Binary Polyazides of Zinc

Abstract

Herein, we report on the synthesis, isolation, and comprehensive characterization (m.p., ATR-IR/Raman, elemental analysis, 14 N NMR) of tetraazidozincate anions [Zn(N 3 ) 4 ] 2in a series of [Ph 4 P] + and [PNP] + [PNP = bis(triphenylphosphine)iminium] salts. The phase polymorphism in [Ph 4 P] 2 -[Zn(N 3 ) 4 ] was investigated by temperature-dependent Raman spectroscopy and by powder and single-crystal X-ray diffraction experiments, which indicate the occurrence of five roomtemperature-stable, and one common high-temperature phase, [a]

Dichloro‐Cycloazatriphosphane: The Missing Link between N2P2 and P4 Ring Systems in the Systematic Development of NP Chemistry

“…Similarly to the known synthesis of the cyclotetraphosphane 6 Mes* via intermediate 12 Mes* , the isomerization of 10 Mes* to 7 Mes* was found to be favored in polar solvents such as THF or CH 2 Cl 2 and was complete within eight hours (Scheme , Figure S14 in the Supporting Information). After recrystallization from n ‐hexane, the ring system 7 Mes* could then be isolated in 29 % yield (see below).…”

“…Additionally, 10 Mes* exhibited a third signal (160.8 ppm, AMX spin system) indicative of a −PCl 2 functionality . The four‐membered ring system 7 Mes* was characterized by an AX 2 spin system (−26.4, 207.2 ppm; −174 Hz), which can be compared to the NMR data of the related compound 6 Mes* (A 2 X 2 : −8.1, 131.1 ppm; −217 Hz) …”

“…The (pseudo)halogen substituents allow for facile functionalization of the ring system, which is why these species have become versatile reagents in NP chemistry. Recently, we could show that a similar conceptual approach is valid for the heavier congeners, [XP(μ‐PR)] 2 (e.g., 6 Mes* ), thus offering complementary access to the chemistry of cyclophosphanes, which was previously mainly investigated by methods of direct activation of white phosphorus (P 4 ) …”

“…Compound 10 Mes* is especially interesting, as it can be regarded as a constitutional isomer of the desired ring system 7 Mes* . It is also closely related to the transient intermediates 11 Dipp (Dipp=2,6‐diisopropylphenyl) and 12 Mes* (Scheme ), which were previously observed spectroscopically during the syntheses of [ClP(μ‐NDipp)] 2 ( 5 Dipp ) and [ClP(μ‐PMes*)] ( 6 Mes* ); however, those intermediates could not be isolated.…”

“…The structural parameters relate well to analogous N 2 P 2 or P 4 ring systems, for example, 5 Ter and 6 Mes* : In case of 5 Ter , the central N 2 P 2 ring system was perfectly planar, with either cis ‐ or trans ‐arrangement of the Cl substituents. The cyclophosphane 6 Mes* , on the other hand, incorporated a distinctly butterfly‐shaped cyclic scaffold with fold angles in the range of 120–143° and cis ‐arrangement of the Cl atoms.…”