Sequential H/D Exchanges Resulting from Rollover-Cyclometallation during Photoirradiation of Rhodium(III) Complex in Methanol-d 4 .

Autor: Tanaka S; Department of Materials Sciences, Graduate School of Nanobioscience, Yokohama City University, 22-2 Seto, Kanazawa-ku, Yokohama, 236-0027, Japan., Hattori S; Department of Materials Sciences, Graduate School of Nanobioscience, Yokohama City University, 22-2 Seto, Kanazawa-ku, Yokohama, 236-0027, Japan., Shinozaki K; Department of Materials Sciences, Graduate School of Nanobioscience, Yokohama City University, 22-2 Seto, Kanazawa-ku, Yokohama, 236-0027, Japan.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2024 Nov 12; Vol. 30 (63), pp. e202402067. Date of Electronic Publication: 2024 Oct 29.
DOI: 10.1002/chem.202402067
Abstrakt: We present the photoreaction of newly prepared bis(6,6'-dimethyl-2,2'-bipyridine)(oxalato)rhodium(III) ([Rh(N N) 2 (ox)] + ) in CD 3 OD. Photoirradiation of this complex causes the dissociation of ox, followed by the formation of the unprecedented Rh(III) complex with Rh-H and Rh-C σ bonds, [Rh(N N)(C N)(H)(CD 3 OD)] + (C N=[6,6'-dimethyl-2,2'-bipyridine]-3-yl-κC 3 ,κN 1' ). This hydride formation and cyclometallation spontaneously proceed owing to the conflict between the steric hindrance arising from the methyl groups of N N and the driving force for the structural change due to [Rh(N N) 2 ] + formation. Although [Rh(N N)(C N)(H)(CD 3 OD)] + is initially converted to [Rh(N N) 2 ] + by photoirradiation, it is immediately regenerated by the rollover cyclometallation of the [Rh(N N) 2 ] + complex. [Rh(N N)(C N)(H)(CD 3 OD)] + undergoes H/D exchange for the H atoms in the Rh-H bond and at the 3, 3'-positions of the N N ligand during the photoirradiation. DFT calculations predict with reasonable certainty the spontaneous structural change of [Rh(N N) 2 ] + to [Rh(N N)(C N)(H)(CD 3 OD)] + and the subsequent photodriven Rh-C bond rupture leading to the formation of [Rh(N N) 2 ] + accompanied by H/D exchange reactions.
(© 2024 Wiley-VCH GmbH.)
Databáze: MEDLINE
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