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1.
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
4.
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
5.
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
6.
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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Tosylmethylisocyanide, when coordinated to osmium(II), reacts with aldehydes and ketones in the presence of sodium methoxide, to produce oxazol-2-ylidene and oxazolidin-2-ylidene complexes. 相似文献
10.
Liaoran Cao Xinyu Zhang Alix Grimley Anna R. Lomasney Michael G. Roper 《Analytical and bioanalytical chemistry》2010,398(5):1985-1991
A microfluidic device was developed to produce temporal concentration gradients of multiple analytes. Four on-chip pumps delivered
pulses of three analytes and buffer to a 14-cm channel where the pulses were mixed to homogeneity. The final concentration
of each analyte was dependent on the temporal density of the pulses from each pump. The concentration of each analyte was
varied by changing the number of pump cycles from each reservoir while maintaining the total number of pump cycles per unit
time to ensure a constant total flow rate in the device. To gauge the independent nature of each pump, sinusoidal waves of
fluorescein concentration were produced from each pump with independent frequencies and amplitudes. The resulting fluorescence
intensity was compared with a theoretical summation of the waves and the experimental data matched the theoretical waves within
1%, indicating that the pumps were operating independently and outputting the correct frequency and amplitude. The device
was used to demonstrate the role of adenosine triphosphate-sensitive K+ channels in glucose-stimulated increases in intracellular [Ca2+] in islets of Langerhans. Perfusion of single islets of Langerhans with combinations of glucose, diazoxide, and K+ resulted in intracellular Ca2+ patterns similar to what has been observed using conventional perfusion devices. The system will be useful in other studies
with islets of Langerhans, as well as other assays that require the modulation of multiple analytes in time. 相似文献