SYNTHESIS AND CHARACTERIZATION OF PHENYLIMIDORHEMIUM(V) COMPOUNDS CONTAINING POLYPYRIDYL LIGANDS - CRYSTAL-STRUCTURES OF MER-[RE(NPH)CL-3(BIPY)], TRANS-[RE(NPH)-(OET)(BIPY)(2)][PF6](2) AND TRANS-[RE(NPH)CL-2(TERPY)]PF6 (BIPY=2,2'-BIPYRIDINE, TERPY=2,2'/6',2''-TERPYRIDINE)

The reaction between mer-[Re(O)Cl-3(L-L)] [L-L = 2,2'-bipyridine (bipy) or 4,4'-dimethyl-2,2'-bypyridine] and aniline in refluxing o-xylene gave phenylimido compounds formulated as mer-[Re(NPh)-Cl-3(L-L)]. These compounds do not react with an alcohol (ROH) to form alkoxyimido compounds of the type cis-[Re(NPh)(OR)Cl-2(L-L)], but in the presence of an excess of the polypyridyl ligand, salts of the cation trans-[Re(NPh)(OEt)(L-L)(2)](2+) were obtained. When salts of trans-[Re(NPh)(OEt)(L-L)(2)](2+) were dissolved in MeCN solutions containing a few drops of concentrated hydrochloric acid rapid reactions occurred that resulted in the isolation of mer-[Re(NPh)Cl-3(L-L)]. The salt trans-[Re(NPh)Cl-2(terpy)]PF6 was prepared from the reaction between mer-trans-[Re(NPh)-Cl-3(PPh(3))(2)] and 2,2':6'2 ''-terpyridine (terpy) in refluxing ethanol. The spectroscopic and electro-chemical properties of these compounds were investigated and the structures of mer-[Re(NPh)-Cl-3(bipy)], trans-[Re(NPh)(OEt)(bipy)(2)][PF6](2) and trans-[Re(NPh)Cl-2(terpy)]PF6 determined by x-ray crystallography.