Coupling is possible under three different conditions: (1) Room temperature – reaction time 7h to 5 days depending on the substrates. (2) Thermal heating above 60^oC – reaction time >2h. (3) Microwave heating (in air) – reaction time >5-10 minutes. This protocol can also be used with aryl chlorides (albeit with much slower rates at room temperature and lower yields) or with aryl iodides. Best rates/yields were achieved with cyclic secondary amines or short chain acyclic secondary amines. Coupling will not occur at room temperature for primary amines with aryl bromides, but is possible with certain selected amines (e.g. 1-adamantylamine) and aryl iodides. Coupling with primary amines generally requires heating above 60^oC and a greater excess of amine (4eq or more) to subdue bisarylation caused by the secondary aniline product being more reactive than the primary amine. This excess of amine will slow the reaction, so higher catalytic loading is recommended to compensate for this. The catalyst is required for coupling to occur (especially at room temperature) although coupling may be possible without the catalyst for some highly activated aryl bromides. No reaction occurs with other N-H containing molecules that were tested, such as indole, carbamates or amides. The use of 5-bromoindole (as the aryl halide) with piperidine afforded only the dehalohydrogenation product, indole. Dehalohydrogenation is not usually observed (should it occur) on TLC due to the products being benzene or toluene etc. Whilst reactions were carried out in Schlenk tubes and cycled with argon/vacuum, it is possible to carry out the reaction in a round-bottom flask and simply by purging with argon or nitrogen (as for most other room temperature reactions). The use of a glovebox is not required at all and all reagents may be weighed in air. The saturated imidazolium salts were prepared using procedures on synthetic pages (see [[31|Page 31]]), but can also be purchased. SIPr.HBF₄ can be used in place of SIPr.HCl, as can the unsaturated salt 1,3-bis(2,6-diisopropylphenyl)imidazolium chloride (IPr.HCl) or the 1,3-bis(2,4,6-trimethylphenyl)imidazolinium salt (SIMes). Pd₂(dba)₃.CHCl₃ can be used in place of Pd₂(dba)₃ with the same results. Pd(OAc)₂ and Pd(dba)₂ were found to work too but gave slower reaction rates and lower yields. A 1:2 palladium to ligand ratio was found to give the fastest rates here (contrary to other reports). This was not due to adventitious moisture, as the imidazolinium salts were stored in desiccators. The aryl halides were used as received without further purification, as were any solid amines. However, if liquid at room temperature, the amines were filtered through alumina before use. The LHMDS (lithium hexamethyldisilazide) base was used as a 1M solution in THF (purchased from Aldrich). It could also be used as a 1M solution in toluene, which afforded lower yields and slower rates, but was useful when heating well above the boiling point of THF. LHMDS was found to be preferable over NaHMDS and KHMDS. No evidence was observed of the silylamide ion coupling with the halide (which after work-up would afford ArNH₂). The use of the oil bath was not necessary. It was simply used to be sure that all “room temperature” reactions were conducted under equivalent conditions.