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The synthesis and structural characterization of an electron poor Au(III) trication bearing 2 imidazole and 2 acetonitrile ligands is described. The new complex is capable of aryl C–H metalation with the formation of a monomesitylene complex and also demonstrated to be highly oxidizing in the rapid room temperature conversion of cyclohexene to benzene. [ABSTRACT FROM AUTHOR]

A series of nine luminescent iridium(III) complexes with pH-responsive imidazole and benzimidazole ligands have been prepared and characterized. The first series of complexes were of the form [Ir(ppy)2(N^N)]+ or [Ir(ppy)2(C^N)]+ (where ppy is 2-phenylpyridine and N^N is 2-(2-pyridyl)imidazole or 2-(2-pyridyl)benzimidazole and C^N represents a pyridyl-triazolylidene-based N-heterocyclic carbene ligand). For these complexes, the benzimidazole group was either unsubstituted or substituted with electron-withdrawing (Cl) or electron-donating (Me) groups. The second series of complexes were of the form [Ir(phbim)2(N^N)]+ or [Ir(phbim)2(C^N)]+ (where phbim is 2-phenylbenzimidazole and N^N is either 2,2′-bipyridine or 1,10-phenanthroline and C^N is either a pyridyl-imidazolylidene or pyridyl-triazolylidene N-heterocyclic carbene ligand). UV-visible and photoluminescence pH titration studies showed that changing the protonation state of these complexes results in significant changes in the photoluminescence emission properties. The pKa values of prepared complexes were estimated from the spectroscopic pH titration data and these values show that the nature of the pH-sensitive ligands (either main or ancillary ligands) resulted in a significant capacity to modulate the pKa values for these compounds with values ranging from 5.19–11.22. Theoretical investigations into the nature of the electronic transitions for the different protonation states of compounds were performed and the results were consistent with the experimental results. [ABSTRACT FROM AUTHOR]

The recently discovered I(III) reagent NO2-C6H4-I(OTf)2 is found to rapidly react with hydride sources, including HSiEt3 and relatively hydridic C–H precursors. These represent the first distinct reactions involving direct hydride abstraction by I(III) under ambient conditions. Direct C–F abstraction is also demonstrated, as well as oxidation of cyclic alkenes to aromatic rings, all representing new reactions for I(III) demonstrating the very high reactivity of NO2-C6H4-I(OTf)2. [ABSTRACT FROM AUTHOR]

Synthesis and crystallographic characterization of NO2–C6H4–I(NTf2)2 (NTf2 = bistriflimide) is reported. Experimental results find that this compound can perform oxidation reactions that ArI(OTf)2 is unable to and theoretical analysis indicates Ar–I(NTf2)2 is the most oxidizing in the ArIL2 class of compounds known and may also be the most oxidizing compound in the class practically possible. [ABSTRACT FROM AUTHOR]

The structure of Stang's reagent [PhI(CN)][OTf] is confirmed by X-ray crystallography and is determined to be best described as an ion-pair in organic solution. It is found to be a strong Lewis acid, but reaction with pyridine ligands gives [Pyr-CN][OTf] salts via oxidation of pyridine giving a new derivative of the CDAP reagent widely used as an activation agent for polysaccharides. [ABSTRACT FROM AUTHOR]

Both mixed λ3-iodoarenes and λ3-iodoarenes possessing –OTf ligands are coveted for their enhanced reactivities. Here we describe the synthesis, reactivity, and comprehensive characterisation of two new ArI(OTf)(X) species, a class of compound that were previously only invoked as reactive intermediates where X = Cl, F and their divergent reactivity with aryl substrates. A new catalytic system for electrophilic chlorination of deactivated arenes using Cl2 as the chlorine source and ArI/HOTf as the catalyst is also described. [ABSTRACT FROM AUTHOR]

The combination of 4-hydroxybenzoic acid (H2hba) with Li+, Mg2+ and Cu2+ yields coordination polymers in which metal centres are bridged by an anion of the acid, either Hhba− or hba2−. In the case of Li+, a 3D network of composition Li2(hba)DMF was isolated in which parallel channels are occupied by coordinated DMF molecules. Mg2+ combines with H2hba to form a 2D square grid network with the formula Mg(Hhba)2(H2O)2. The alignment of parallel sheets results in the formation of channels filled with 1,4-dioxane molecules that hydrogen bond to coordinated water molecules. The compound Cu3(hba)2(OH)2(1,4-dioxane)1.5·0.5(1,4-dioxane) is a complex 3D network formed from the combination of Cu2+ with H2hba under basic conditions. The crystal structure determination reveals bridging 1,4-dioxane molecules. A reversible phase change occurs in the temperature range 200–220 K. The investigation highlights the key role of the solvent molecules in the structures of this series of compounds. [ABSTRACT FROM AUTHOR]

