Steric effects on the mode of aggregation and reactivity of clusters formed from the lithiation of trisamidothiophosphates

Lithiation of SP[N(H)R]3 with LiBun produces the dimers [(THF)LiSP(NR)(NHR)2]2 (R = Pri) or ([LiSP(NR)-(NHR)2][(THF)LiSP(NR)2(NHR)])2 (R = But) with central Li2N2 or Li2S2 rings, respectively; further lithiation yields the dianion [SP(NR)2(NHR)]2- (R = Pri) or leads to sulfur extrusion when R = But.     

Preparation, Crystal Structures, and Isomerization of the Tellurium Diimide Dimers RNTe(&mgr;-NR')(2)TeNR (R = R' = (t)Bu; R = PPh(2)NSiMe(3), R' = (t)Bu, (t)Oct): X-ray Structure of the Telluradiazole Dimer [(t)Bu(2)C(6)H(2)N(2)Te](2)

The reaction of R'NHLi (R = (t)Bu, (t)Oct) with Ph(2)P(NSiMe(3))(2)Te(Cl)NPPh(2)NSiMe(3) in toluene at -78 degrees C, followed by warming to 23 degrees C, produces the tellurium diimide dimers RNTe(&mgr;-NR')(2)TeNR (2a, R' = (t)Bu, R = NPPh(2)NSiMe(3); 2b, R' = (t)Oct, R = NPPh(2)NSiMe(3)) and Ph(2)P(NHSiMe(3))(NSiMe(3)). X-ray analyses revealed that 2a and 2b have centrosymmetric structures containing a planar four-membered Te(2)N(2) ring and short exocyclic tellurium-nitrogen bond lengths (d(Te-N) = 1.900(5) and 1.897(4) or 1.905(4) ? for 2a and 2b, respectively). The exocyclic imido substituents adopt a trans arrangement with respect to the Te(2)N(2) ring. By contrast, the reaction of 2,4,6-(t)Bu(3)C(6)H(2)NHLi with Ph(2)P(NSiMe(3))(2)Te(Cl)NPPh(2)NSiMe(3) in toluene under similar conditions produces the telluradiazole ((t)Bu(2)C(6)H(2)N(2)Te)(2) (3), which exists as a weakly associated dimer in the solid state with intramolecular Te-N distances of 2.628(4) ?. The tellurium diimide dimer (t)BuNTe(&mgr;-N(t)Bu)(2)TeN(t)Bu (2c'), prepared by the reaction of TeCl(4) with (t)BuNHLi in a 1:4 molar ratio, consists of a folded Te(2)N(2) ring with exocyclic N(t)Bu groups in a cis orientation. The (1)H, (31)P, and (125)Te NMR spectra of 2a and 2b indicate that the trans isomers slowly transform into the corresponding cis isomers in solution. Crystals of 2b are triclinic, space group P&onemacr; (No. 2), with a = 13.304(3) ?, b = 16.927(3) ?, c = 13.292(5) ?, alpha = 98.94(2), beta = 109.27(2), gamma = 69.04(2) degrees, V = 2636(1) ?(3), and Z = 4. The final R and R(w) values were 0.034 and 0.033, respectively. Crystals of 2c' are orthorhombic, space group Pnma (No. 62), with a = 9.535(3) ?, b = 14.264(3) ?, c = 16.963(4) ?, V = 2307.1(9) ?(3), and Z = 4. The final R and R(w) values were 0.040 and 0.040, respectively. Crystals of 3 are monoclinic, space group P2(1)/n (No. 14), with a = 9.117(3) ?, b = 11.481(4) ?, c = 16.550(4) ?, beta = 97.76(2) degrees, V = 1716.5(8) ?(3), and Z = 4. The final R and R(w) values were 0.031 and 0.034, respectively.     

Experimental and theoretical investigations of tellurium(IV) diimides and imidotelluroxanes: X-ray structures of B(C6F5)3 adducts of OTe(mu-NtBu)2TeNtBu, [OTe(mu-NtBu)2Te(mu-O)]2 and tBuNH2

