Photoluminescence, photoredox properties and crystal structures of rhenium(V)-benzylidyne complexes with phosphine ligands

DOI: 10.1039/DT9960002827

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 2827 - 2834 (1996)

Update date:2022-08-03

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Authors:

Xue, Wen-Mei

Wang, Yue

Mak, Thomas C. W.

Che, Chi-Ming

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Article abstract of DOI:10.1039/DT9960002827

Several rhenium(V)-benzylidyne complexes [Re(CR)(pdpp)₂Cl]⁺ [R = C₆H₂Me₃-2,4,6, pdpp = o-phenylenebis(diphenylphosphine)], [Re(CR)L₂(CO)(H₂O)Cl]⁺ [L = PPh₃, P(C₆H₄OMe-p)₃ or PMe₂Ph] and trans-[Re(CR)(dppe)(CO)₂Cl]⁺ [dppe = 1,2-bis(diphenylphosphino)ethane] have been prepared. The structures of trans-[Re(CR)(pdpp)₂Cl]ClO₄·CHCl ₃·0.25MeOH and [Re(CR)(PPh₃)₂(CO)(H₂O)Cl]ClO ₄· 1.5MeOH have been determined by X-ray analyses. The Re≡C distances are 1.802(5) and 1.784(8) A respectively. In acetonitrile and dichloromethane the complexes show intense absorption bands at 318-330 nm and weak ones at 405-450 nm, the latter being tentatively assigned to d_xy → d_π* (d_xz,d_yz) transitions. Photoexcitation in the solution, solid or glassy state gives intense orange to red emissions, and the emitting states are tentatively assigned to ³[(d_xy)¹(d_π*)¹]. The variation in non-radiative decay rate constants for the emissions of the rhenium(V)-benzylidyne complexes are consistent with a prediction from the energy-gap law. The excited states are better oxidants and reductants than the ground states. The values of E^o(Re^V*-Re^IV) and E^o(Re^VI-Re^V*) in acetonitrile have been determined using spectroscopic and electrochemical data as well as by Stern-Volmer quenching experiments.

Full text of DOI:10.1039/DT9960002827

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