230,082 research outputs found
Quaterpyridine Ligands for Panchromatic Ru(II) Dye Sensitizers
No full textA new general synthetic access to carboxylated quaterpyridines (qpy), of interest as ligands for panchromatic dyesensitized solar cell organometallic sensitizers, is presented. The strategic step is a Suzuki−Miyaura cross-coupling reaction,
which has allowed the preparation of a number of representative unsubstituted and alkyl and (hetero)aromatic substituted qpys.
To bypass the poor inherent stability of 2-pyridylboronic acid derivatives, we successfully applied N-methyliminodiacetic acid
(MIDA) boronates as key reagents, obtaining the qpy ligands in good yields up to (quasi)gram quantities. The structural,
spectroscopic (NMR and UV−vis), electrochemical, and electronic characteristics of the qpy have been experimentally and
computationally (DFT) investigated. The easy access to the bis-thiocyanato Ru(II) complex of the parent species of the qpy
series, through an efficient route which bypasses the use of Sephadex column chromatography, is shown. The bis-thiocyanato
Ru(II) complex has been spectroscopically (NMR and UV−vis), electrochemically, and computationally investigated, relating its
properties to those of previously reported Ru(II)−qpy complexes.“This document is the Accepted Manuscript version of a Published Work that appeared in final form in [The Journal of Organic Chemistry], copyright © American Chemical Society after peer review and technical editing by the publisher
EXAFS, DFT, light-induced nucleobase binding, and cytotoxicity of the photoactive complex cis-[Ru(bpy)2(CO)Cl]+
No full textThe aqueous photochemistry of cis-[Ru(bpy)2(CO)Cl]+ (1) was investigated at 310 K and under visible light (white) irradiation by NMR and ESI-HR-MS. Complex 1 releases a Cl ligand, coordinates a solvent molecule, and forms the complex cis-[Ru(bpy)2(CO)(H2O)]2+ (2). Also, irradiation experiments were performed in the presence of the nucleobase derivatives 9-ethylguanine (9-EtG) and 9-ethyladenine (9-EtA). Formation of Ru-9-EtG adducts was observed after 3 h irradiation by NMR and HR-MS, while only very small amounts of a Ru-9-EtA adduct could be detected by HR-MS. Solution structural data were obtained by X-ray absorption spectroscopy (XAS) for both 1 and 2. EXAFS gave a Ru−Cl distance of 2.416(7) Å for 1 and a Ru−OH2O distance of 2.102(6) Å for 2. DFT and TDDFT were employed to study the photophysical and photochemical properties of 1. Calculations show that dissociative metal-centered states can be related to the light-induced release of a Cl ligand and subsequent coordination of a solvent molecule. The compound showed no antiproliferative activity in three human carcinoma cell lines (lung, bladder, pancreas) under the testing conditions, either with or without irradiation with UV light
Outsourcing and Skill Imports: Foreign High-Skilled Workers on H-1B and L-1 Visas in the United States
No full textThis working paper looks in detail at the H-1B and L-1 visa programs for temporary employment in the United States. Based on official data from the US Citizenship and Immigration Services and the US Department of State, H-1B and L-1 visa issuance rapidly increased in the late 1990s, followed by a marked slowdown after 2001. This points to the highly cyclical nature of both visa programs. Indian nationals and immigrants working in computer-related occupations dominate the H1-B and L-1 population in the United States, but these two groups are also found to be the most cyclical segment, with very large declines in inflows after 2001. The total population of H-1B visaholders in 2003 is estimated to range between 387,000 and 746,000, of which 160,000 to 306,000 were Indian nationals. As all data on H-1B/L-1 visaholders are gross numbers and gross jobs data for comparable categories are absent, the extent of the impact of these visa programs on the US labor market cannot be gauged precisely. A broad range of US industries and educational institutions are found to be employing H-1B recipients, with the IT industry being the dominant sector. Evidence of aggressive wage-cost cutting, including paying H-1B recipients only the legally mandated 95 percent of the prevailing US wage, is found among some H-1B employers, although no systematic abuse of the system is present.Outsourcing, offshoring, high-skilled labor, immigration, H1B/L-1 visas
Electrodeposition of arrays of Ru, Pt, and PtRu Alloy 1D metallic nanostructures
No full textArrays of Ru, Pt, and PtRu one dimensional 1D nanowires NWs and nanotubes NTs were prepared by electrodeposition through the porous structure of an anodic aluminum oxide AAO membrane. In each case, micrometer-long NW and NT were formed with an outer diameter of ca. 200 nm, close to the interior diameter of the porous AAO membrane. Arrays of NW and NT can be formed by varying the metallic salt concentration, the applied potential, and the conductivity of the electrolyte. The Ru and Pt deposition rates were measured in the various deposition conditions, using an electrochemical quartz crystal microbalance. The mechanisms responsible for the formation of Ru and Pt NW and NT are discussed based on the observed deposition rates and models found in the literature. Finally, it is shown that arrays of PtRu alloy NT and NW can be readily prepared and their compositions can be varied over the whole compositional range by changing the metallic salt concentration of the electrodeposition bath
Ru-Catalyzed Enantioselective Hydrogenation of 2Pyridyl-Substituted Alkenes and Substrate-Mediated H/D Exchange
No full textA highly
efficient and enantioselective asymmetric hydrogenation
catalyzed by Ru-DTBM-segphos is reported for a broad range of pyridine–pyrroline
trisubstituted alkenes. Kinetic, spectroscopic, and computational
studies suggest that addition of H2 is rate-determining,
alkene insertion is enantio-determining, and that the presence and
position of the pyridine nitrogen is critical to enantioselectivity.
