| dc.description | The preparation and characterization of various cationic species containing arsenic and antimony in low-coordinate environments are reported. These species, known as arsylidenes and stibylidenes, may be viewed as carbene analogues and consequently are of general interest to many chemists. Stabilization techniques involving inclusion of the low-coordinate pnicogen atom in a heteronaphthalenic framework result in monomeric species. Attempts to isolate monomers without a heteronaphthalenic framework, instead using charge repulsion or steric effects as methods of stabilization, have been less successful. Investigations indicate that such reactions produce monomeric systems in solution and dimeric species in the solid state, however this dimerization does not involve As=As or Sb=Sb double bonds akin to carbene dimerizations, but rather a weak coordination from the electron-rich atom adjacent to the pnicogen is observed. Amino- or thia-chloroarsolidines, when reacted with the chloride ion abstractors GaCl$\sb3$ or AlCl$\sb3$, produce either dicationic dimers or monocationic complexes dependent upon the stoichiometry of the addition. Similar reactivity is observed with chloroarsenanes. Preliminary studies indicate that the thia-chlorostibolidine reacts in a similar manner, however the systems are complex and are not yet fully understood. Investigations into the chemistry of these compounds have revealed new and unexpected traits. Cycloaddition reactions in particular have produced surprising results that differ significantly from those observed in the associated carbenes or well-known phosphylidenes. | en_US |
