Ligand‐Stabilized Chalcogen Dications

Chalcogen‐transfer reagents? The bonding in the dicationic rings C₂N₂E²⁺ (see picture) differs from that in N‐heterocyclic carbenes and their isovalent p‐block analogues in accommodating a lone pair of electrons with π symmetry, as well as σ symmetry, on the chalcogen center. The labile electrophilic chalcogenium dications (E²⁺) are potentially versatile chalcogen‐transfer reagents in reactions with a variety of inorganic and organic substrates.

     

The cyclic [N(PiPr2E)2]+ (E = Se, Te) cations: a new class of inorganic ring system

The two-electron oxidation of [(tmeda)NaN(PiPr2E)2] with iodine produces the cyclic [N(PiPr2E)2]+ (E = Se, Te) cations, which exhibit long E-E bonds in the iodide salts.     

Synthesis, spectroscopic, and structural investigation of the cyclic [N(PR2E)2]+ cations (E = Se, Te; R = iPr, Ph): the effect of anion and R-group exchange

Two-electron oxidation of the [N(PiPr2E)2]- anion with iodine produces the cyclic [N(PiPr2E)2]+ (E =Se, Te) cations, which exhibit long E-E bonds in the iodide salts [N(PiPr2Se)2]I (4) and [N(PiPr2Te)2]I (5). The iodide salts 4 and 5 are converted to the ion-separated salts [N(PiPr2Se)2]SbF6 (6) and [N(PiPr2Te)2]SbF6 (7) upon treatment with AgSbF6. Compounds 4-7 were characterized in solution by multinuclear NMR, vibrational, and UV-visible spectroscopy supported by DFT calculations. A structural comparison of salts 4-7 and [N(PiPr2Te)2]Cl (8) confirms that the long E-E bonds in 4, 5, and 8 can be attributed primarily to the donation of electron density from a lone pair of the halide counterion into the E-E sigma* orbital (LUMO) of the cation. The phenyl derivative [N(PPh2Te)2]I (9) was prepared in a similar manner. However, the attempted synthesis of the selenium analogue, [N(PPh2Se)2]I, produced a 1:1 mixture of [N(PPh2Se)2(mu-Se)][I] (10) and [SeP(Ph2)N(Ph2)PI] (11). DFT calculations of the formation energies of 10 and 11 support the observed decomposition. Compound 10 is a centrosymmetric dimer in which two six-membered NP2Se3 rings are bridged by two I- anions. Compound 11 produces the nine-atom chain {[N(PPh2)2Se]2(mu-O)} (12) upon hydrolysis during crystallization. The reaction between [(TMEDA)NaN(PiPr2Se)2] and SeCl2 in a 1:1 molar ratio yields the related acyclic species [SeP(iPr2)N(iPr2)PCl] (13), which was characterized by multinuclear NMR spectroscopy and an X-ray structural determination.     

Phosphorus(III)-Nitrogen-Sulphur Compounds: Synthesis and Metal Complexes

Abstract

The preparation and X-ray structure (M=Mo) of complexes of the type M(CO)₅(Ph₂PNSO) (M=Cr,Mo) are described. These complexes are used in the synthesis of homo- and hetero-dinuclear complexes of Ph₂PNSNPPh₂. A ³¹P DNMR study of these dinuclear complexes indicates a cis, trans → trans, cis isomerization in solution. The preparation and X-ray structure (M=Cr) of the mononuclear complexes, cis-M(CO)₄(P(Ph)₂NSN(Ph)₂P), (M=Cr,Mo) are also described.     

Cycloaddition Reactions of (NSCl)3 with Organic Nitriles

Abstract

The six-membered ring system RCN(NSCl)₂ (R= ^tBu, CCl₃, Me₂N, Et₂N, ⁱPr₂N) can be prepared by a cycloaddition reaction of the free nitrile, RCN, with cyclo-(NSCl)₃ at mom temperature. This reaction is slow for R= ^tBu and CCl₃, but it can be accelerated by UV light. The six-membered rings are converted to five-membered rings RCN₂S₂ ⁺ Cl^- by thermolysis. By varying the conditions of the cycloaddition reaction, 1,3-(RCN)₂(NSCl)₂ (R= Me₂N, Et₂N) and 1,5- RCN(NSN)₂SCl can be obtained.     