These studies also reveal an intriguing Ru-catalyzed H/D exchange
process that is facilitated by a substrate at room temperature and
low pressure, where hydrogenation activity is suppressed. These studies
lead to a mechanistic proposal that further defines the roles of hydrogen
gas, Ru–H species, and protic solvents in this catalytic system
Size-controlled synthesis of thermal stable single-cored Ru@H-SiO2 core-shell nanoparticles
No full textSingle-cored Ru@H-SiO2 (H: hollow) core-shell nanoparticles (NPs) with around 4.3 nm Ru cores and hollow SiO2 shells were prepared successfully. In this synthetic process, we obtained multi-cored Ru@SiO2 NPs initially, single-cored RuO2@H-SiO2 NPs during treatment, and single-cored Ru@H-SiO2 NPs in the end. The Ru@SiO2 NPs were prepared by water-in-oil microemulsion method, and the size and core number of Ru@SiO2 NPs can be controlled. Single-cored RuO2@H-SiO2 NPs and Ru@H-SiO2 NPs were successively obtained by calcination and reduction. The structure showed promising aggregate-resistant performance and potential application in catalysis. (C) 2016 Published by Elsevier B.V
Coordinatively unsaturated ruthenium complexes as efficient alkyne-azide cycloaddition catalysts
No full textThe performance of 16-electron ruthenium complexes with the general formula Cp*Ru(L)X (in which L = phosphine or N-heterocyclic carbene ligand; X = Cl or OCH2CF3) was explored in azide−alkyne cycloaddition reactions that afford the 1,2,3- triazole products. The scope of the Cp*Ru(PiPr3)Cl precatalyst was investigated for terminal alkynes leading to new 1,5-disubstituted 1,2,3-triazoles in high yields. Mechanistic studies were conducted and revealed a number of proposed intermediates. Cp*Ru- (PiPr3)(η2-HCCPh)Cl was observed and characterized by 1H, 13C, and 31P NMR at temperatures between 273 and 213 K. A rare example of N,N-κ2-phosphazide complex, Cp*Ru(κ2-iPr3PN3Bn)Cl, was fully characterized, and a single-crystal X-ray diffraction structure was obtained. DFT calculations describe a complete map of the catalytic reactivity with phenylacetylene and/or benzylazide.Peer reviewe
Sequential formation of [Ru(IPr)2(CO)H(OH2)] + and [Ru(IPr)(η6-6H6)(CO)H] + upon protonation of Ru(IPr)2(CO)H(OH) (IPr = l,3-bis(2,6- diisopropylphenyl)imidazol-2-ylidene)
No full textProtonation of the N-heterocyclic carbene (NHC) complex Ru(IPr) 2(CO)H(OH) (IPr = l,3-bis(2,6-diisopropy-lphenyl)imidazol-2-ylidene) with HBF4 OEt2 in thf affords the cationic aqua hydride complex [Ru(IPr)2(CO)H(OH2)](BF2), whereas if the solvent is changed to benzene, loss of imidazolium salt and H20 occurs to leave the 12e fragment [Ru(IPr)-(CO)H]+, which is isolated as the cationic arene species [Ru(IPr)(η6- C6H 6)(CO)H](BF6). © 2009 American Chemical Society
Metallkomplexe mit biologisch wichtigen Liganden, LXV
No full textCp*Co(CO)I2 (Cp* = 5-C5Me5), [(6-arene)RuCl2]2 (arene = p-cymene, hexamethylbenzene), and [Cp*MCl2]2 (M = Rh, Ir) react with -amino amides and various peptide esters to give the N,O-chelate complexes [Cp*(I)Co - NH2C(H)(R1)C(NHR2)-O]+ (1), [(6-arene)(Cl)Ru - NH2C(H)(R1)C(NHR2)O]+ (2), and [CP*(Cl)M - NH2CH2C(NHR)O]+ (M = Rh, Ir) (5, in solution), respectively. In the solid state the ligands are 1N-bonded in 5. By deprotonation of the peptide bond in 2 and 5 the neutral N, N-chelate complexes (6-arene)(Cl)Ru - NH2C(H)(R1)C(O)-2 (6) and Cp*(Cl)M - NH2C(H)(R1)C(O)NR2 (M = Rh, Ir) (7) have been obtained. Glycinenitrile is 1-bonded in (6-p-cymene)(Cl)2Ru(NH2CH2CN) (3) and Cp*(Cl)2Rh(NH2CH2CN) (4). Double deprotonated triglycine methyl ester is a N,N,N-tridentate ligand in (6-C6Me6)Ru(NH2CH2C(O)NCH2C(O)-NCH2CO2Me) (8). The anions of L-asparagine and of aspartame (L-aspartyl-L-phenylalanine methyl ester) give the complexes 9-12 with tridentate O,N,O- or O,N,N-chelate ligands. The crystal structures of 1d (L = glyglyOEt), 5a (L = glycinamide), 6e (L = glyglyOEt), and 7k (L = glyglyglyOEt) have been determined by X-ray structural analysis
Letter from H. L. Russell to Carl Hayden
No full textLetter from H. L. Russell to Carl Hayden regarding fines in the park
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