Synthesis and crystallographic characterization of NO2–C6H4–I(NTf2)2 (NTf2 = bistriflimide) is reported. Experimental results find that this compound can perform oxidation reactions that ArI(OTf)2 is unable to and theoretical analysis indicates Ar–I(NTf2)2 is the most oxidizing in the ArIL2 class of compounds known and may also be the most oxidizing compound in the class practically possible. [ABSTRACT FROM AUTHOR]

A series of solid-state structural transformations are found to accompany desolvation of relatively simple coordination polymers to yield materials that exhibit unexpected gas sorbing properties. Reaction of 1,2,4,5-tetrahydroxybenzene with MII salts (M = Mg, or Zn) in an alcohol/water solution in the presence of air affords cis-MII(C6H2O4−II)(H2O)2·2H2O·xROH, (M = Mg, or Zn), crankshaft-like chains in which the absolute configurations of the chiral metal centres follow the pattern …ΔΔΛΛΔΔΛΛ…, and are hydrogen bonded together to generate spacious channels. When crystals of the crankshaft chain are air dried the crystals undergo a single crystal-to-powder rearrangement to form linear trans-MII(C6H2O4−II)(H2O)2 chains. Further dehydration yields microporous solids that reversibly sorb H2, CH4 and CO2 with high sorption enthalpies. [ABSTRACT FROM AUTHOR]

A new piperazine-derived ligand has been prepared and used to synthesise a porous coordination polymer which displays selective carbon dioxide uptake after solvent exchange and thermal activation. The ligand N,N′-bis(4-carboxyphenylmethylene)piperazine H2L1 was prepared from piperazine in three steps and good yield. A structure containing the deprotonated form K2L1·2H2O was determined and consists of a three-dimensional coordination polymer containing inorganic K2(COO)2(OH2) layers separated by the long organic bridging linker. The free compound H2L1 displays a one-dimensional hydrogen-bonded polymeric structure in the solid state with hydrogen bonding interactions between carboxylic acids and piperazine groups tightly linking molecules together. The two-dimensional polymeric complex [Zn3(L1)2(OH)2]·2DMF·0.5H2O 1 was prepared and analysed in the solid state to reveal tubular one-dimensional channels which, when activated by solvent exchange and evacuation, displayed selective affinity for CO2 over N2 and H2. [ABSTRACT FROM AUTHOR]

The monoanion of 1,3-bis(carboxymethyl)imidazolium (H2imdc+) combines with Cu(ii) to produce an undulating 2D coordination polymer of composition [Cu2(imdc)2(CH3OH)2](BF4)2·(CH3OH)(H2O) (1) in which copper acetate-like dimers, linked by imdc− ligands, act as 4-connecting centres. Cationic sheets stack on top of each other in an A, B, A, B… fashion and produce a structure that contains channels running parallel to the plane of network. Tetrafluoroborate anions are located in channels between sheets. Upon removal of coordinated and non-coordinated solvent molecules a single crystal-to-single crystal transformation occurs to yield a similar compound but with BF4− anions now coordinated. CO2 isotherms measured at 258 and 273 K show only modest uptake of CO2 but provide an indication that the sheets move apart at elevated pressures in order to accommodate the guest molecules. A compound of composition [Cu3(OH)2(imdc)2]·SiF6·2H2O·2MeOH (3), which possesses a 3D network, is formed by the combination of copper(ii) acetate, copper(ii) hexafluorosilicate and Himdc. In this structure infinite parallel Cu3(OH)2 chains are linked by bridging imdc− ligands to form channels that have an approximately triangular cross-section. These channels are occupied by SiF62− anions in addition to solvent molecules. When copper(ii) acetate is combined with Himdc in the appropriate ratio, a 1D coordination polymer of composition Cu(imdc)2 (4) is formed in which pairs of imdc− anions bridge Cu(ii) centres. When the reaction is performed in the presence of NaBF4 a minor crystalline product with tetragonal symmetry is isolated in addition to the 1D coordination polymer. This compound of composition Cu2(imdc)4NaBF4·7H2O (5) consists of 2D Cu(imdc)2 networks and features an unusual mode of interpenetration. [ABSTRACT FROM AUTHOR]

