Tsurugi Hayato, Mori Hiroki, Mori Haruna, Nakamoto Masami, Tanaka Shinji, Mashima Kazushi
Department of Chemistry, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan.
Innovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), Osaka University, Suita, Osaka 565-0871, Japan.
Dalton Trans. 2024 May 21;53(20):8546-8549. doi: 10.1039/d4dt00932k.
The Lewis basicity of a μ-oxo ligand for (μ-O)Rh(cod)M (cod = 1,5-cyclooctadiene) complexes was controllable by metal species on the μ-oxo ligand locating at the opposite site of the μ-oxo ligand. Coordination of the μ-oxo ligand of [(μ-O){Rh(cod)}(μ-O){Au(PPh)}][BF] (1) to [Au(PPh)] indicated sufficient Lewis basicity of the μ-oxo ligand in 1 to form [{(PhP)Au}(μ-O){Rh(cod)}(μ-O){Au(PPh)}][BF] (2). In contrast, the addition of Li to 1 induced elimination of the originally coordinated [Au(PPh)] due to the weak Lewis basicity of the μ-oxo ligand for (μ-O){Rh(cod)}(μ-O)Li(THF), in which a pentanuclear species, [{(PhP)Au}(μ-O){Rh(cod)}(μ-O){Li(THF)}][BF] (3), was assumed to be generated before the dissociation of [Au(PPh)].
对于(μ - O)[Rh(cod)](μ - O)M（cod = 1,5 - 环辛二烯）配合物，μ - 氧配体的路易斯碱性可通过位于μ - 氧配体相对位点的金属物种来控制。[(μ - O){Rh(cod)}(μ - O){Au(PPh)}][BF]（1）的μ - 氧配体与[Au(PPh)]配位表明1中μ - 氧配体具有足够的路易斯碱性以形成[{(PhP)Au}(μ - O){Rh(cod)}(μ - O){Au(PPh)}][BF]（2）。相反，向1中加入锂会导致原本配位的[Au(PPh)]消除，这是由于对于(μ - O){Rh(cod)}(μ - O)Li(THF)，μ - 氧配体的路易斯碱性较弱，其中在[Au(PPh)]解离之前假定生成了一种五核物种[{(PhP)Au}(μ - O){Rh(cod)}(μ - O){Li(THF)}][BF]（3）。
