RESUMO
Over the course of the last six years, research on the synthesis and reactivity of molecular metal phosphaketenes (M-PCO) has gained increasing attention. However, lanthanide complexes of the heavier group 15 cyanate analogue PCO- have not been investigated so far. Herein we present exemplar studies on the nature and reactivity of rare-earth phosphaethynolato-complexes using three characteristic representatives of the rare-earth metals: Y, Nd and Sm. Our investigations comprise both +2 and +3 redox states, and one defined amidinate-based ligand set, as well as novel reaction pathways in the presence of the sequestering agents 18-crown-6 and 2,2,2-crypt.
RESUMO
The reactivity of the heavier group 15 tribromides, SbBr3 and BiBr3, towards 1,3-bis(2,6-diisopropylphenyl)-imidazol-2-ylidene (IPr) is described. These reactions quantitatively afford Lewis acid-base adducts, (IPr)EBr3 (E = Sb 1; Bi 2), which readily react with AlBr3 yielding cationic species [(IPr)EBr2]+ (E = Sb 3; Bi 4). Under thermal treatment, the N-heterocyclic carbene ligands in 1 and 2 will readily isomerise to afford the abnormally-bonded (or mesoionic) complexes (aIPr)EBr3 (E = Sb 5; Bi 6). As with 1 and 2, bromide abstraction from such compounds readily affords the cationic complexes [(aIPr)EBr2]+ (E = Sb 7; Bi 8). Finally, in an effort to elucidate the isomerisation process which allows for the conversion of 1 and 2 to the abnormally bonded systems (compounds 5 and 6), compound 1 was reacted with a further equivalent of IPr to afford the cationic species [(aIPr)2SbBr2]+ (9). This strongly suggests that the normal to abnormal isomerisation of the N-heterocylic carbene ligands in compounds 1 and 2 is mediated by the presence of free IPr. Compound [9]Br can be used to access the dicationic species [(aIPr)2SbBr]2+ (10), which we have identified spectroscopically. Single crystal X-ray structures and spectroscopic data for all compounds are discussed.