A series of solid-state structural transformations are found to accompany desolvation of relatively simple coordination polymers to yield materials that exhibit unexpected gas sorbing properties. Reaction of 1,2,4,5-tetrahydroxybenzene with MII salts (M = Mg, or Zn) in an alcohol/water solution in the presence of air affords cis-MII(C6H2O4−II)(H2O)2·2H2O·xROH, (M = Mg, or Zn), crankshaft-like chains in which the absolute configurations of the chiral metal centres follow the pattern …ΔΔΛΛΔΔΛΛ…, and are hydrogen bonded together to generate spacious channels. When crystals of the crankshaft chain are air dried the crystals undergo a single crystal-to-powder rearrangement to form linear trans-MII(C6H2O4−II)(H2O)2 chains. Further dehydration yields microporous solids that reversibly sorb H2, CH4 and CO2 with high sorption enthalpies. [ABSTRACT FROM AUTHOR]

A series of nine luminescent iridium(III) complexes with pH-responsive imidazole and benzimidazole ligands have been prepared and characterized. The first series of complexes were of the form [Ir(ppy) 2 (N^N)] + or [Ir(ppy) 2 (C^N)] + (where ppy is 2-phenylpyridine and N^N is 2-(2-pyridyl)imidazole or 2-(2-pyridyl)benzimidazole and C^N represents a pyridyl-triazolylidene-based N-heterocyclic carbene ligand). For these complexes, the benzimidazole group was either unsubstituted or substituted with electron-withdrawing (Cl) or electron-donating (Me) groups. The second series of complexes were of the form [Ir(phbim) 2 (N^N)] + or [Ir(phbim) 2 (C^N)] + (where phbim is 2-phenylbenzimidazole and N^N is either 2,2'-bipyridine or 1,10-phenanthroline and C^N is either a pyridyl-imidazolylidene or pyridyl-triazolylidene N-heterocyclic carbene ligand). UV-visible and photoluminescence pH titration studies showed that changing the protonation state of these complexes results in significant changes in the photoluminescence emission properties. The p K a values of prepared complexes were estimated from the spectroscopic pH titration data and these values show that the nature of the pH-sensitive ligands (either main or ancillary ligands) resulted in a significant capacity to modulate the p K a values for these compounds with values ranging from 5.19-11.22. Theoretical investigations into the nature of the electronic transitions for the different protonation states of compounds were performed and the results were consistent with the experimental results.

Synthesis and crystallographic characterization of NO 2 -C 6 H 4 -I(NTf 2 ) 2 (NTf 2 = bistriflimide) is reported. Experimental results find that this compound can perform oxidation reactions that ArI(OTf) 2 is unable to and theoretical analysis indicates Ar-I(NTf 2 ) 2 is the most oxidizing in the ArIL 2 class of compounds known and may also be the most oxidizing compound in the class practically possible.

The structure of Stang's reagent [PhI(CN)][OTf] is confirmed by X-ray crystallography and is determined to be best described as an ion-pair in organic solution. It is found to be a strong Lewis acid, but reaction with pyridine ligands gives [Pyr-CN][OTf] salts via oxidation of pyridine giving a new derivative of the CDAP reagent widely used as an activation agent for polysaccharides.

Both mixed λ 3 -iodoarenes and λ 3 -iodoarenes possessing -OTf ligands are coveted for their enhanced reactivities. Here we describe the synthesis, reactivity, and comprehensive characterisation of two new ArI(OTf)(X) species, a class of compound that were previously only invoked as reactive intermediates where X = Cl, F and their divergent reactivity with aryl substrates. A new catalytic system for electrophilic chlorination of deactivated arenes using Cl 2 as the chlorine source and ArI/HOTf as the catalyst is also described.

A series of solid-state structural transformations are found to accompany desolvation of relatively simple coordination polymers to yield materials that exhibit unexpected gas sorbing properties. Reaction of 1,2,4,5-tetrahydroxybenzene with M(II) salts (M = Mg, or Zn) in an alcohol/water solution in the presence of air affords cis-M(II)(C6H2O4(-II))(H2O)2·2H2O·xROH, (M = Mg, or Zn), crankshaft-like chains in which the absolute configurations of the chiral metal centres follow the pattern Δ Δ Λ Λ Δ Δ Λ Λ, and are hydrogen bonded together to generate spacious channels. When crystals of the crankshaft chain are air dried the crystals undergo a single crystal-to-powder rearrangement to form linear trans-M(II)(C6H2O4(-II))(H2O)2 chains. Further dehydration yields microporous solids that reversibly sorb H2, CH4 and CO2 with high sorption enthalpies.

The synthesis, structural and gas sorption studies of a porous Cu(II) coordination polymer featuring 1H-indazole-5-carboxylic acid (H(2)L) are presented. [Cu(HL)(2)] is a thermally and hydrolytically robust 4-connected 3D coordination polymer of NbO topology and is replete with 1D channels that permit selective and hysteretic sorption of CO(2).