The hydrolysis of (t)BuNTe(mu-N(t)Bu)(2)TeN(t)Bu (1) with 1 or 2 equiv of (C(6)F(5))(3)B.H(2)O results in the successive replacement of terminal imido groups by oxo ligands to give the telluroxane-Lewis acid adducts (C(6)F(5))(3)B.OTe(mu-N(t)Bu)(2)TeN(t)Bu (2) and [(C(6)F(5))(3)B.OTe(mu-N(t)Bu)(2)Te(mu-O)](2) (3), which were characterized by multinuclear NMR spectroscopy and X-ray crystallography. The Te=O distance in 2 is 1.870(2) A. The di-adduct 3 involves the association of four (t)()BuNTeO monomers to give a tetramer in which both terminal Te=O groups [d(TeO) = 1.866(3) A] are coordinated to B(C(6)F(5))(3). The central Te(2)O(2) ring in 3 is distinctly unsymmetrical [d(TeO) = 1.912(3) and 2.088(2) A]. The X-ray structure of (C(6)F(5))(3)B.NH(2)(t)()Bu (4), the byproduct of these hydrolysis reactions, is also reported. The geometries and energies of tellurium(IV) diimides and imido telluroxanes were determined using quantum chemical calculations. The calculated energies for the reactions E(NR)(2) + Te(NR)(2) (E = S, Se, Te; R = H, Me, (t)Bu, SiMe(3)) confirm that cyclodimerization of tellurium(IV) diimides is strongly exothermic. In the mixed-chalcogen systems, the cycloaddition is energetically favorable for the Se/Te combination. The calculated energies for the further oligomerization of the dimers XE(mu-NMe)(2)EX (E = Se, Te; X = NMe, O) indicate that the formation of tetramers is strongly exothermic for the tellurium systems but endothermic (X = NMe) or thermoneutral (X = O) for the selenium systems, consistent with experimental observations.     

The practical design of ultrasonic test tanks

A systematic approach to the design of ultrasonic test tanks is outlined in which criteria are given first for the choice of tank length and subsequently for the choice of tank width and height. Calculations are presented for typical transducer beam measurements in the low megahertz frequency range, indicating the individual and combined effects of side lobe inclusion and excitation pulse length. The methods used may be easily extended to determine, for a given situation, either the minimum tank size that needs to be used, or the limits imposed by an existing tank on the experiments that can be performed in it.     

Asymmetric vortex solitons in nonlinear periodic lattices

We reveal the existence of asymmetric vortex solitons in ideally symmetric periodic lattices and show how such nonlinear localized structures describing elementary circular flows can be analyzed systematically using the energy-balance relations. We present the examples of rhomboid, rectangular, and triangular vortex solitons on a square lattice and also describe novel coherent states where the populations of clockwise and anticlockwise vortex modes change periodically due to a nonlinearity-induced momentum exchange through the lattice. Asymmetric vortex solitons are expected to exist in different nonlinear lattice systems, including optically induced photonic lattices, nonlinear photonic crystals, and Bose-Einstein condensates in optical lattices.     

Stille Catalyst‐Transfer Polycondensation Using Pd‐PEPPSI‐IPr for High‐Molecular‐Weight Regioregular Poly(3‐hexylthiophene)

A commercially available palladium N‐heterocyclic carbene (Pd‐NHC) precatalyst is used to initiate chain‐growth polymerization of 2‐bromo‐3‐hexyl‐5‐trimethylstannylthiophene. The molecular weight of the resultant poly(3‐hexylthiophene) can be modulated (7 to 73 kDa, Đ = 1.14 to 1.53) by varying the catalyst concentration. Mass spectrometry data confirm control over the polymer end groups and ¹H NMR spectroscopy reveals that the palladium catalyst is capable of “ring‐walking”. A linear relationship between M_n and monomer conversion is observed. Atomic force microscopy and X‐ray scattering verify the regioregular nature of the resultant polythiophene.

     

Formation of a stable dicarbenoid and an unsaturated C2P2S2 ring from two-electron oxidation of the [C(PPh2S)2]2- dianion

Two-electron oxidation of the [C(PPh(2)S)(2)](2-) dianion with iodine afforded an unexpected mixture of a dimeric Li-I carbenoid [(Et(2)O)(mu-Li)][(mu(4)-Li){IC(PPh(2)S)(2)}(2)] and a novel, unsaturated six-membered C(2)P(2)S(2) ring in [(SPh(2)P)(2)C(2)(PPh(2))(2)S(2)].     

Formation and X-ray structure of a seven-membered C4OBN heterocycle by a THF ring-expansion process

The reaction of BCl(3) with two equivalents of LiN(H)Dipp (Dipp = 2,6-diisopropylphenyl) in THF produces DippN(H)BO(CH(2))(4)NDipp, which contains a puckered seven-membered C(4)OBN ring.     

Multivortex solitons in triangular photonic lattices

We introduce a novel class of stable lattice solitons with a complex phase structure composed of many single-charge discrete vortices in a triangular photonic lattice. We demonstrate that such nonlinear self-trapped states are linked to the resonant Bloch modes, which bear a honeycomb pattern of phase dislocations.