Kinetic Isotope Effects in the Thermal C2−C6Cyclization of Enyne-allenes:  Experimental Evidence Supports a Stepwise Mechanism

2005 ◽  
Vol 70 (12) ◽  
pp. 4865-4868 ◽  
Author(s):  
Michael Schmittel ◽  
Chandrasekhar Vavilala
Keyword(s):  
Experimental Evidence ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Stepwise Mechanism ◽  
Kinetic Isotope

scholarly journals Experimental Evidence for Heavy-Atom Tunneling in the Ring-Opening of Cyclopropylcarbinyl Radical from Intramolecular12C/13C Kinetic Isotope Effects

2010 ◽  
Vol 132 (36) ◽  
pp. 12548-12549 ◽  
Author(s):  
Ollie M. Gonzalez-James ◽  
Xue Zhang ◽  
Ayan Datta ◽  
David A. Hrovat ◽  
Weston Thatcher Borden ◽  
...  
Keyword(s):  
Experimental Evidence ◽  
Ring Opening ◽  
Isotope Effects ◽  
Heavy Atom ◽  
Kinetic Isotope Effects ◽  
Kinetic Isotope

Intramolecular and Intermolecular Kinetic Isotope Effects (KIE) in the Nitrosoarene Ene Reaction:  Experimental Evidence for Reversible Intermediate Formation

2003 ◽  
Vol 68 (6) ◽  
pp. 2420-2425 ◽  
Author(s):  
Waldemar Adam ◽  
Oliver Krebs ◽  
Michael Orfanopoulos ◽  
Manolis Stratakis ◽  
Georgios C. Vougioukalakis
Keyword(s):  
Experimental Evidence ◽  
Isotope Effects ◽  
Intermediate Formation ◽  
Kinetic Isotope Effects ◽  
Ene Reaction ◽  
Kinetic Isotope

scholarly journals Kinetics and mechanism of the anilinolysis of aryl phenyl isothiocyanophosphates in acetonitrile

2013 ◽  
Vol 9 ◽  
pp. 615-620 ◽  
Author(s):  
Hasi Rani Barai ◽  
Hai Whang Lee
Keyword(s):  
Isotope Effects ◽  
Bond Formation ◽  
Kinetic Studies ◽  
Kinetic Isotope Effects ◽  
Bond Breaking ◽  
Stepwise Mechanism ◽  
Kinetic Isotope ◽  
Energy Relationships ◽  
Break Region ◽  
Rate Limiting

Kinetic studies on the reactions of Y-aryl phenyl isothiocyanophosphates with substituted X-anilines and deuterated X-anilines were carried out in acetonitrile at 55.0 °C. The free-energy relationships with X in the nucleophiles were biphasic concave upwards with a break region between X = H and 4-Cl, giving unusual positive ρX and negative βX values with less basic anilines (X = 4-Cl and 3-Cl). A stepwise mechanism with rate-limiting bond breaking for more basic anilines and with rate-limiting bond formation for less basic anilines is proposed based on the positive and negative ρXY values, respectively. The deuterium kinetic isotope effects involving deuterated anilines (XC6H4ND2) showed primary normal and secondary inverse DKIEs for more basic and less basic anilines, rationalized by frontside attack involving hydrogen-bonded four-center-type TSf and backside attack TSb, respectively. The positive ρX values with less basic anilines are substantiated by the tight TS, in which the extent of the bond formation is great and the degree of the bond breaking is considerably small.

Kinetic Isotope Effects Provide Experimental Evidence for Proton Tunneling in Methylammonium Lead Triiodide Perovskites

2017 ◽  
Vol 139 (45) ◽  
pp. 16359-16364 ◽  
Author(s):  
Yan-Fang Chen ◽  
Yu-Tang Tsai ◽  
Lionel Hirsch ◽  
Dario M. Bassani
Keyword(s):  
Experimental Evidence ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Proton Tunneling ◽  
Kinetic Isotope

Primary and secondary kinetic isotope effects in proton (H+/D+) and chloronium ion (35Cl+/37Cl+) affinities

2001 ◽  
Vol 36 (10) ◽  
pp. 1140-1148 ◽  
Author(s):  
F�bio Cesar Gozzo ◽  
Marcos N. Eberlin
Keyword(s):  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Kinetic Isotope

Theoretical Simulations of Heavy-Atom Kinetic Isotope Effects in Aliphatic Claisen Rearrangement

2020 ◽  
Vol 124 (51) ◽  
pp. 10678-10686
Author(s):  
Yuqing Xu ◽  
Kin-Yiu Wong ◽  
Meishan Wang ◽  
Desheng Liu ◽  
Wenkai Zhao ◽  
...  
Keyword(s):  
Claisen Rearrangement ◽  
Isotope Effects ◽  
Heavy Atom ◽  
Kinetic Isotope Effects ◽  
Kinetic Isotope ◽  
Theoretical Simulations

Direct dynamics calculations of reaction rate and kinetic isotope effects in enzyme catalysed reactions

2002 ◽  
Vol 122 ◽  
pp. 223-242 ◽  
Author(s):  
Gary Tresadern ◽  
Sara Nunez ◽  
Paul F. Faulder ◽  
Hong Wang ◽  
Ian H. Hillier ◽  
...  
Keyword(s):  
Reaction Rate ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Direct Dynamics ◽  
Kinetic Isotope
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