Effect of distal metal species on lewis basicity of a μ3-oxo ligand in a doubly oxo-bridged (μ3-O)[Rh(cod)]3(μ4-O)M core

Hayato Tsurugi; Hiroki Mori; Haruna Mori; Masami Nakamoto; Shinji Tanaka; Kazushi Mashima

doi:10.1039/d4dt00932k

Effect of distal metal species on lewis basicity of a μ₃-oxo ligand in a doubly oxo-bridged (μ₃-O)[Rh(cod)]₃(μ₄-O)M core

Dalton Trans. 2024 May 21;53(20):8546-8549. doi: 10.1039/d4dt00932k.

Authors

Hayato Tsurugi^{1

2}, Hiroki Mori¹, Haruna Mori¹, Masami Nakamoto¹, Shinji Tanaka³, Kazushi Mashima⁴

Affiliations

¹ Department of Chemistry, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan. tsurugi@chem.eng.osaka-u.ac.jp.
² Innovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), Osaka University, Suita, Osaka 565-0871, Japan.
³ Interdisciplinary Research Center for Catalytic Chemistry (IRC3), National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Ibaraki 305-8565, Japan.
⁴ Graduate School of Pharmaceutical Sciences, Osaka University, Suita, Osaka 565-0871, Japan.

PMID: 38712880
DOI: 10.1039/d4dt00932k

Abstract

The Lewis basicity of a μ₃-oxo ligand for (μ₃-O)[Rh(cod)]₃(μ₄-O)M (cod = 1,5-cyclooctadiene) complexes was controllable by metal species on the μ₄-oxo ligand locating at the opposite site of the μ₃-oxo ligand. Coordination of the μ₃-oxo ligand of [(μ₃-O){Rh(cod)}₃(μ₄-O){Au(PPh₃)}][BF₄] (1) to [Au(PPh₃)]⁺ indicated sufficient Lewis basicity of the μ₃-oxo ligand in 1 to form [{(Ph₃P)Au}(μ₃-O){Rh(cod)}₃(μ₄-O){Au(PPh₃)}][BF₄] (2). In contrast, the addition of Li⁺ to 1 induced elimination of the originally coordinated [Au(PPh₃)]⁺ due to the weak Lewis basicity of the μ₃-oxo ligand for (μ₃-O){Rh(cod)}₃(μ₄-O)Li(THF)₃, in which a pentanuclear species, [{(Ph₃P)Au}(μ₃-O){Rh(cod)}₃(μ₄-O){Li(THF)₃}][BF₄] (3), was assumed to be generated in situ before the dissociation of [Au(PPh₃)]⁺.