Ammonium Hexachloroiridate(IV)

Kauffman, George B.; Teter, Larry A.; Hogarth, J. W.; Dwyer, Francis Patrick John

doi:10.1002/9780470132395.ch59

Cited by 20 publications

(8 citation statements)

References 4 publications

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“…Higher generations were achieved by repetitive acidic deprotections and additions with the anhydride 9. trans-PtCl 2 (PBu 3 ) 2 (18) was synthesized by stirring PtCl 2 (17) and PBu 3 in water to 80 °C for 8 h, which gave a mixture of cis-and trans-PtCl 2 (PBu 3 ) 2 (Scheme 4). The crude product was melted and converted to the trans isomer 18 68 and purified by flash chromatography over silica. The synthesis of the dendron decorated Pt acetylide compounds 19a-d was carried out by a Sonogashira-type coupling reaction of the suitable decorated arylalkynyl ligands (10,12,14,16) to PtCl 2 (PBu 3 ) 2 with CuI as catalyst.…”

Section: Resultsmentioning

confidence: 99%

Dendron Decorated Platinum(II) Acetylides for Optical Power Limiting

et al. 2006

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The effect of dendritic substituents on a nonlinear optical chromophore for optical power limiting (OPL) has been investigated. Synthesis and characterization of bis((4-(phenylethynyl)phenyl)ethynyl)bis-(tributylphosphine)platinum(II) with dendritic end groups are described. Polyester dendrimers up to the fourth generation were grown divergently using the anhydride of 2,2-bis(methylol)propionic acid (bis-MPA). The introduction of the dendritic moieties onto the NLO chromophore enables further processing of the materials using polymeric and related techniques. OPL measurements performed at 532, 580, and 630 nm show that the OPL properties improve with increasing size of the dendritic substituent. It is also shown that the addition of the dendrons increase the OPL as compared to the nondecorated bis((4-(phenylethynyl)phenyl)ethynyl)bis-(tributylphosphine)platinum(II). By use of femtosecond z-scan measurements carried out at different pulse-repetition frequencies, it is shown that the two-photon absorption cross section is ∼10 GM. Using pulse repetition frequencies (100 kHz-4.75 MHz) so that the time between the pulses is comparable with the triplet excited lifetime, the z-scans become dominated by excited-state absorption of excited triplet states.

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Section: Resultsmentioning

confidence: 99%

Dendron Decorated Platinum(II) Acetylides for Optical Power Limiting

et al. 2006

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“…Hydrogen tetrachloroaurate(III) trihydrate (HAuCl 4 .3H 2 O, Aldrich, 99.9+%), potassium tetrachloroplatinate (K 2 PtCl 4 , Aldrich, 99.9+%), tributylphosphine (PBu 3 , Aldrich, 98%), allylmercaptane (AM, Aldrich 98% pure), potassium thioacetate (CH 3 COSK, Aldrich, 98%), tetraoctylammonium bromide (TOAB, Aldrich, 98%), sodium borohydride (NaBH 4 , Aldrich, 99%), and organic solvents (Aldrich reagent grade) were used as received. Platinum complex trans - [dichlorobis(tributylphosphine)platinum(II)] and 4,4′-diethynylbiphenyl (H–CC–C 6 H 4 –C 6 H 4 –CC–H, DEBP) were prepared by reported methods. , Preparative thin-layer chromatography (TLC) separation was performed on 0.7 mm silica plates (Merck Kieselgel 60 GF254), and chromatographic separations were obtained with 70-230 mesh silica (Merck) by using n-hexane/dichloromethane mixtures. Deionized water, obtained from Millipore-SIMPAKOR1 (Simplicity185), was degassed for 30 min with Argon before use.…”

Section: Methodsmentioning

confidence: 99%

“…Platinum complex trans-[dichlorobis(tributylphosphine)platinum(II)] and 4,4 0 -diethynylbiphenyl (HÀCtCÀC 6 H 4 ÀC 6 H 4 ÀCtCÀH, DEBP) were prepared by reported methods. 17,18 Preparative thin-layer chromatography (TLC) separation was performed on 0.7 mm silica plates (Merck Kieselgel 60 GF254), and chromatographic separations were obtained with 70-230 mesh silica (Merck) by using n-hexane/dichloromethane mixtures. Deionized water, obtained from Millipore-SIMPAKOR1 (Simplicity185), was degassed for 30 min with Argon before use.…”