Homoleptic, heteroleptic and mixed-valent thallium and indium complexes of multidentate chalcogen-centred PCP-bridged ligands

The metathetical reaction of [Li(TMEDA)][HC(PPh(2)Se)(2)] ([Li(TMEDA)]1) with TlOEt in a 1:1 molar ratio afforded a homoleptic Tl(I) complex as an adduct with LiOEt, Tl[HC(PPh(2)Se)(2)]·LiOEt (7), which undergoes selenium-proton exchange upon mild heating (60 °C) to give the mixed-valent Tl(I)/Tl(III) complex {[Tl][Tl{(Se)C(PPh(2)Se)(2)}(2)]}(∞) (8). Treatment of TlOEt with [Li(TMEDA)](2)[(SPh(2)P)(2)CE'E'C(PPh(2)S)(2)] (3b, E' = S; 3c, E' = Se) in a 2:1 molar ratio produced the binuclear Tl(i)/Tl(i) complexes Tl(2)[(SPh(2)P)(2)CE'E'C(PPh(2)S)(2)] (9b, E' = S; 9c, E' = Se), respectively. Selenium-proton exchange also occurred upon addition of [Li(TMEDA)]1 to InCl(3) to yield the heteroleptic complex (TMEDA)InCl[(Se)C(PPh(2)Se)(2)] (10a). Other examples of this class of In(III) complex, (TMEDA)InCl[(E')C(PPh(2)E)(2)] (10b, E = E' = S; 10c, E = S, E' = Se) were obtained via metathesis of InCl(3) with [Li(TMEDA)](2)[(E')C(PPh(2)E)(2)] (2b, E = E' = S; 2c, E = S, E' = Se, respectively). All new compounds have been characterized in solution by (1)H and (31)P NMR spectroscopy and the solid-state structures have been determined for 8, 9c and 10a-c by single-crystal X-ray crystallography. Complex 8 is comprised of Tl(+) ions that are weakly coordinated to octahedral [Tl{(Se)C(PPh(2)Se)(2)}(2)](-) anions to give a one-dimensional polymer. The complex 9c is comprised of two four-coordinate Tl(+) ions that are each S,S',S',Se bonded to the hexadentate [(SPh(2)P)(2)CSeSeC(PPh(2)S)(2)](2-) ligand in which d(Se-Se) = 2.531(2) ?. The six-coordinate In(III) centres in the distorted octahedral complexes 10a-c are connected to a tridentate [(E')C(PPh(2)E)(2)](2-) dianion, a chloride ion and a neutral bidentate TMEDA ligand.     

Spirocyclic Boraamidinate Complexes of Lanthanide(III) Metals

The reaction of Li₂[Phbam^Dipp] (Phbam^Dipp = PhB(NDipp)₂; Dipp = 2,6‐iPr₂C₆H₃) with lanthanum(III) triiodides LnI₃(THF)_3.5 (Ln = La, Sm) in THF produces complexes of the type [Li(THF)₄]₂[(Phbam^Dipp)₂LnI], which were characterized in solution by multinuclear NMR spectroscopy and in the solid state by single‐crystal X‐ray structural determinations. The ion‐separated complexes are comprised of a spirocyclic anion in which two Phbam^Dipp ligands and an iodide ion are linked to the five‐coordinate metal atom; charge balance is provided by two tetrasolvated lithium ions [Li(THF)₄]⁺.     

Observation of nonlinear self-trapping of broad beams in defocusing waveguide arrays

We demonstrate experimentally the localization of broad optical beams in periodic arrays of optical waveguides with defocusing nonlinearity. This observation in optics is linked to nonlinear self-trapping of Bose-Einstein-condensed atoms in stationary periodic potentials being associated with the generation of truncated nonlinear Bloch states, existing in the gaps of the linear transmission spectrum. We reveal that unlike gap solitons, these novel localized states can have an arbitrary width defined solely by the size of the input beam while independent of nonlinearity.