These features combine so that the weakest potassium-to-arene interaction observed is that with benzene.

Six arene anions in a cationic [K6Mg6N12]6+ ring (see picture, arene=benzene) are reported in the mixed‐metal macrocyclic amide of 24 (!) ring atoms. The macrocycle is produced through a very effective synthesis, in which the anions are selectively monodeprotonated.