Enthalpies of Formation of Gas-Phase N3, N3-, N5+, and N5- from Ab Initio Molecular Orbital Theory, Stability Predictions for N5+N3- and N5+N5-, and Experimental Evidence for the Instability of N5+N3-

Ab initio molecular orbital theory has been used to calculate accurate enthalpies of formation and adiabatic electron affinities or ionization potentials for N3, N3-, N5+, and N5- from total atomization energies. The calculated heats of formation of the gas-phase molecules/ions at 0 K are ΔHf(N3(2Π)) = 109.2, ΔHf(N3-(1∑+)) = 47.4, ΔHf(N5-(1A1‘)) = 62.3, and ΔHf(N5+(1A1)) = 353.3 kcal/mol with an estimated error bar of ±1 kcal/mol. For comparison purposes, the error in the calculated bond energy for N2 is 0.72 kcal/mol. Born−Haber cycle calculations, using estimated lattice energies and the adiabatic ionization potentials of the anions and electron affinities of the cations, enable reliable stability predictions for the hypothetical N5+N3- and N5+N5- salts. The calculations show that neither salt can be stabilized and that both should decompose spontaneously into N3 radicals and N2. This conclusion was experimentally confirmed for the N5+N3- salt by low-temperature metathetical reactions between N5SbF6 and alkali metal azides in different solvents, resulting in violent reactions with spontaneous nitrogen evolution. It is emphasized that one needs to use adiabatic ionization potentials and electron affinities instead of vertical potentials and affinities for salt stability predictions when the formed radicals are not vibrationally stable. This is the case for the N5 radicals where the energy difference between vertical and adiabatic potentials amounts to about 100 kcal/mol per N5

Zirconium(IV) and thorium (IV) bis(fluorosulphuryl)imides: Preparation and characterization

232-235Metal (IV) bis(fluorosulphuryl) imides [M=Zr(IV) and Th(IV)] have been prepared by reacting the corresponding trifluoroacetates with HN(SO2F)2 at 100-130°C for ~ 10 hours. These are thermally stable, white hygroscopic solids (m.p. > 210°C) and are insoluble in common organic solvents and HN(SO2F)2. These properties reflect their polymeric nature. M[N(SO2F)2]4 form coordination complexes with some nitrogen and oxygen donors

Bis(fluorosulphuryl)imide derivatives of zinc(II), cadmium(II), mercury(II) and their coordination complexes with oxygen and nitrogen donors

890-892Bis(fluorosulphuryl)imides of zinc(II) and cadmium(II), [M{N(SO2F)2}2], have been prepared in > 90% yield by reacting the metal trifluoroacetates with excess bis(fluorosulphuryl)imide in trifluoroacetic acid medium. These compounds and [Hg{N(SO2F)2}2], which has been prepared by a known method, have been characterized by their elemental analyses and infrared spectral data. These are found to be thermally stable up to 200°C and are insoluble in non-coordinating solvents and HN(SO2F)2. These form coordination complexes of the type [M(L)x{N(SO2F) 2}2] where M = Zn(II), Cd(II) and Hg(II); x = 4, L = pyridine, acetonitrile and triphenylphosphine oxide; x = 2, L= 2,2'-bipyridyl

CCDC 642077: Experimental Crystal Structure Determination

Related Article: S.C.Kettwich, S.N.Pierson, A.J.Peloquin, J.M.Mabry, S.T.Iacono|2012|New J.Chem.|36|941|doi:10.1039/c2nj20922e,An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.,Related Article: S.T.Iacono, A.Vij, W.Grabow, D.W.Smith Junior, J.M.Mabry|2007|Chem.Commun.||4992|doi:10.1039/b712976

CCDC 629369: Experimental Crystal Structure Determination

Related Article: S.C.Kettwich, S.N.Pierson, A.J.Peloquin, J.M.Mabry, S.T.Iacono|2012|New J.Chem.|36|941|doi:10.1039/c2nj20922e,An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.,Related Article: S.T.Iacono, A.Vij, W.Grabow, D.W.Smith Junior, J.M.Mabry|2007|Chem.Commun.||4992|doi:10.1039/b712976