Self-complementary nickel halides enable multifaceted comparisons of intermolecular halogen bonds: fluoride ligands other halides.

The syntheses of three series of complexes designed with self-complementary motifs for formation of halogen bonds between an iodotetrafluorophenyl ligand and a halide ligand at square-planar nickel are reported, allowing structural comparisons of halogen bonding between all four halides CFI···X-Ni (X = F, Cl, Br, I). In the series -[NiX(2,3,5,6-CFI)(PEt)] and -[NiX(2,3,4,5-CFI)(PEt)] (X = F, Cl, Br, I) , the iodine substituent on the benzene ring was positioned and to the metal, respectively. The phosphine substituents were varied in the series, -[NiX(2,3,5,6-CFI)(PEtPh)] (X = F, I) .

Concise Xanthine Synthesis through a Double-Amidination Reaction of a 6-Chlorouracil with Amidines using Base-Metal Catalysis.

A new and concise route towards xanthines through a double-amidination reaction is described; consecutive intermolecular C-Cl and intramolecular oxidative C-H amidination. N-uracil amidines are obtained through S AE on a 6-chlorouracil with amidines. Direct Cu-catalyzed oxidative C-H amidination on these N-uracil amidines yields polysubstituted xanthines.

The Contrasting Character of Early and Late Transition Metal Fluorides as Hydrogen Bond Acceptors.

The association constants and enthalpies for the binding of hydrogen bond donors to group 10 transition metal complexes featuring a single fluoride ligand (trans-[Ni(F)(2-C5NF4)(PR3)2], R = Et 1a, Cy 1b, trans-[Pd(F)(4-C5NF4)(PCy3)2] 2, trans-[Pt(F){2-C5NF2H(CF3)}(PCy3)2] 3 and of group 4 difluorides (Cp2MF2, M = Ti 4a, Zr 5a, Hf 6a; Cp*2MF2, M = Ti 4b, Zr 5b, Hf 6b) are reported. These measurements allow placement of these fluoride ligands on the scales of organic H-bond acceptor strength. The H-bond acceptor capability β (Hunter scale) for the group 10 metal fluorides is far greater (1a 12.

Metal hydrides form halogen bonds: measurement of energetics of binding.

The formation of halogen bonds from iodopentafluorobenzene and 1-iodoperfluorohexane to a series of bis(η(5)-cyclopentadienyl)metal hydrides (Cp2TaH3, 1; Cp2MH2, M = Mo, 2, M = W, 3; Cp2ReH, 4; Cp2Ta(H)CO, 5; Cp = η(5)-cyclopentadienyl) is demonstrated by (1)H NMR spectroscopy. Interaction enthalpies and entropies for complex 1 with C6F5I and C6F13I are reported (ΔH° = -10.9 ± 0.

A thermally stable gold(III) hydride: synthesis, reactivity, and reductive condensation as a route to gold(II) complexes.

Going for gold: The first thermally stable gold(III) hydride [(C N C)*AuH] is presented. It undergoes regioselective insertions with allenes to give gold(III) vinyl complexes, and reductive condensation with [(C N C)*AuOH] to the air-stable Au(II) product, [(C N C)*(2)Au(2)], with a short nonbridged gold-gold bond.

Cyclometallated gold(III) hydroxides as versatile synthons for Au-N, Au-C complexes and luminescent compounds.

The gold(III) hydroxide κ(3)-(C^N^C)*Au(OH) reacts with C-H and N-H compounds and arylboronic acids to produce a range of perfluoroaryls, N-heterocyclic and alkynyl compounds in high yields; some of which show unexpectedly strong modulation of their photoluminescence from yellow to blue [(C^N^C)* = 2,6-(C(6)H(3)Bu(t))(2)pyridine].

C-H and C-O oxidative addition in reactions of aryl carboxylates with a PNP pincer-ligated Rh(I) fragment.

Reactions of a series of phenyl esters with a (PNP)Rh fragment have been studied. PhO(2)CPh only underwent C-H oxidative addition (OA). PhO(2)CCF(3) chiefly underwent acyl-oxygen OA.

Early-late heterobimetallic Rh-Ti and Rh-Zr complexes via addition of early metal chlorides to mono- and divalent rhodium.

Addition of TiCl(4) or ZrCl(4) to (PNP)Rh(CH(2)==CH(t)Bu) (1) rapidly gives complexes (PNP)Rh(MCl(3))(Cl) (M = Ti, 2; Zr, 3) in 75-77% yield (PNP = (4-Me-2-((i)Pr(2)P)-C(6)H(3))(2)N). Compound 2 can also be synthesized via a reaction of (PNP)RhCl with TiCl(3) or of (PNP)TiCl(3) with 1/2 [(cod)RhCl](2).