Organothallium compounds. VII. β-Diketonatobis(pentafluorophenyl)-thallium(III) compounds and their coordination derivatives

Abstract

The complexes (C₆F₅)₂TlX [X = MeCOCHCOMe (acac), CF₃COCHCOMe (tfac), CF₈COCHCOCF₃ (hfac), PhCOCHCOMe (bzac), PhCOCHCOPh (dbm), or quinolin-8- olate (oxinate or ox)], have been prepared by reactions between bromobis(pentafluorophenyl)thallium(III) and the appropriate sodium or thallous β-diketonates or sodium quinolin-8-olate, and react with equimolar amounts of 1,10-phenanthroline (phen) or 2,2?-bipyridyl (bipy) to give the complexes (C₆F₅)₂- (phen or bipy)TlX (X = acac, tfac, or hfac), (C₆F₅)₂(phen)TlX (X = bzac, dbm, or ox), but not (C₆F₅)₂(bipy)TlX (X = bzac, dbm, or ox). On reaction with triphenyl- phosphine oxide or triphenylarsine oxide, the complexes (C₆F₅)₂(Ph₃PO or Ph₃AsO)-TlX (X = acac, tfac, hfac, or dbm) and (C₆F₅)₂Ph₃AsOTl(ox) have been obtained. From conductance and molecular weight measurements and spectroscopic data, the complexes (C₆F₅)₂TlX (except X = ox), (C₆F₅)₂(Ph₃PO or Ph₃AsO)TlX, and (C₆F₅)₂(phen or bipy)TlX, are considered to be monomeric with chelated β-diketonate or oxinate groups, and hence to contain four-, five-, and six-coordinate thallium respectively, whereas (C₆F₅)₂Tl(ox) is considered to have an associated structure with bridging oxinate groups.