Experimental and theoretical investigations of structural trends for selenium(IV) imides and oxides: X-ray structure of Se3(NAd)2

The thermal decomposition of Se(NAd)(2) (Ad = 1-adamantyl) in THF was monitored by (77)Se NMR and shown to give the novel cyclic selenium imide Se(3)(NAd)(2) as one of the products. An X-ray structural determination showed that Se(3)(NAd)(2) is a puckered five-membered ring with d(Se-Se) = 2.404(1) A and |d(Se-N)| = 1.873(4) A. On the basis of (77)Se NMR data, other decomposition products include the six-membered ring Se(3)(NAd)(3), and the four-membered rings AdNSe(micro-NAd)(2)SeO and OSe(micro-NAd)(2)SeO. The energies for the cyclodimerization of E(NR)(2) and RNEO (E = S, Se; R = H, Me, (t)Bu, SiMe(3)), and the cycloaddition reactions of RNSeO with E(NR)(2), RNSO(2) with Se(NR)(2), and S(NR)(2) with Se(NR)(2) have been calculated at MP2, CCSD, and CCSD(T) levels of theory using the cc-pVDZ basis sets and B3PW91/6-31G* optimized geometries. Sulfur(IV) and selenium(IV) diimide monomers are predicted to be stable, the sole exception being Se(NSiMe(3))(2) that shows a tendency toward cyclodimerization. The cyclodimerization energy for RNSeO and the cycloaddition reaction energies of RNSeO with Se(NR)(2) as well as that of RNSO(2) with Se(NR)(2) are negative, consistent with the observed formation of OSe(micro-N(t)Bu)(2)SeO, OSe(micro-N(t)Bu)(2)SeN(t)Bu, and O(2)S(micro-N(t)Bu)(2)SeN(t)Bu, respectively. Cycloaddition is unlikely when one of the reactants is a sulfur(IV) diimide.     

Eight- and 16-membered cyanuric-sulfanuric ring systems: C2N4S2-->C2N3S ring contraction

Eight- and 16-membered cyanuric-sulfanuric ring systems of the type Ar2C2N4S2(O)2Ar'2 (3a, Ar = 4-BrC6H4, Ar' = Ph; 3b, Ar = 4-CF3C6H4, Ar' = Ph; 3c, Ar = 4-CF3C6H4, Ar' = 4-CH3C6H4) and Ar4C4N8S4(O)4Ar'4 (4b, Ar = 4-CF3C6H4, Ar' = Ph; 4c, Ar = 4-CH3C6H4, Ar' = Ph; 4d, Ar = 4-CF3C6H4, Ar' = 4-CH3C6H4), respectively, were prepared in good yields by the reaction of the corresponding sulfur(IV) systems with m-chloroperbenzoic acid. The X-ray structures of 3b, 3c.C7H14, 4b.CH2Cl2, 4c, and the S(IV) system Ar4C4N8S4Ar'4 (2c, Ar = 4-CH3C6H4, Ar' = Ph) were determined. Upon oxidation the two oxygen atoms in 3b and 3c.C7H14 adopt endo positions leading to a twist boat conformation for the C2N4S2 ring. The 16-membered C4N8S4 rings in 4b and 4c retain a cradle conformation upon oxidation. The S-N bond distances are ca. 0.06 A shorter in all the S(VI) systems compared to those in the corresponding S(IV) rings. The thermolysis of 3b at ca. 220 degrees C occurs primarily via loss of a sulfanuric group, NS(O)Ph, to give the six-membered ring (4-CF3C6H4)2C2N3S(O)Ph (6). The structure of 6 was confirmed by X-ray crystallography. Crystal data: 2c, triclinic, space group P1 with a = 13.917(2) A, b = 15.610(4) A, c = 13.491(3) A, alpha = 95.77(2) degrees, beta = 114.82(1) degrees, gamma = 76.21(2) degrees, V = 2583(1) A3, and Z = 2; 3b, monoclinic, space group P2(1)/a with a = 7.316(2) A, b = 29.508(5) A, c = 12.910(2) A, beta = 101.30(2) degrees, V = 2733(1) A3, and Z = 4; 3c.C7H14, triclinic, space group P1 with a = 12.849(4) A, b = 12.863(4) A, c = 12.610(7) A, alpha = 110.61(3) degrees, beta = 105.77(3) degrees, gamma = 62.77(2) degrees, V = 1719(1) A3, and Z = 2; 4b.CH2Cl2, triclinic, space group P1 with a = 12.647(3) A, b = 19.137(3) A, c = 12.550(2) A, alpha = 105.765(11) degrees, beta = 93.610(15) degrees, gamma = 88.877(16) degrees, V = 2917.2(9) A3, and Z = 2; 4c, orthorhombic, space group Pba2 with a = 22.657(2) A, b = 10.570(2) A, c = 10.664(3) A, alpha = beta = gamma = 90 degrees, V = 2554(1) A3, and Z = 2; 6, triclinic, space group P1 with a = 7.4667(8) A, b = 11.3406(12) A, c = 13.5470(14) A, alpha = 108.000(2) degrees, beta = 105.796(2) degrees, gamma = 94.300(2) degrees, V = 1033.8(2) A3, and Z = 2.     

