Low‐Temperature Isolation of An Azidophosphenium Cation

Phosphine and carbene azido-cations: [(L)N3]+and [(L)2N3]+

“…The molecular structure of 1 shows a distorted tetrahedral environment about the phosphorus atom with angles at P ranging from 102.3(1)–112.6(1)°. The P(1)–N(1) bond length of 1.651(2) Å is shorter than those observed in azido-substituted phosphenium cations (1.67 Å) 22 and azido-phosphines (1.73 Å), 23 consistent with the electron deficient nature of the phosphonium center and the strongly polarized nature of the P–N bond. The azido moiety shows an N(1)–N(2)–N(3) angle that slightly deviates from the ideal 180° (172.4(2)°) while the N(1)–N(2) (1.260(2) Å) and N(2)–N(3) bond length (1.114(2) Å) are in the expected range for azide substituents.…”

“…The azido moiety shows an N(1)–N(2)–N(3) angle that slightly deviates from the ideal 180° (172.4(2)°) while the N(1)–N(2) (1.260(2) Å) and N(2)–N(3) bond length (1.114(2) Å) are in the expected range for azide substituents. Compound 1 is a rare example of a crystallographically characterized salt of a cationic azido-phosphonium species 24 while several neutral, azido-substituted P( iii ) and P( v ) derivatives have been reported to date. 25 Other examples of monocationic nitrogen species, reported in the literature, include diazonium ions, 26 the homoleptic [N 5 ] + of Christe, 27 [N 2 F] + , 28 Hünig's stable triazenium ions [R 2 N 3 R 2 ] + 29 and aminodiazonium ions of the form [(R 2 N)N 2 ] + 30 (R = H, silyl, alkyl, aryl).…”

The chemistry of cationic polyphosphorus cages – syntheses, structure and reactivity

“… 19 Phosphenium ions of type 6 + featuring one amino-substituent are borderline cases between both of the aforementioned types and are only scarcely investigated. Only a few fully characterized derivatives are reported to date bearing either (pseudo-) halogens 20 or sterically demanding aryl-moieties 21 as the second substituent R′ on phosphorus ( Fig. 3 ).…”

Synthesis of Aminobismuthanes via Me3SnCl Elimination

“…Because Me 3 SnCl is readily eliminated from amines, N-trimethylstannyl anilines are considered as promising starting materials for the synthesis of low-valent inter-pnictogen compounds. Since our group is especially interested in nitrogenrich heavy pnictogen species, [23][24][25][26][27][28][29][30][31][32][33][34] we wanted to investigate The elimination of the Me 3 Si group could not be facilitated, [33] in contrast to results obtained with lighter homologues, RN(SiMe 3 )ECl 2 (E = P, As; R = Mes*). [25,29,34] Hence, we hoped that the elimination of Me 3 SnCl might represent a more favorable reaction pathway.…”