Hampa─Versatile Chelator for [Pb]Pb, [Bi]Bi, and [Ac]Ac.

A new decadentate chelator, Hampa, was designed to be a potential radiopharmaceutical chelator component. The chelator involves both amide and picolinate functional groups on a large non-macrocyclic, ether-bridged backbone. With its large scaffold, Hampa was paired with [Pb]Pb, [Bi]Bi, and La/[Ac]Ac ions.

Direct, Catalytic α-Alkylation of -Heterocycles by Hydroaminoalkylation: Substrate Effects for Regiodivergent Product Formation.

Saturated -heterocycles are prevalent in pharmaceutical and agrochemical industries, yet remain challenging to catalytically alkylate. Most strategies for C-H activation of these challenging substrates use protected amines or high loadings of precious metal catalysts. We report an early transition-metal system for the broad, robust, and direct alkylation of unprotected amine heterocycles with simple alkenes.

Controlling photocatalytic reduction of CO in Ru(II)/Re(I) dyads linker oxidation state.

Electronic communication between the linked metal centers in Ru(ii)-Re(i) dyads is tuned using the oxidation state (S and SO2) of sulfur-bridged ligands. Higher catalytic activity is seen for the SO2-bridged dyad in the photocatalytic reduction of CO2.

Tunable Emission of Iridium(III) Complexes Bearing Sulfur-Bridged Dipyridyl Ligands.

A series of six new cyclometalated iridium(III) complexes [Ir(ppy)(NN)][PF] (ppy = 2-phenylpyridine) is reported herein. Proligands bis(pyridin-2-yl)sulfane (1a), 2,2'-sulfinyldipyridine (1b), 2,2'-sulfonyldipyridine (1c), bis(4-methylpyridin-2-yl)sulfane (2a), 2,2'-sulfinylbis(4-methylpyridine) (2b), and 2,2'-sulfonylbis(4-methylpyridine) (2c) were synthesized, characterized, and employed as the NN ancillary ligand. Changing the oxidation state of the sulfur atom serves as a switch to alter the emissive state from that of mainly LC character (blue-green emission) to one of MLCT/LLCT character (yellow emission).

[HL][P(1,2-OCCl)] (L = THF, DMF): Brønsted acid initiators for the polymerization of n-butyl vinyl ether and p-methoxystyrene.

The development of solid, weighable Brønsted acids featuring the hexacoordinated phosphorous(v) anion [TRISPHAT] are reported. H(DMF)[1] and H(THF)[1] {[1] = [P(1,2-OCCl)]} were synthesized and fully characterized by H, P, C and 2D-NOESY NMR spectroscopy, X-ray crystallography, mass spectrometry and elemental analysis. Both, H(DMF)[1] and H(THF)[1] are found to be suitable initiators for the polymerization of n-butyl vinyl ether and p-methoxystyrene.

Interactions of Rh(III)-dihydrido-bis(phosphine) complexes with semicarbazones.

Interaction of cis,trans,cis-[Rh(H)2(PR3)2(acetone)2]PF6 complexes (R = aryl or R3 = Ph2Me, Ph2Et) under H2 with E-semicarbazones gives the Rh(III)-dihydrido-bis(phosphine)-semicarbazone species cis,trans-[Rh(H)2(PR3)2{R'(R' ')C=N-N(H)CONH2}]PF6, where R' and R' ' are Ph, Et, or Me. The complexes are generally characterized by elemental analysis, 31P{1H} NMR, 1H NMR, and IR spectroscopies, and MS. X-ray analysis of three PPh3 complexes reveals chelation of E-semicarbazones by the imine-N atom and the carbonyl-O atom.