The reaction between diphosphorus derivatives [( Im )P (Dipp)]OTf (1[OTf]) and [( Im )P (Dipp)Cl] (1[Cl]) with the cyclotetraphosphido cobalt complex [K(18c-6)][(PHDI)Co(η -cyclo-P )] (2) leads to the formation of complex [(PHDI)Co{η -cyclo-P (Dipp)( Im )}] (3), which features an unusual hexaphosphido ligand [ Im =4,5-dichloro-1,3-bis(2,6-diisopropylphenyl)imidazol-2-yl, Dipp=2,6-diisopropylphenyl, 18c-6=18-crown-6, PHDI=bis(2,6-diisopropylphenyl)phenanthrene-9,10-diimine]. Complex 3 was obtained as a crystalline material with a moderate yield at low temperature. Upon exposure to ambient temperature, compound 3 slowly transforms into two other compounds, [K(18c-6)][(PHDI)Co(η -P Dipp)] (4) and [(PHDI)Co{cyclo-P ( Im )}] (5).
View Article and Find Full Text PDFThe activation of white phosphorus (P ) by transition-metal complexes has been studied for several decades, but the functionalization and release of the resulting (organo)phosphorus ligands has rarely been achieved. Herein we describe the formation of rare diphosphan-1-ide anions from a P ligand by treatment with cyanide. Cobalt diorganopentaphosphido complexes have been synthesized by a stepwise reaction sequence involving a low-valent diimine cobalt complex, white phosphorus, and diorganochlorophosphanes.
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