Section: Introductionmentioning

confidence: 99%

Gold Nanoparticle Dyads Stabilized with Binuclear Pt(II) Dithiol Bridges

et al. 2011

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The synthesis and characterization of gold nanoparticles (AuNPs-1) stabilized by a novel bifunctional thiolate organometallic complex containing Pt(II) centers, that is, trans,trans-[(CH(3)COS) (PBu(3))(2)Pt-C equivalent to C-C(6)H(4)-C(6)H(4)-C equivalent to C Pt(PBu(3))(2)(SCOCH(3))] (complex 1), has been carried out. As a comparison, gold nanoparticles stabilized with an organic thiol, allylmercaptane, that is, AuNPs-2, and self-assembled monolayers (SAMs) of both thiols were also prepared and investigated. The AuNPs-1 show a direct link between Pt(II) and Au nanoparticles through a single S bridge and are candidates for the achievement of 2D or 3D networks. The size control of the Au nanoparticles was achieved by careful control of synthesis parameters, and the hybrids were characterized by means of high-resolution transmission electron microscopy (HR-TEM) and synchrotron radiation induced X-ray photoelectron spectroscopy (SR-XPS). SR-XPS measurements allowed the assessment of the anchoring of the organic or organometallic thiols onto gold substrates as well as onto gold nanoparticles. AuNPs-2 with diameters in the range from 1.6 to 3.9 nm were obtained. AuNPs-1 with an average diameter in the range of 4.5-3.6 nm were obtained, and linkage between the nanoparticles can be envisaged with the formation of dyads supported by SR-XPS measurements. In fact, S2p core-level data indicate that both sulfur atoms of the organometallic thiol chemically interact with gold grafting vicinal natioparticles

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“…Certain commercial samples of Na 2 IrCl 6 •6H 2 O were found by spectrophotometric analysis of chlorinated solutions to contain as much as 10% Ir(III) and thus were not used further. (NH 4 ) 2 [IrCl 6 ] was prepared according to the literature by addition of NH 4 Cl to a solution of Na 2 IrCl 6 •6H 2 O. Chemicals of reagent and analytical grade were stored in the dark or under subdued light conditions.…”

Section: Methodsmentioning

confidence: 99%

Kinetic Isotope Effect and Extended pH-Dependent Studies of the Oxidation of Hydroxylamine by Hexachloroiridate(IV): ET and PCET

Makarycheva-Mikhailova

Stanbury

McKee

2007

J. Phys. Chem. B

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The oxidation of hydroxylamine by [IrCl6]2- has been studied spectrophotometrically in deoxygenated aqueous solutions in the range of pH 4-9 at 25 degrees C. The reaction is catalyzed by Cu2+, Fe2+, and impurities of aquochloroiridium complexes. Oxalate is a very effective inhibitor of catalysis by copper and iron ions. With excess hydroxylamine, the reaction follows pseudo-first-order kinetics, and the stoichiometric ratio (DeltanIr(IV)/Deltanhydroxylamine) is 1.05 at pH 5.9. Over the pH range 4.2-8.8, the empirical rate law is -d[IrCl(6)2-]/dt=k[IrCl6(2-)][NH2OH]tot, with k=k1Ka1/([H+]+Ka1)+k'Ka1/([H+]([H+]+Ka1)), where Ka1 is the dissociation constant of NH3OH+. Least-squares fitting yields k1=(17.05+/-0.47) M-1 s(-1) and k'=(2.59+/-0.09)x10(-6) s(-1) at ionic strength of 0.1 M (adjusted by NaClO4) and 25 degrees C. The kinetic isotope effects (KIE) (kH/kD) for k1 and k' are 4.4 and 9.8, correspondingly. A mechanism is inferred in which k1 corresponds to concerted proton-coupled electron transfer (PCET) and k' corresponds to electron transfer from NH2O-. In this mechanism, the large KIE for k' is due almost entirely to the equilibrium isotope effect for the pKa of NH2OH.

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Ammonium Hexachloroiridate(IV)

Cited by 20 publications

References 4 publications

Dendron Decorated Platinum(II) Acetylides for Optical Power Limiting

Dendron Decorated Platinum(II) Acetylides for Optical Power Limiting

Gold Nanoparticle Dyads Stabilized with Binuclear Pt(II) Dithiol Bridges

Kinetic Isotope Effect and Extended pH-Dependent Studies of the Oxidation of Hydroxylamine by Hexachloroiridate(IV): ET and PCET

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