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1.
E. E. Roper W. P. White H. P. Brown O. A. Sliskonskaja F. Lieneweg I. Schrodt M. Benedict und P. Neubert 《Fresenius' Journal of Analytical Chemistry》1940,120(1-2):17-18
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G.R. Clark T.J. Collins K. Marsden W.R. Roper 《Journal of organometallic chemistry》1983,259(2):215-232
Reaction of HgR2 with OsHCl(CS)(PPh3)3 yields red, five-coordinate, OsRCl-(CS)(PPh3)2 (R = p-tolyl). From this have been derived the compounds OsRX(CS)(PPh3)2 with X = Br, I, S2CNEt2, O2CMe, O2CCF3. These compounds add an additional ligand, MeCN, CO or CNR to form colourless, six coordinate arylthiocarbonyl complexes, which undergo migratory-insertion reactions to form red, dihapto-thioacyl complexes. The crystal structure of a representative example, Os(η2-CSR)(η1-O2CCF3)(CO)PPh3)2 has been determined. The red equant crystals are orthorhombic, space group P212121, a 11.584(1), b 19.184(2), c 18.90(1) Å, V 4199 Å3, Z 4. The structure was solved by conventional heavy-atom methods and refined by full-matrix least-squares employing anisotropic thermal parameters for all non-hydrogen atoms except the carbon atoms of the triphenylphosphines. The final R factor is 0.057 for 2868 observed reflections.The coordination geometry in the monomeric complex is that of an octahedron distorted by the constraints of the ligands. The triphenyl phosphine ligands are mutually trans; the equatorial plane contains carbonyl, monohapto-trifluoroacetate, and dihapto-thioacyl ligands. Bond distances and angles are OsP 2.405, 2.407(4) Å; POsP 173.9(1)°; OsCO 1.83(2) Å; Os-O (trifluoroacetate) 2.206(11) Å; OsC (thioacyl) 1.91(2); OsS 2.513(6); CS 1.72 Å. The CS bond length implies a reduction in bond order from 2.0 to approx. 1.5 upon coordination to the metal.The η2-thioacyl ligand in Os(η2-CSR)Cl(CNR)(PPh3)2 is methylated with methyl triflate and further reaction with LiCl produces the thiocarbene complex OsCl2(C[SMe]R)(CNR)(PPh3)2. 相似文献
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Talanova GG Roper ED Buie NM Gorbunova MG Bartsch RA Talanov VS 《Chemical communications (Cambridge, England)》2005,(45):5673-5675
A new fluorogenic, dansyl group-containing derivative of 1,3-alternate calix[4]arene-bis(crown-6-ether) provides optical recognition of Tl+ with selectivity over many other metal cations, including Na+, K+, Ca2+, Ag+, Hg2+ and Pb2+, and embodies the first example of a calixarene-based fluorescent Tl+-chemosensor. 相似文献
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G.R. Clark C.M. Cochrane W.R. Roper L.J. Wright 《Journal of organometallic chemistry》1980,199(2):C35-C38
The osmium carbyne complex, Os(CR)Cl(CO)(PPh3)2, (R p-tolyl) reacts with Group I halides to form the mixed dimetallocyclopropene species, R)Cl(CO)(PPh3)2, R)Cl(CO)(PPh3)2, R)Cl(CO)(PPh3)2, and [R)Cl(CO)(MeCN)(PPh3)2] ClO4 X-ray crystal structure determination of R)Cl(CO)(PPh3)2 confirms the presence of a three-membered ring and the structure can be viewed as the “acetylene-like” interaction of an osmium—carbon triple bond with AgCl. In acid solution AgCl is precipitated and an alkylidene complex results from proton addition to the carbyne ligand. 相似文献
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Microfluidic devices have found a unique place in cellular studies due to the ease of fabrication, their ability to provide long-term culture, or the seamless integration of downstream measurements into the devices. The accurate and precise control of fluid flows also allows unique stimulant profiles to be applied to cells that have been difficult to perform with conventional devices. In this review, we describe and provide examples of microfluidic systems that have been used to generate temporal gradients of stimulants, such as waveforms or pulses, and how these profiles have been used to produce biological insights into mammalian cells that are not typically revealed under static concentration gradients. We also discuss the inherent analytical challenges associated with producing and maintaining temporal gradients in these devices. 相似文献
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Donglin He Chengxi Zhao Dr. Linjiang Chen Dr. Marc A. Little Dr. Samantha Y. Chong Rob Clowes Katherine McKie Mark G. Roper Graeme M. Day Dr. Ming Liu Prof. Andrew I. Cooper 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(41):10589-10594
Ethyl acetate is an important chemical raw material and solvent. It is also a key volatile organic compound in the brewing industry and a marker for lung cancer. Materials that are highly selective toward ethyl acetate are needed for its separation and detection. Here, we report a trianglimine macrocycle ( TAMC ) that selectively adsorbs ethyl acetate by forming a solvate. Crystal structure prediction showed this to be the lowest energy solvate structure available. This solvate leaves a metastable, “templated” cavity after solvent removal. Adsorption and breakthrough experiments confirmed that TAMC has adequate adsorption kinetics to separate ethyl acetate from azeotropic mixtures with ethanol, which is a challenging and energy-intensive industrial separation. 相似文献
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Iodomethyl-, chloromethyl-, and fluoromethyldimethylsulfonium salts, 4b-d, have been synthesized and are observed to be highly reactive molecules that exhibit extraordinary diversity with respect to the nature of their reactivity, undergoing facile direct substitution (S(N)2) reactions, but also being highly susceptible to electron-transfer reactions. Cyclic voltametry experiments indicated that the iodomethyldimethylsulfonium compound, 4b, is a potent electron acceptor, even surpassing the reactivity of perfluoro-n-alkyl iodides in that capacity. The iodo- and chloromethyldimethylsulfonium salts, 4b,c, as well as the analogous iodomethyltrimethylammonium salt, 3a, are shown to be reactive SET acceptors. 相似文献