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UV-induced photochemical transformations of the paramagnetic [Cr(CO) 4 (Ph 2 PCH 2 CH 2 CH 2 PPh 2 )] + complex (abbreviated [Cr(CO) 4 (dppp)] + ) in dichloromethane was investigated by CW EPR spectroscopy. Room-temperature UV irradiation results in the rapid transformation of [Cr(CO) 4 (dppp)] + into trans -[Cr(CO) 2 (dppp) 2 ] + . However, low-temperature (77-120 K) UV irradiation reveals the presence of an intermediate mer -[Cr(CO) 3 (κ 1 -dppp)(κ 2 -dppp)] + complex which photochemically transforms into trans -[Cr(CO) 2 (dppp) 2 ] + . The derived spin Hamiltonian parameters for these complexes were confirmed by DFT calculations. The photoinduced reaction is shown to be concentration-dependent, leading to a distribution of the three complexes ([Cr(CO) 4 (dppp)] + , mer -[Cr(CO) 3 (κ 1 -dppp)(κ 2 -dppp)] + , and trans -[Cr(CO) 2 (dppp) 2 ] + ). A bimolecular photoinduced mechanism is proposed to account for the formation of mer -[Cr(CO) 3 (κ 1 -dppp)(κ 2 -dppp)] + and trans -[Cr(CO) 2 (dppp) 2 ] + .

Unravelling the Photochemical Transformations of Chromium(I) 1,3 Bis(diphenylphosphino), [Cr(CO)4(dppp)]+, by EPR Spectroscopy

Unravelling the Photochemical Transformations of Chromium(I) 1,3 Bis(diphenylphosphino), [Cr(CO)₄(dppp)]⁺, by EPR Spectroscopy