Recent developments in the chemistry of homoleptic azido complexes of the main group elements

Borane Adducts of Hydrazoic Acid and Organic Azides: Intermediates for the Formation of Aminoboranes

“…"Atthe beginning of azide chemistry,HN 3 was assumed to have ac yclic 1H-triazirine structure,t hat is,athreemembered N 3 ring attached to ahydrogen atom. [6,[11][12][13][14][15][16][17][18][19] Thef irst report on the reaction of organic azides with borane (Et 3 B) was published by Brown and co-workers in 1971. [8,9] Only in 2011, the solid-state structure of HN 3 confirmed unequivocally the presence of hydrogen-bonded tetramers of (HN 3 ) 4 in an early planar network of eight-membered rings always featuring trans-bent HN 3 molecules.…”

Reductive Coupling and Loss of N2 from Magnesium Diazomethane Derivatives

“…The pseudo-tetrahedral Mg II centers are coordinated to the NacNac Mes ligand and to alternating nitrogen atoms of the N 4 linkage. The MgÀNd istances for the NacNac Mes ligands were found to range from 2.006(3) to 2.025(3) ,w hereas the MgÀN to the reduced diazomethane are 2.178(4), 2.010(4), 2.139(4), and 2.024(5) .T he correspondingN -Mg-N angles in the sixand four member-rings were found to be 94.41 (12), 96.54(12), 63.84 (16), and6 4.51(16)8,r espectively.T he chelation in the MgN 3 rings give rise to transannularM g ÀNd istances of 2.588(5) and 2.551(4) .T he exocycle Ph 2 Cf ragments give rise to CÀNd istances of 1.351(6) and 1.335(5) ,w hereas the adjacent NÀNd istances were found to be 1.316(6) and 1.327(6) with ac entral NÀNd istance of 1.454(6) .I ti sn oteworthy that the central CN 4 Cl inkage is approximately co-planar suggestive of extended conjugation,w hereas the phenyl rings on either end are canteda ta ngles of 27.78,5 2.58,3 3.28,a nd 43.68 with respective to the CN 4 Cp lane.…”

“…[10] Otherm ain-group azides [11] are isolable and lose N 2 to give element-nitrided erivatives. Similarly,p hotochemical reactions of azide precursors have been used in the synthesis of heavier main-group-Nf rag-mentsa nd shown to often prompts ubstituent migration to N. [12] Other main-group speciest hat evolveN 2 are rare.T he speciesP h 3 PNNPPh 3 is reported to lose N 2 at 215 8C. [13] We and others have shown that reactions of diazomethanesw ith boranes effect carbene insertion into BÀCb onds with loss of N 2 .…”

Azide Chemistry – An Inorganic Perspective, Part I Metal ­Azides: Overview, General Trends and Recent Developments

“…), on the other 70. The former scope has fully and adequately been covered in the brand‐new review article by Portius and Davis 71…”