Konstantin Karaghiosoff

3‐Bromomethyl‐3‐hydroxymethyloxetane represents an inexpensive and versatile precursor for the synthesis of 3,3‐disubstituted oxetane derivatives. In the present work, its synthesis was improved and energetic oxetanes based on the explosive LLM‐116 (4‐amino‐3,5‐dinitro‐1 H ‐pyrazole) prepared. Reaching detonation velocities and pressures of up to 7335 ms −1 and 20.9 GPa in combination with a high thermostability and insensitivity, these surpass the prior art by far. Next to a symmetric LLM‐116 derivative, three asymmetric compounds were prepared using azido‐, nitrato‐ and tetrazolyl‐moieties. All compounds were intensively characterized by vibrational‐, mass‐ and multinuclear ( 1 H, 13 C, 14 N) NMR spectroscopy, differential scanning calorimetry and elemental analysis. The molecular structures were elucidated by single crystal X‐ray diffraction. Hirshfeld analysis allowed to estimate their sensitivity next to a practical evaluation using BAM standard procedures. Their performance was calculated using the EXPLO5 V6.04 code and a small‐scale shock reactivity test and initiation test demonstrated their insensitivity and performance.

The different coordination behavior of the flexible yet sterically demanding, hemilabile P,N ligand bis(quinoline‐2‐ylmethyl)phenylphosphine ( bqmpp ) towards selected Cu I , Ag I and Au I species is described. The resulting X‐ray crystal structures reveal interesting coordination geometries. With [Cu(MeCN) 4 ]BF 4 , compound 1 [Cu 2 (bqmpp) 2 ](BF 4 ) 2 is obtained, wherein the copper(I) atoms display a distorted square planar and square pyramidal geometry. The steric demand and π‐stacking of the ligand allow for a short Cu⋅⋅⋅Cu distance (2.588(9) Å). Cu I complex 2 [Cu 4 Cl 3 (bqmpp) 2 ]BF 4 contains a rarely observed Cu 4 Cl 3 cluster, probably enabled by dichloromethane as the chloride source. In the cluster, even shorter Cu⋅⋅⋅Cu distances (2.447(1) Å) are present. The reaction of Ag[SbF 6 ] with the ligand leads to a dinuclear compound ( 3 ) in solution as confirmed by 31 P{ 1 H} NMR spectroscopy. During crystallization, instead of the expected phosphine complex 3 , a tris(quinoline‐2‐ylmethyl)bisphenyl‐phosphine ( tqmbp ) compound [Ag 2 (tqmbp) 2 ](SbF 6 ) 2 4 is formed by elimination of quinaldine. The Au(I) compound [Au 2 (bqmpp) 2 ]PF 6 ( 5 ) is prepared as expected and shows a linear arrangement of two phosphine ligands around Au I .