The first crystal structures of the highly energetic tetraazidoborate anion and boron triazide adducts with quinoline and pyrazine as well as of tetramethylpiperidinium azide have been determined. Synthesis procedures and thorough characterization by spectroscopic methods of these hazardous materials are given. Quantum chemical calculations were carried out for B(N(3))(4)(-), B(N(3))(3), C(5)H(5)N.B(N(3))(3), (N(3))(3)B.NC(4)H(4)N.B(N(3))(3), and the hypothetical C(3)H(3)N(3).[B(N(3))(3)](3) at HF, MP2, and B3-LYP levels of theory. The structure of tetraazidoborate was optimized to S(4) symmetry and confirmed the results obtained from the X-ray diffraction analysis. The dissociation enthalpies for the pyridine (model for quinoline) as well as for the pyrazine adduct were calculated. For pyridine-boron triazide a value of 10.0 kcal mol(-1) (for pyrazine-bis(boron triazide) an average of 2.35 kcal mol(-1) per BN unit) was obtained.

The literature known, but not fully characterized, silver dinitramide transfer reagents AgN(NO 2 ) 2 (1), [Ag(NCCH 3 )]-[N(NO 2 ) 2 ] (2), and [Ag(py) 2 ][N(NO 2 ) 2 ] (3) have been investigated by 109 Ag, 14 N NMR and vibrational spectroscopy (IR, Raman). In addition, the poorly understood [Cu(NH 3 ) 4 ][N(NO 2 ) 2 )] 2 (4) and [Pd(NH 3 ) 4 ][N(NO 2 ) 2 ] 2 , (5) have also been prepared and characterized by 14 N NMR and vibrational spectroscopy (IR, Raman). Synthese, Charakterisierung und Kristallstrukturen von Cu-, Ag-und Pd-DinitramidsalzenInhaltsübersicht. Die aus der Literatur bekannten, aber nicht völlig charakterisierten Silberdinitramid-Transferreagenzien AgN(wurden mittels 109 Ag-, 14 N-NMR und IR-sowie Raman-Spektroskopie 1) present address: Glasgow, untersucht. Ferner wurden die wenig verstandenen Verbindungen [Cu(NH 3 ) 4 ][N(NO 2 ) 2 )] 2 (4) und [Pd(NH 3 ) 4 ][N(NO 2 ) 2 ] 2 (5) dargestellt und charakterisiert ( 14 N-NMR, IR, Raman). Die Strukturen von 2 Ϫ 5 wurden röntgenographisch bestimmt. dinitramide transfer reagents [5]. AgN(NO 2 ) 2 (1), [Ag(NCCH 3 )][N(NO 2 ) 2 ] (2) and [Ag(py) 2 ][N(NO 2 ) 2 ] (3) were first prepared by Lykanov [1], however, these compounds were only characterized by elemental analysis and melting point. Therefore, we have undertaken the first extensive study of 1Ϫ3, in order to fully characterize these salts and furthermore to investigate their ability to act as dinitramide transfer reagents. Characterization included 109 Ag, 14 N NMR, vibrational spectroscopy (IR, Raman) and X-ray diffraction studies (of 2 and 3 only). The only heavy metal dinitramide salts which have been studied using X-ray diffraction techniques so far are fac-[Re(bpy)-(CO) 3 N 3 O 4 ] [6], hexaaquomanganese and hexaaquozinc dihydrate dinitramide [7]. Therefore, due to the surprisingly interesting structure of 2, [Cu(NH 3 ) 4 ][N(NO 2 ) 2 )] 2 (4) [1] and [Pd(NH 3 ) 4 ][N(NO 2 ) 2 ] 2 , (5) have also been prepared and characterized by 14 N NMR, vibrational spectroscopy (IR, Raman) and X-ray diffraction studies . Results and Discussion Preparation and spectroscopic characterizationAll compounds, with the exception of [Cu(NH 3 ) 4 ]-[N(NO 2 ) 2 ] 2 (4), were prepared by a metathesis reaction using KN(NO 2 ) 2 . 4 was prepared by the reaction of

No abstract

The dichloroborane C 6 F 5 BCl 2 reacted with two equivalents trimethylsilyl azide to form C 6 F 5 B(N 3 ) 2 which trimerizes in the solid state to give [C 6 F 5 B(N 3 ) 2 ] 3 1, the first example of an azido substituted N,NЈ,NЉ-tris(diazo)triazatriboratacyclohexane. Its monomer was trapped by pyridine yielding C 6 F 5 B(N 3 ) 2 ؒpy 2. This is in contrast to (BF 2 N 3 ) 3 3 which is trimeric in solution and in the solid state, as shown by 11 B NMR spectroscopy.

No abstract