Syntheses and X‐ray Crystal Structures of Organoantimony Diazides

Abstract

Antimony(III) complexes of the general type LSbF(2) (3: L(1) =[tBuC(NiPr)(2)]; 4: L(2) =[tBuC(NDipp)(2) , Dipp=2,6-iPr(2)C(6)H(3)) and LSb(N(3))(2) (6: L(1); 7: L(2)) were prepared in high yields and characterized by elemental analyses, NMR and IR spectroscopy and single-crystal X-ray diffraction. Moreover, the solid-state structures of [L(2)SbF(2)][L(2)Li] (5), [L(2) AlH(2)] (1), and [L'H][L'K(thf)(3)] (2; L'=HC(NDipp)(2)) are described, in which the Li (5) and K atoms (2) adopt rather unusual coordination modes.

Synthesis and Structural Characterization of Antimony Polyazides

“…Recently we became interested in the synthesis of Group 15 polyazides and reported on the X-ray crystal structures of several organoantimony diazides RSb(N 3 ) 2 [6] and the triazide Sb(N 3 ) 3 . [4] Moreover, the structure of Pyr 2 Bi(N 3 ) 3 , which represents the only structurally characterized base-stabilized, neutral binary polyazide of a Group 15 element, was reported.…”

“…[5] However, even though these ionic binary complexes are less heat-and shock-sensitive compared with their neutral derivatives, only P(N 3 ) 6 À , [5d] As(N 3 ) 6 À , [5g] Sb(N 3 ) 6 À , [2d] Bi(N 3 ) 4 À , [2f] and Bi(N 3 ) 6 3À[2f] were structurally characterized.…”

Potassium C–F Interactions and the Structural Consequences in N,N′-Bis(2,6-difluorophenyl)formamidinate Complexes

“…Complex 1 was repeatedly obtained by simple exposure of thf solutions of "[K(DFForm)(thf) x ]" to vacuum, giving 1 upon drying. The poor solubility in non-coordinating solvents made analysis by 1 H NMR and 19 F NMR spectroscopy difficult, giving only broad resonances in both spectra (NCHN at 8.88 ppm and F2,6 at −127.2 ppm).All fluorine atoms of the DFForm ligand are equivalent, but clear spectra were generated when 1 was dissolved in thf-d 8 . In this solvent, the NCHN resonance appeared as a pentet, owing to 5 J H-F coupling with the ortho-fluorine atoms, as the pentet collapsed to a singlet with 19 F decoupling.…”

“…Not only does the anionic NCHN bite provide a variety of different nitrogen-based coordination modes (e.g., monodentate κ(N), bidentate κ(N,N ), or various bridging modes e.g., µ-1κ(N):2κ(N ), µ-1κ(N,N ):2κ(N,N ) to list a few) [6,7], the nitrogen-bound aromatic substituents can also provide additional coordination modes. The potential to form metal-arene interactions, such as η 6 coordination, has been largely observed in group one chemistry [8][9][10][11][12][13], though some examples are known in f -block chemistry [14]. In almost all examples of this aromatic coordination, the phenyl rings contained alkyl-substituents in either the 2,6 positions (e.g., iPr, Et, Me), or in the 2,4,6 positions (e.g., Me).…”

Antimony(iii) and bismuth(iii) amides containing pendant N-donor groups – a combined experimental and theoretical study

“…8 There exists a significant amount of structurally characterized antimony and bismuth amides 9 including interesting examples of related amidinates and β-diketiminates. 10 Nevertheless, there are, to the best of our knowledge, no examples of antimony or bismuth compounds supported by a monoanionic N,N,N pincer-type ligand bonded to the central metal via a nitrogen-metal bond. 11 We herein report the synthesis and structure of N,N-and N,N,N-chelated antimony(III) and bismuth(III) chlorides containing ligands L 1-3 derived from the pyrrole ring ( Fig.…”