Recently I am researching about H BOND ACTIVATION; SELECTIVE CATALYTIC-HYDROGENATION; HEXAHYDRIDE COMPLEX; LIGANDS PREPARATION; N-H; DEHYDROGENATION; HYDRIDE; VINYLIDENE; RUTHENIUM; REACTIVITY, Saw an article supported by the MINECO of Spain [CTQ2017-82935-P, RED2018-102387-T]; Gobierno de AragonGobierno de Aragon [E06_20R, LMP148_18]; FEDEREuropean Commission; European Social FundEuropean Social Fund (ESF). Category: benzodioxans. Published in AMER CHEMICAL SOC in WASHINGTON ,Authors: Babon, JC; Esteruelas, MA; Lopez, AM; Onate, E. The CAS is 86-29-3. Through research, I have a further understanding and discovery of 2,2-Diphenylacetonitrile
The transformation of alkyl nitriles to symmetrical and asymmetrical secondary aliphatic amines promoted by the hexahydride complex OsH6 ((PPr3)-Pr-i)(2) (1) is described, and the mechanisms of the reactions involved are established. Complex 1 catalyzes the aforementioned transformations of aryl-, pyridyl-, and alkoxy-functionalized alkyl nitriles with linear or branched chains. The formation of the secondary amines involves primary imines, primary amines, and secondary imines as organic intermediates. The reactions take place under mild conditions (toluene, 100 degrees C, and 4 bar of H-2). Stoichiometric reactions of 1 with pivalonitrile and 2-methoxyacetonitrile have allowed us to isolate the trihydride azavinylidene derivatives OsH3{=N=CHR}((PPr3)-Pr-i)(2) (R = Bu-t (3), CH2OMe (4)). Their formation involves the insertion of the N-C triple bond of the substrates into an Os-H bond of the unsaturated tetrahydride OsH4 ((PPr3)-Pr-i)(2) (A), which is generated by reductive elimination of H-2 from the hexahydride precursor. The reaction of these trihydride azavinylidene species with H-2 is the key step for the reduction of the N-C triple bond of the nitriles. In the absence of H-2, the attack of A to the azavinylidene ligand produces the rupture of its C(sp(2))-C(sp(3)) bond. As a consequence of this attack and the presence of primary imines and amines in the reaction media, the binuclear complexes ((PPr3)-Pr-i)(2) H4Os(mu-CN)OsH3{kappa(1)-N-(NH= CHCH2OMe)}((PPr3)-Pr-i)(2) (5) and ((PPr3)-Pr-i)(2)H4Os(mu-CN)OsH3{kappa(1)-N-(NH2CH2CH2OMe)}((PPr3)-Pr-i)(2) (6) have been isolated and characterized by X-ray diffraction analysis, for 2-methoxyacetonitrile. DFT calculations reveal noticeable similarities between the hydrogenations of nitriles to primary imines and those of primary imines to primary amines.
Category: benzodioxans. About 2,2-Diphenylacetonitrile, If you have any questions, you can contact Babon, JC; Esteruelas, MA; Lopez, AM; Onate, E or concate me.
Reference:
Benzodioxan,
,1,4-Benzodioxane | C8H8O2 – PubChem