Monitoring the Formation and Reactivity of Organometallic Alkane and Fluoroalkane Complexes with Silanes and Xe Using Time-Resolved X-ray Absorption Fine Structure Spectroscopy.

Complexes with weakly coordinating ligands are often formed in chemical reactions and can play key roles in determining the reactivity, particularly in catalytic reactions. Using time-resolved X-ray absorption fine structure (XAFS) spectroscopy in combination with time-resolved IR (TRIR) spectroscopy and tungsten hexacarbonyl, W(CO)6, we are able to structurally characterize the formation of an organometallic alkane complex, determine the W-C distances, and monitor the reactivity with silane to form an organometallic silane complex. Experiments in perfluorosolvents doped with xenon afford initially the corresponding solvated complex, which is sufficiently reactive in the presence of Xe that we can then observe the coordination of Xe to the metal center, providing a unique insight into the metal-xenon bonding. These results offer a step toward elucidating the structure, bonding, and chemical reactivity of transient species by X-ray absorption spectroscopy, which has sensitivity to small structural changes. The XAFS results indicate that the bond lengths of metal-alkane (W-H-C) bond in W(CO)5(heptane) as 3.07 (±0.06) Å, which is longer than the calculated W-C (2.86 Å) for binding of the primary C-H, but shorter than the calculated W-C (3.12 Å) for the secondary C-H. A statistical average of the calculated W-C alkane bond lengths is 3.02 Å, and comparison of this value indicates that the value derived from the XAFS measurements is averaged over coordination of all C-H bonds consistent with alkane chain walking. Photolysis of W(CO)6 in the presence of HSiBu3 allows the conversion of W(CO)5(heptane) to W(CO)5(HSiBu3) with an estimated W-Si distance of 3.20 (±0.03) Å. Time-resolved TRIR and XAFS experiments following photolysis of W(CO)6 in perfluoromethylcyclohexane (PFMCH) allows the characterization of W(CO)5(PFMCH) with a W-F distance of 2.65 (±0.06) Å, and doping PFMCH with Xe allows the characterization of W(CO)5Xe with a W-Xe bond length of 3.10 (±0.02) Å.

Cross-Conjugated Systems Based On An (E)-Hexa-3-en-1,5-diyne-3,4-diyl Skeleton: Spectroscopic and Spectroelectrochemical Investigations.

A series of cross-conjugated compounds based on an (E)-4,4'-(hexa-3-en-1,5-diyne-3,4-diyl)bis(N,N-bis(4-methoxyphenyl)aniline) skeleton (1-6) have been synthesized. The linear optical absorption properties can be tuned by modification of the substituents at the 1 and 5 positions of the hexa-3-en-1,5-diynyl backbone (1: Si(CH(CH3)2)3, 2: C6H4C≡CSi(CH3)3, 3: C6H4COOCH3, 4: C6H4CF3, 5: C6H4C≡N, 6: C6H4C≡CC5H4N), although attempts to introduce electron-donating (C6H4CH3, C6H4OCH3, C6H4Si(CH3)3) substituents at these positions were hampered by the ensuing decreased stability of the compounds. Spectroelectrochemical investigations of selected examples, supported by DFT-based computational studies, have shown that one- and two-electron oxidation of the 1,2-bis(triarylamine)ethene fragment also results in electronic changes to the perpendicular π-system in the hexa-3-en-1,5-diynyl branch of the molecule. These properties suggest that (E)-hexa-3-en-1,5-diynyl-based compounds could have applications in molecular sensing and molecular electronics.

Evaluation of Transmission Raman spectroscopy and NIR Hyperspectral Imaging for the assessment of content uniformity in solid oral dosage forms✰.

PURPOSE: The objective of the present study was to explore and compare fast and non-destructive Transmission Raman Spectroscopy (TRS) and Near Infrared Hyperspectral imaging (NIR HSI) for the development of predictive quantitative methods to determine content uniformity (CU) of tablets. METHODS: A set of single Active Pharmaceutical Ingredients (API) tablets with nine concentration levels of caffeine ranging from 12.75%w/w to 17.75%w/w and another set of double API tablets with five concentration levels of model API A* (5.25%w/w - 9.25%w/w) and caffeine (7%w/w - 13%w/w) were prepared. Chemometric prediction models were developed using partial least square (PLS 1) and later tested using a test set for both single and double API tablets. RESULTS: Calibration PLS1 models were developed for both single and double APIs using a combination of S-G 1st derivative and SNV data pre-processing steps that offer an optimal model performance with the lowest cross-validation error and bias. The root mean square error of prediction (RMSEP) for the PLS1 model for single API caffeine tablets using TRS and NIR HSI was 0.27% and 0.36% respectively. The RMSEP for the PLS1 models built using TRS for the double API tablets was 0.29% for API A and 0.34% for caffeine. Similarly, for the NIR HIS prediction models the RMSEP was 0.43% for API A and 0.56% for caffeine. CONCLUSION: Overall TRS presented a 25-30% more accurate prediction capability compared to NIR HSI in this specific sample sets. Nevertheless, both TRS ad NIR HSI possess the potential to be employed as rapid, nondestructive techniques to replace classical wet- chemistry methods for at- or off-line determination of tablet CU.