349-75-7Relevant articles and documents
Evidence for the Incursion of Intermediates in the Hydrolysis of Tertiary, Secondary, and Primaty Substrates
Blandamer, Michael Jesse,Robertson, Ross Elmore,Scott, John Marshall William,Vrielink, Alice
, p. 2585 - 2592 (1980)
The temperature dependence related to a series of solvolytic displacement reactions of primary, secondary, and tertiary carbon centers are examined using a new equation.The equation is derived by integrating the van't Hoff isochore in a form related to the absolute rate theory on the assumption that the heat capacity of activation (ΔGp) is constant.Unexpectedly, the new equation is capable of correctly sensing changes in ΔCp with temperature.The new equation is used to show that in some instances ΔCp is partly abnormal and derives from the nonunitary nature of the displacement in a way outlined previously by Albery and Robinson.The significance of this new mechanistic tool is considered in relation to the displacement reaction of 2-bromopropane in heavy water and the reactions of adamantyl nitrate, tert-butyl chloride, S-propyl methanesulphonate, m-trifluoromethylbenzyl nitrate, and ethyl bromide with ordinary water.
Nickel(II) Catalyzed Hydroboration: A Route to Selective Reduction of Aldehydes and N-Allylimines
Hossain, Istiak,Schmidt, Joseph A. R.
, p. 1877 - 1884 (2020/05/25)
A cationic [(iminophosphine)nickel(allyl)]+ complex was found to be sufficiently electrophilic to activate aldehydes and N-allylimines to undergo hydroboration with pinacolborane (HBpin) under mild reaction conditions. The catalyst displayed excellent selectivity toward aldehydes in the presence of ketones. A wide variety of functional groups were tolerated, including halogens, NO2, CN, OMe, and alkenes for both aldehydes and imines. Electron-rich substrates were found to be significantly more reactive than their electron poor counterparts, a feature that was correlated to their enhanced ability to coordinate to the Lewis acidic nickel center.
Study of Precatalyst Degradation Leading to the Discovery of a New Ru0 Precatalyst for Hydrogenation and Dehydrogenation
Anaby, Aviel,Schelwies, Mathias,Schwaben, Jonas,Rominger, Frank,Hashmi, A. Stephen K.,Schaub, Thomas
supporting information, p. 2193 - 2201 (2018/07/25)
The complex Ru-MACHO (1) is a widely used precatalyst for hydrogenation and dehydrogenation reactions under basic conditions. In an attempt to identify the active catalyst form, 1 was reacted with a strong base. The formation of previously unreported species was observed by NMR and mass spectrometry. This observation indicated that complex 1 quickly degraded under basic conditions when no substrate was present. X-ray crystallography enabled the identification of three complexes as products of this degradation of complex 1. These complexes suggested degradation pathways which included ligand cleavage and reassembly, along with reduction of the ruthenium atom. One of the decomposition products, the Ru0 complex [Ru(N(CH2CH2PPh2)3)CO] (5), was prepared independently and studied. 5 was found to be active, entirely additive-free, in the acceptorless dehydrogenation of aliphatic alcohols to esters. The hydrogenation of esters catalyzed by 5 was also demonstrated under base-free conditions with methanol as an additive. Protic substrates were shown to add reversibly to complex 5, generating RuII-hydrido species, thus presenting a rare example of reversible oxidative addition from Ru0 to RuII and reductive elimination from RuII to Ru0.