A second-generation janus scorpionate ligand: controlling coordination modes in iron(II) complexes by steric modulation.

The second-generation Janus scorpionate ligand [HB(mtda (Me)) 3] (-) (mtda (Me) = 2-mercapto-5-methyl-1,3,4-thiadiazolyl) with conjoined ( N, N, N-) and ( S, S, S-) donor faces has been prepared. This second-generation Janus scorpionate ligand [HB(mtda (Me)) 3] (-) differs from the first-generation [HB(mtda) 3] (-) ligand by the replacement of hydrogens on the heterocyclic rings proximal to the nitrogenous face with methyl groups. This study probed whether steric interactions introduced by such methyl group substitution could modulate the reactivity and coordination preferences of these ambidentate ligands.

BORAZANs: tunable fluorophores based on 2-(pyrazolyl)aniline chelates of diphenylboron.

The reaction between 2-pyrazolyl-4-X-anilines, H(pzAnX), (X = para-OMe (L1), Me (L2), H (L3), Cl (L4), CO2Et (L5), CF3 (L6), CN (L7)) and triphenylboron in boiling toluene affords the respective, highly emissive N,N'-boron chelate complexes, BPh2(pzAnX) (X = para-OMe (1), Me (2), H (3), Cl (4), CO2Et (5), CF3 (6), CN (7)) in high yield. The structural, electrochemical, and photophysical properties of the new boron complexes can be fine-tuned by varying the electron-withdrawing or -donating power of the para-aniline substituent (delineated by the substituent's Hammett parameter). Those complexes with electron-withdrawing para-aniline substituents such as CO2Et (5), CF3 (6), and CN (7) have more planar chelate rings, more 'quinoidal' distortion in the aniline rings, greater chemical stability, higher oxidation potentials, and more intense (phiF = 0.

A 'metallic tape' stabilized by an unprecedented (mu5-kappa2,kappa2,kappa2,kappa1,kappa1-) scorpionate binding mode.

The Janus scorpionate ligand, tris(mercaptothiadiazolyl)borate, exhibits extraordinary coordination capacity and versatility, binding from two up to five metal cations as demonstrated by its thallium(i) salt, a compound that serves as a model for metal-surface binding.

Janus scorpionates: supramolecular tectons for the directed assembly of hard-soft alkali metallopolymer chains.

A new scorpionate ligand [HB(mtda)3-] containing mercaptothiadiazolyl (mtda) heterocyclic rings with both hard nitrogen donors and soft sulfur donors has been prepared. This new ligand, the Janus scorpionate, is a hybrid of a tris(pyrazolyl)borate and a tris(mercaptoimidazolyl)borate. The differential hard/soft character of the dissimilar donor groups in this bridging ligand was exploited for the controlled solid-state organization of homometallic and heterometallic alkali metal coordination polymers.

Ligand-promoted solvent-dependent ionization and conformational equilibria of Re(CO)3Br[CH2(S-tim)2] (tim = 1-methylthioimidazolyl). Crystal structures of Re(CO)3Br[CH2(S-tim)2] and {Re(CO)3(CH3CN)[CH2(S-tim)2]}(PF6).

The compounds Re(CO)3Br[CH2(S-tim)2] (1) and {Re(CO)3(CH3CN)[CH2(S-tim)2]}(PF6) (2), where tim is 1-methylthioimidazolyl, were prepared in high yields and characterized both in the solid state and in solution. The solid-state structures show that the ligand acts in a chelating binding mode where the eight-member chelate ring adopts twist-boat conformations in both compounds. A comparison of both solid-state IR data for CO stretching frequencies and the solution-phase voltammetric measurements for the Re(1+/2+) couples between 1, 2, and related N,N-chelates of the rhenium tricarbonyl moiety indicate that the CH2(S-tim)2 ligand is a stronger donor than even the ubiquitous dipyridyl ligands.

A triclinic polymorph of 1,3-thiazolidine-2-thione (2-mercaptothiazoline).

A planar conformation of 1,3-thiazolidine-2-thione (TZDTH), C3H5NS2, was crystallized for the first time. The new triclinic polymorph (P\overline 1) obtained was compared in terms of its intra- and intermolecular geometry with three previous reports of a monoclinic polymorph (P2(1)/n). The packing is based on centrosymmetric dimers of TZDTH, linked by N-H.

Anion- and solvent-directed assembly in silver bis(thioimidazolyl)methane chemistry and the silver-sulfur interaction.

The effect of metal complexation on the structure and properties of the electroactive bis(1-methylthioimidazolyl)methane linkage isomers CH2(N-tim)2 (L1) and CH2(S-tim)2 (L2) has been explored. Coordination polymers {[Ag(L1)2]X}n (X = BF4, PF6) are formed by bridging L1 between tetrahedral silver centers giving two-dimensional cationic sheets composed of AgS(4) linkages; the anions are sandwiched between sheets. Cyclic dimers {[Ag2(L2)2]X2} (X = BF4, PF6, OSO2CF3) are formed when L2:AgX ratios are lower than 1.

Unexpected new chemistry of the bis(thioimidazolyl)methanes.

[reaction: see text] The synthesis of the linkage isomers of the bis(thioimidazolyl)methane family of compounds, namely CH(2)(N-tim)(2) (1) and CH(2)(S-tim)(2) (2) (where tim = thio(methyl)imidazolyl) has been reinvestigated in order to optimize the yields, to complete the characterization of these known compounds, and also to ascertain the effect of varying heteroatom binding on their electrochemistry. During the course of these studies, the reactive intermediate ClCH(2)(S-tim) (3) was isolated and characterized. The chloromethyl derivative 3 readily decomposes on warming to give the ionic compound [CH(2)(mu-C(4)H(5)N(2)S)(2)CH(2)](Cl)(2) (4), which was converted to the hexafluorophosphate salt (5) and then was characterized by single-crystal X-ray diffraction.