Transient absorption spectral evidence for phenyl nitrene as the chain propagator in the photo-initiated autocatalytic chain decomposition of phenyl azide and phenyl isocyanate

Identification and Chemistry of Phenylnitrene in Premixed Pyridine/Oxygen/Argon Flame with Tunable Synchrotron Photoionization

“…According to the calculations of this study, the two spin-parallel electrons of 3 PhN is 120.607 • , a little larger than the SCF and CISD calculations [7]. When in doublet ionic state 2 B 2 PhN + , this angle becomes 1.133 • smaller.…”

“…Many previous investigations of PhN were related to spectroscopy studies [1,4,10,11]. In 1966, Reiser et al reported the first electronic spectrum of PhN [1] and their studies were extended by subsequent researchers [2][3][4]. Porter and Ward assigned a UV absorption band of triplet PhN in 1968, which was supported by other groups [5,6,12].…”

“…Experimental and theoretical studies of phenylnitrene (PhN) have been subjects of great interest to both organic and physical chemists over the past 40 years [1][2][3][4][5][6] because of its useful synthetic and industrial applications [7]. PhN is a diradical with C 2v symmetry, which is generally produced by pyrolysis or photolysis of phenyl azide [1,[7][8][9].…”

A Singlet Phosphinidene Stable at Room Temperature

“…Because of the sensitivity of PP bonds to acidic and reducing conditions, we chose a photolytic method to prepare the desired phosphinidenes A. Transient carbenes and nitrenes are usually generated from the corresponding diazo derivatives and azides, but there are a few examples using ketenes 29 and isocyanates, 30,31 respectively, as precursors. By analogy, we first prepared the phosphaketene 2a by mixing the chlorodiazaphospholidine 1a, 25 featuring Dipp groups at nitrogen, with the 2-phosphaethynolate anion (Figure 2, top; Figures S1-S3).…”

Main-Group Metallomimetics: Transition Metal-like Photolytic CO Substitution at Boron

“…Equally important is the ability of carbonyl ligands to liberate selectively a coordination site by photodissociation from a metal center in a process that is a crucial step of many catalytic reactions . By contrast, few CO adducts of the main group elements are known, and π-backbonding is not significant in many of them. − CO photodissociation has also found limited applications in main group chemistry, notably to generate nitrenes and phosphinidenes from isocyanates and phosphaketenes. − More recently, associative CO substitution at a phosphaketene by different Lewis bases was demonstrated …”