Flexible coordination of carbodiphosphorane-based pincer ligands in chromium(0) carbonyl complexes

A series of chromium(0) complexes was obtained by subsequent irradiation of [Cr(CO)(6)] in the presence of [(Ph2P-CH2-PPh2)(2)CH](+). Depending on the reaction conditions and the duration of irradiation, complexes with different coordination modes of the potentially tridentate ligand can be isolated. Shorter irradiation times lead to the coordination of the terminal PPh2 groups and the formation of [(kappa P-2,P'-{Ph2P-CH2-PPh2}CH)Cr(CO)(4)](+) (2), whereas after longer irradiation duration, the formation of fac- and mer-[(kappa P-3,C,P'-{Ph2P-CH2-PPh2}CH)Cr(CO)(3)](+) (3) can be observed. In the presence of base, the neutral complex [(kappa P-3,C,P'-{Ph2P-CH2-PPh2}C)Cr(CO)(3)] (4) can be isolated, enabling the analysis of the central CDP group's net donor strength through the C-O stretching vibration. Finally, the utilization of reductants like potassium graphite lead to the loss of hydrogen and generation of an anionic chromium(0) complex (5). Using quantum chemical methods, the stability of possible isomers is explored.