Recent Studies of Multiply Bonded Selenium and Tellurium Compounds

Abstract

Several aspects of recent developments in the chemistry of multiply bonded selenium and tellurium compounds are surveyed in this article. These include (a) tellurium(IV)-nitrogen compounds, (b) complexes with two (or more) terminal Group 14–Group 16 linkages, and (c) a new approach to previously inaccessible ligands containing Group 15–Group 16 functionalities.     

Synthetic and Structural Studies of Cyclophosphathiazenes and their Adducts with Lewis Acids

Abstract

The reactions of (Me₃SiNR)PPh₂ (NSiMe₃) (R=H, SiMe₃) with (NSCl)₃ or S_xCl₂ (x=1, 2) provide improved preparative routes to mixed phosphazene-thia-zene ring systems, e.g. (Ph₂PN) (SN)₂, 1,3- and 1,5-(Ph₂PN)₂(SN)₂. The interaction of these heterocycles with protonic and Lewis acids, e.g. HBF₄, BCl₃, MeSO₃CF₃, has been investigated in order to determine the site of attack and the effect of adduct formation on the molecular and electronic structures of these ring systems. These reactions have been monitored by UV-visible and ³¹P NMR spectroscopies and the structures of crystalline adducts have been determined by X-ray crystallography. For example, the interaction of 1,3-(Ph₂PN)₂(SN)₂ with MeSO₃CF₃ gives a product in which the methyl group is attached to a nitrogen atom between phosphorus and sulfur. The resulting structural distortion in this and related adducts will be analyzed in the context of the electronic structures of mixed phosphazene-thiazene systems and their adducts with Lewis acids.     

Periodic behavior in families of numerical and affine semigroups via parametric Presburger arithmetic

Semigroup Forum - Let $$f_1(n), \ldots , f_k(n)$$ be polynomial functions of n. For fixed $$n\in \mathbb {N}$$ , let $$S_n\subseteq \mathbb {N}$$ be the numerical semigroup generated by...     

A new route to antimony telluride nanoplates from a single-source precursor

Aerosol-assisted chemical vapor deposition (AACVD) of Sb[(TePiPr2)2N]3 results in pure hexagonal Sb2Te3 nanoplates between 375 and 475 degrees C on glass substrates, with a potential for enhanced thermoelectric properties for novel nanodevices.     

Pentafluorophenylboron halides: 40 years later

The pentafluorophenylboron halides C₆F₅BX₂ (X=Cl, F) and (C₆F₅)₂BCl were first reported in the early 1960s. After a period of inactivity these perfluoroarylboron derivatives have been employed for the synthesis of a variety of important compounds, including monomeric iminoboranes, a highly electrophilic hydroboration reagent, strong Lewis acids (with one or two acceptor sites) that activate alkyl metallocene polymerization catalysts, and the first organoxenon(IV) compounds. These recent developments provide a cogent example of the time lag that often occurs between discovery and applications in fundamental research.