Utilization of molecular nitrogen in the synthesis of organic amines and nitriles

Abstract

National Institutes of Health (Grant No. GM 13797) for financial support.(9) In the pictorial presentation of titanocene monomer, the structure featuring noncoplanar CtHs units is used, as suggested by Hiickel calculations of Brintzinger and Bartell.8

Early-Transition-Metal-Mediated Activation and Transformation of White Phosphorus

“…While much research has been targeted at the direct incorporation of N 2 -derived nitrogen atoms into main group molecules, the analogous chemistry with elemental phosphorus has been explored far less. [69][70][71][72][73][74] The incorporation of P 4 -derived phosphorus atoms into organic frameworks by P-atom transfer reactions mediated by transition-metal complexes could circumvent the need for PCl 3 …”

Activation of nitrogen for organic synthesis

“…Later, van Tamelen and Rudler [8] succeeded in obtaining diethylamine and benzonitrile from diethylketone and benzoyl chloride, respectively using Cp 2 TiCl 2 and Mg under nitrogen (Eq. (2)).…”

“…Since the handling of complex 2 was easier than that of 1, we used 2 as a nitrogenation agent and succeeded in synthesizing various heterocycles (Eqs. (8) and (9) …”

Electrochemical Studies of Organotitanium Nitrogen Fixation Systems

“…The identity of the reduced titanium species responsible for nitrogen fixation has not been definitely established, however, although numerous suggestions have been made (Table 1). Brintzinger and co-workers (12,13) have provided supporting evidence for the role of titanocene monomer in the coordination step, originally suggested by van Tamelen and co-workers (5)(6)(7)(8), by isolation of the intensely blue complex [(n-Cp),Ti],N, stable at room temperature. It is not certain, however, that the identity or even the oxidation state of the active titanium intermediate is the same for all the reducing systems described in Table 1.…”