25150-61-2Relevant articles and documents
Syntheses and Structures of [CH2(NCnH2n)2]Mo(CO)4 (n = 4,5) Complexes with Bis(cycloamine) Ligands Easily Prepared from CH2Cl2
Kyran, Samuel J.,Sanchez, Sergio G.,Arp, Christopher J.,Darensbourg, Donald J.
, p. 3598 - 3602 (2015)
Dipyrrolidylmethane, CH2(pyr)2, and dipiperidylmethane, CH2(pip)2, are synthesized via the condensation of their respective secondary amine precursors and dichloromethane at room temperature in the absence of light. Their use as chelating ligands is shown by the isolation and complete characterization of [CH2(pyr)2]Mo(CO)4 and [CH2(pip)2]Mo(CO)4 complexes. X-ray analysis reveals the methylene bis(cycloamines) to possess a sharp bite angle between 61° and 63° and a strong steric impact on the surrounding carbonyl ligands as a result of their ring conformations. (Chemical Equation Presented).
ENANTIOSELECTIVE AMINATION AND ETHERIFICATION___________________
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Page 70, (2010/02/06)
The present invention is directed to a catalyst composition, comprising: (1) a catalyst precursor having the general structure MSXn wherein M is a transition metal selected from the group consisting of iridium, molybdenum, and tungsten; S is a coordinating ligand; X is a counterion; and n is an integer from 0 to 5; and (2) a phosphoramidite ligand having the structure wherein O-Cn-O is an aliphatic or aromatic diolate and wherein R1, R2, R3 and R4 are selected from the group consisting of substituted or unsubstituted aryl groups, substituted or unsubstituted heteroaryl groups, substituted or unsubstituted aliphatic groups, and combinations thereof, with the proviso that at least one of R1, R2, R3, or R4 must be a substituted or unsubstituted aryl or heteroaryl group. The present invention is also directed to activated catalysts made from the above catalyst composition, as well as methods of allylic amination and etherification using the above catalysts.
KINETICS AND ISOTOPE EFFECTS OF THE β-ELIMINATION REACTIONS OF 1,1-DICHLORO-2,2-BIS-(4-NITROPHENYL)-ETHANE PROMOTED BY PIPERIDINE, PYRROLIDINE AND QUINUCLIDINE BASES IN ACETONITRILE SOLVENT
Dworniczak, Miroslaw,Jarczewski, Arnold
, p. 599 - 604 (2007/10/02)
The kinetics of the reaction of 1,1-dichloro-2,2-bis-(4-nitrophenyl)ethane (I) with piperidine, pyrrolidine and quinuclidine bases in acetonitrile solvent are reported.The reaction is complex, leading to 1-amino-2,2-bis-(4-nitrophenyl)ethene (III) as the final product via the intermediate 1-chloro-2,2-bis-(4-nitrophenyl)ethene (II).The reaction shows a 100percent conversion of the substrate (I) to (II).The rate of reaction of I to II is several times faster than II to III, allowing for kinetic measurements of the initial step.The entropies of activation (ΔS*/J mol-1K-1) are negative and large (-184, -149, -145) for the reaction with piperidine, pyrrolidine and quinuclidine respectively.The free enthalpy of activation (ΔG*/kJ mol-1) are rather small, oscillating between 75-79 kJ mol-1.The kinetic isotope effects kH/kD fall between 6.8 and 7.6 at 20 deg C.The results obtained are interpreted in terms of E2H with a contribution of (E1cB)I mechanism.