A simple route to phosphamethine cyanines from S,N-heterocyclic carbenes.

Although salts of thiazolium cations are known, many readily prepared iodide salts have eluded spectroscopic and structural characterization; herein, data for a variety of such salts are reported. It has been demonstrated that thiazolium cations can be deprotonated to generate S,N-heterocyclic carbenes and their "electron rich olefin" dimers, but use of the former has been largely overshadowed by that of the more common N-heterocyclic carbenes. We report herein that the deprotonation of thiazolium iodides and their subsequent reaction with a conveniently prepared triphosphenium precursor grants phosphamethine cyanine cations with solid-state geometry and electronic structure unlike those of NHC-stabilized cations.

Lanthanide complexes of boraamidinate ligands: synthesis and X-ray structures of {[Li(THF)4][bamLnCl2(THF)]}2 (bam = [PhB(NDipp)2](2-); Ln = Y, Pr, Nd, Sm, Ho, Er, Yb) and {bamLnCl(THF)2}2 (Ln = Y, Sm).

The first examples of the incorporation of the boraamidinate ligand into lanthanide complexes have been prepared by reaction of equimolar amounts of [Li(2)][PhB(NDipp)(2)] and LnCl(3) in tetrahydrofuran (THF), which produces "ate" complexes of the form {[Li(THF)(4)][bamLnCl(2)(THF)]}(2) [Ln = Y (9a), Pr (9b), Nd (9c), Sm (9d), Ho (9e), Er (9f), Yb (9g)] through the inclusion of the LiCl by-product. The isostructural complexes 9a-g were characterized in the solid state by X-ray crystallography, which revealed ion-separated complexes composed of a dimeric anion with a terminal and a bridging chloride ligand on each metal center and a tetrasolvated cation, [Li(THF)(4)](+). In solution, the yttrium complex 9a was characterized by multinuclear ((1)H, (13)C, (7)Li, and (11)B) NMR spectroscopy.

Boraguanidinates: synthesis, X-ray structures, and reactions of {Li2[(i)Pr2NB(NDipp)2]}2 with p-block and group 12 element halides.

The new Dipp-substituted boranes (Dipp = 2,6-diisopropylphenyl) (i)Pr2NB(NHDipp)2 (5), BrB(NHDipp)2 (7b), and B(NHDipp)3 (8) have been prepared in high yields and characterized in solution by multinuclear NMR spectroscopy ((1)H, (11)B and (13)C) and in the solid state by X-ray crystallography. Reaction of 5 with 2 equiv of (n)BuLi in n-hexane produces {Li2[(i)Pr2NB(NDipp)2]}2 (6) the first example of a stable dilithiated boraguanidinate. The unsolvated complex 6 has a dimeric structure in the solid state.

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

The reaction of BCl3 with two equivalents of LiN(H)Dipp (Dipp = 2,6-diisopropylphenyl) in THF produces DippN(H)BO(CH2)4NDipp, which contains a puckered seven-membered C4OBN ring.

In search of the [PhB(mu-N(t)Bu)2]2As. radical: experimental and computational investigations of the redox chemistry of group 15 bis-boraamidinates.

DFT calculations for the group 15 radicals [PhB(mu-N(t)Bu)2]2M. (M = P, As, Sb, Bi) predict a pnictogen-centered SOMO with smaller contributions to the unpaired spin density arising from the nitrogen and boron atoms. The reactions of Li 2[PhB(mu-NR)2] (R = (t)Bu, Dipp) with PCl 3 afforded the unsolvated complex LiP[PhB(mu-N(t)Bu)2] 2 ( 1a) in low yield and ClP[PhB(mu-NDipp)2] (2), both of which were structurally characterized.

Indium(I) trifluoromethanesulfonate and other soluble salts for univalent indium chemistry.

Herein we report the synthesis, structure and preliminary reactivity studies of a series of unusually soluble indium(i) salts that are improved alternatives to indium(i) halide reagents.