期刊
ACS CATALYSIS
卷 11, 期 15, 页码 9043-9051出版社
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.1c02238
关键词
catalyzed hydroboration; hemilabile; manganese; metal-ligand cooperation; DFT
资金
- NSERC [2019-05959]
- OGS award from the province of Ontario
- Institute for Basic Science in Korea [IBS-R010-A1]
The study describes the chemoselective hydroboration of carbonyls using the paramagnetic bis-amido Mn[(SNSMe)-N-Me](2) complex (1). It was found that the bifunctional amido bis(thioether) ligand L plays a crucial role in the success of the reaction, while also ruling out the possibility of side reactions.
A combined experimental and mechanistic study of the chemoselective hydroboration of carbonyls by the paramagnetic bis-amido Mn[(SNSMe)-N-Me](2) complex (1) is described. The catalyst allows for room-temperature hydroboration of carbonyls at low catalyst loadings (0.1 mol %) and reaction times (<30 min). A series of mechanistic studies highlight the significance of bifunctional amido bis(thioether) ligand L to the success of the reaction, insight otherwise difficult to attain in paramagnetic systems. Kinetic studies using variable time normalization analysis revealed no unusual reaction kinetics, indicating the absence of side reactions. A borylated analogue of L was observed and characterized via mass spectrometry. Density functional theory (DFT) calculations showed that thioether hemilability of L is crucial during catalysis for providing the active coordinating site. Also, the frequently proposed Mn-H intermediate was found not to be the active species responsible for catalysis. Instead, an inner-sphere reaction pathway with carbonyl coordination to the metal center and amido-promoted B-H reactivity is proposed to be operative.
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