Synthesis, characterization, and reaction chemistry of new trifluoromethanesulfonato complexes of rhodium and iridium: formation of cationic rhodium-platinum and iridium-platinum heterobinuclear complexes with bridging chloride ligands

An investigation of the Lewis acid mediated 1,3-dipolar cycloaddition between N-benzyl-C-(2-pyridyl)nitrone and allylic alcohol. Direct entry to isoxazolidinyl C-nucleosidesElectronic supplementary information (ESI) available: optimized geometries (PDB format). See http://www.rsc.org/suppdata/ob/b3/b304112c/

“…Their IR spectra showed absorptions that can be assigned to covalent triflate groups 17 in the case of 4 and ionic 18 perchlorate for 5. The presence of covalent triflate groups was confirmed by 19 F{ 1 H} NMR, spectra in which a singlet at Ϫ77.5 ppm, characteristic of OSO 2 CF 3 groups, was observed. 19 The 1 H NMR spectra exhibit a downfield displacement of the nitrone resonances in both cases, owing to the coordination to the metallic centre.…”

“…The presence of covalent triflate groups was confirmed by 19 F{ 1 H} NMR, spectra in which a singlet at Ϫ77.5 ppm, characteristic of OSO 2 CF 3 groups, was observed. 19 The 1 H NMR spectra exhibit a downfield displacement of the nitrone resonances in both cases, owing to the coordination to the metallic centre. The 31 P{ 1 H} NMR of 5 displayed a doublet of doublets as a consequence of the 107 Ag (51.82% isotopic abundance) and 109 Ag (48.18%) nucleus coupling.…”

Synthesis of Novel Heterotetrametallic (d6-d10-d8) Polyalkynyl Complexes Starting from Heterobimetallic Chloride-Bridged (d6-d8) Compounds

“…Thus, the cationic mixed derivative [(bzq) 2 Rh(μ‐Cl) 2 Pt(PBu 3 ) 2 ] + is also considerably bent (29.4°)3o and similar nonplanar structures, albeit less severely distorted, have also been found in [(PMe 3 )Cp*Ir(μ‐Cl) 2 Pt(dppp)] 2+ (ca. 11°)3g and [(ppy) 2 Rh(μ‐Cl) 2 PtCl(PBu 3 )] (13.2°) 3l. However, other theoretical and structural analyses of square‐planar d 8 metal complexes of the type [L 2 M(μ‐Cl) 2 ML 2 ] seem to suggest that attractive metal−metal interactions are one of the main factors responsible for the observed bending 10.…”

“…It should be mentioned that several neutral [(ppy) 2 M(μ‐Cl) 2 M′(PR 3 )Cl] (M = Rh, Ir; M′ = Pt, Pd; ppy = 2‐phenylpyridine anion; R = Bu, Et) or cationic [(chel)M(μ‐Cl) 2 M′(PEt 3 ) 2 ](BF 4 ) (M = Rh, Ir; M′ = Pt, Pd; chel = anion of 2‐phenylpyridine, benzo[4]quinoline, C 6 H 5 CHRNMe 2 , or η 3 ‐allyl) heterobinuclear (d 6 ‐d 8 ) chloride‐bridged complexes have been very recently prepared by metathesis reactions from the respective chloro‐bridged homodimeric compounds 3l,3o. In addition, related dicationic [(PMe 3 )(η 5 ‐C 5 Me 5 )M(μ‐Cl) 2 PtL 2 ] 2+ (OTf) − 2 (M = Rh, Ir; L 2 = dppp, 2 PPh 3 ) complexes have been prepared by a similar route starting from the bis(triflate) species [MCp*(PMe 3 )(OTf) 2 ] (M = Rh, Ir) and the corresponding dichloroplatinum derivatives 3g…”

C-C and C-O Coupling Reactions of Terminal Alkynes by a Water Soluble Organoiridium Electron-transfer Mediator in Thin Layer of Water on Gold Electrode

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2+ was previously reported [38].Since it is well-known that terminal alkynes can be activated by organoiridium compounds [11][12][13][14][15][16][17][18], this voltammetric observation prompted us to look into details of reduced-metal catalyzed activation of alkynes in biphasic (H 2 O/CH 2 ClCH 2 Cl) solution. The biphasic

Abstract

An electrochemical reduction process is described for the rapid and efficient conversion of terminal alkynes into useful products.

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