Fuentes， Paul AU - Fuentes， AMZ ， abstract = "This paper reports experimental and computational studies on the mechanism of a rhodium-catalysed hydroformylation that is selective for branched aldehyde products from unbiased alkene substrates. This highly unusual selectivity relies on a phospholane-phosphite ligand prosaically called BOBPHOS. Kinetic studies using in situ high pressure IR (HPIR) and the reaction progress kinetic analysis methodology suggested two steps in the catalytic cycle were involved as turnover determining. Negative order in CO and positive orders in alkene and H2 were found and the effect of hydrogen and carbon monoxide partial pressures on selectivity were measured. Labeling studies found rhodium hydride addition to the alkene to be largely irreversible. Detailed spectroscopic HPIR and NMR characterization of activated rhodium-hydrido dicarbonyl species were carried out. In the absence of H2， day= "8"， J. A.， José A. AU - Crawford， 15921–15932. https://doi.org/10.1021/jacs.7b09164 Dingwall， 08.11.2017， Buehl M ， Luke et al. In: Journal of the American Chemical Society 。
pages= "15921–15932"， reaction of the rhodium-hydrido dicarbonyl with allylbenzene allowed further detailed spectroscopic characterization of four- and five-coordinate rhodium-acyl species. Under single-turnover conditions the ratios of branched to linear acyl species were preserved in the final ratios of aldehyde products. Theoretical investigations uncovered unexpected stabilizing CH-π interactions between the ligand and substrate which influenced the high branched selectivity by causing potentially low energy pathways to become unproductive. Energy span and degree of TOF control analysis strongly support experimental observations and mechanistic rationale. A three-dimensional quadrant model was built to represent the structural origins of regio- and enantioselectivity. UR - U2 - 10.1021/jacs.7b09164 DO - 10.1021/jacs.7b09164 M3 - Article SN - 0002-7863 VL - 139 SP - 15921 EP - 15932 JO - Journal of the American Chemical Society JF - Journal of the American Chemical Society IS - 44 ER - Dingwall P， Luke AU - Slawin， M. ， Crawford L ， L ， \{Alexandra Martha Zoya\} and Michael Buehl and Clarke， pp. 15921–15932. https://doi.org/10.1021/jacs.7b09164 Understanding a hydroformylation catalyst that produces branched aldehydes from alkyl alkenes. / Dingwall， Slawin， Dingwall， note= "The authors thank the EPSRC for funding (EP/M003868/1). "， Fuentes。
139(44)。
author = "Paul Dingwall and Fuentes， M Clarke， year= "2017"， No. 44. pp. 15921–15932. @article{f49310723b634e1ab262d06ccfbab29b， doi= "10.1021/jacs.7b09164"， reaction of the rhodium-hydrido dicarbonyl with allylbenzene allowed further detailed spectroscopic characterization of four- and five-coordinate rhodium-acyl species. Under single-turnover conditions the ratios of branched to linear acyl species were preserved in the final ratios of aldehyde products. Theoretical investigations uncovered unexpected stabilizing CH-π interactions between the ligand and substrate which influenced the high branched selectivity by causing potentially low energy pathways to become unproductive. Energy span and degree of TOF control analysis strongly support experimental observations and mechanistic rationale. A three-dimensional quadrant model was built to represent the structural origins of regio- and enantioselectivity. "， Slawin， reaction of the rhodium-hydrido dicarbonyl with allylbenzene allowed further detailed spectroscopic characterization of four- and five-coordinate rhodium-acyl species. Under single-turnover conditions the ratios of branched to linear acyl species were preserved in the final ratios of aldehyde products. Theoretical investigations uncovered unexpected stabilizing CH-π interactions between the ligand and substrate which influenced the high branched selectivity by causing potentially low energy pathways to become unproductive. Energy span and degree of TOF control analysis strongly support experimental observations and mechanistic rationale. A three-dimensional quadrant model was built to represent the structural origins of regio- and enantioselectivity. AB - This paper reports experimental and computational studies on the mechanism of a rhodium-catalysed hydroformylation that is selective for branched aldehyde products from unbiased alkene substrates. This highly unusual selectivity relies on a phospholane-phosphite ligand prosaically called BOBPHOS. Kinetic studies using in situ high pressure IR (HPIR) and the reaction progress kinetic analysis methodology suggested two steps in the catalytic cycle were involved as turnover determining. Negative order in CO and positive orders in alkene and H2 were found and the effect of hydrogen and carbon monoxide partial pressures on selectivity were measured. Labeling studies found rhodium hydride addition to the alkene to be largely irreversible. Detailed spectroscopic HPIR and NMR characterization of activated rhodium-hydrido dicarbonyl species were carried out. In the absence of H2， Alexandra Martha Zoya AU - Buehl， Clarke， no. 44， title= "Understanding a hydroformylation catalyst that produces branched aldehydes from alkyl alkenes"， Matthew L N1 - The authors thank the EPSRC for funding (EP/M003868/1). PY - 2017/11/8 Y1 - 2017/11/8 N2 - This paper reports experimental and computational studies on the mechanism of a rhodium-catalysed hydroformylation that is selective for branched aldehyde products from unbiased alkene substrates. This highly unusual selectivity relies on a phospholane-phosphite ligand prosaically called BOBPHOS. Kinetic studies using in situ high pressure IR (HPIR) and the reaction progress kinetic analysis methodology suggested two steps in the catalytic cycle were involved as turnover determining. Negative order in CO and positive orders in alkene and H2 were found and the effect of hydrogen and carbon monoxide partial pressures on selectivity were measured. Labeling studies found rhodium hydride addition to the alkene to be largely irreversible. Detailed spectroscopic HPIR and NMR characterization of activated rhodium-hydrido dicarbonyl species were carried out. In the absence of H2，。
JA， José A. ; Crawford， P， \{Jos{\'e} A.\} and Luke Crawford and Slawin， Paul; Fuentes， issn= "0002-7863"， number = "44"， M. L. (2017). Understanding a hydroformylation catalyst that produces branched aldehydes from alkyl alkenes . Journal of the American Chemical Society ， Crawford， Crawford， Luke et al. / Understanding a hydroformylation catalyst that produces branched aldehydes from alkyl alkenes . In: . 2017 ; Vol. 139， Clarke ML . Understanding a hydroformylation catalyst that produces branched aldehydes from alkyl alkenes . Journal of the American Chemical Society . 2017 Nov 8;139(44):15921–15932. Epub 2017 Oct 25. doi: 10.1021/jacs.7b09164 ， publisher = "American Chemical Society (ACS)"， Buehl， No. 44， p. 15921–15932. Research output : Contribution to journal › Article › peer-review TY - JOUR T1 - Understanding a hydroformylation catalyst that produces branched aldehydes from alkyl alkenes AU - Dingwall， L. ， ML 2017， Michael AU - Clarke， A. M. Z. ， Journal of the American Chemical Society ， Fuentes JA， journal = "Journal of the American Chemical Society"。
Paul ; Fuentes， month= nov， } Dingwall， language = "English"， ' Understanding a hydroformylation catalyst that produces branched aldehydes from alkyl alkenes '， Slawin AMZ 。
volume = "139"， Buehl， \{Matthew L\}"， vol. 139， P.， José A.; Crawford， Vol. 139。