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- W2565352435 endingPage "593" @default.
- W2565352435 startingPage "583" @default.
- W2565352435 abstract "The noninnocent 2-diphenylphosphino-benzenethiolate (DPPBT) ligand containing both phosphorus and sulfur donors delocalizes the electron density in a manner reminiscent of dithiolenes. The electronic structure of the [ReL3]n (L = DPPBT, n = 0, 1+, 2+) complexes was probed with density-functional theory (DFT) and high-level ab initio methods including complete active space self-consistent field (CASSCF and CASPT2) and coupled cluster (CCSD and CCSD(T)). DFT predicts a slight preference for a closed-shell (CS) singlet ground state for the neutral [ReL3]0 and stronger preferences for low-spin ground states for the oxidized [ReL3]+ and [ReL3]2+. High-level ab initio methods confirm a CS singlet with a Re(III) (d4, S = 0) center as the ground state of [ReL3]0. Thus, this neutral Re species has considerably less thiyl radical character than the valence isoelectronic [RuL3]+, which is mainly a Ru(III) (d5, S = 1/2) anti-ferromagnetically (AF) coupled to a thiyl radical (S = 1/2). However, the oxidized derivatives [ReL3]+ and [ReL3]2+ show significant metal-stabilized thiyl radical character like [RuL3]+. Both [ReL3]+ and [ReL3]2+ have major contributions from Re(III) (d4, S = 1) centers AF coupled to thiyl and dithiyl DPPBT ligands. These findings are consistent with the experimental chemistry as [RuL3]+, [ReL3]+, and [ReL3]2+ can add ethylene to form the new C-S bonds, but [ReL3]0 cannot. The thiyl radicals on the S2 position (the S trans to a P donor) serve as the intrinsic electron acceptors in the actual ethylene addition reactions with Ru and Re tris(thiolate) complexes." @default.
- W2565352435 created "2017-01-06" @default.
- W2565352435 creator A5085920995 @default.
- W2565352435 date "2016-12-21" @default.
- W2565352435 modified "2023-10-13" @default.
- W2565352435 title "The Distinctive Electronic Structures of Rhenium Tris(thiolate) Complexes, an Unexpected Contrast to the Valence Isoelectronic Ruthenium Tris(thiolate) Complexes" @default.
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