(575ar) Application of the Btem Family of Algorithms to Reconstruct Individual FTIR Spectra for Fine Chemical Syntheses In a Fast and Accurate Manner

The BTEM family of algorithms, BTEM [1], tBTEM [2] and MREM [3], were successfully applied to reconstruct the pure component spectra from in-situ FTIR spectra in a fast and accurate way. The reaction of Rh2(CO)4Cl2 with 1-pentyne was performed in anhydrous hexane under argon atmosphere. Multiple perturbations of Rh2(CO)4Cl2 and alkyne were also performed in this semi-batch experiment. To reconstruct the pure component spectra, MREM was first applied to survey the underlying spectra patterns. 250 automated searchers in the whole full spectral range 1600-2200cm-1 were executed without targeting any specific extrema. The recovered MREM estimates are plotted in Fig. 1.Then further refinement of the spectral estimates was achieved one-at-a-time using BTEM or tBTEM. Good estimated pure spectra were recovered by the application of these three algorithms without recourse to a priori information. Reasonable relative concentration profiles of the major species were achieved by multivariate least square analysis. The assignment of the pure component spectra reconstructed was obtained with the assistance of GC-MS and DFT calculation. Cyclotrimization of 1-pentyne was observed via GC-MS analysis. References 1. (a) W. Chew, E. Widjaja and M. Garland, Organometallics 21(9) (2002) 1982. (b) E. Widjaja, C.Z. Li and M. Garland, Organometallics 21(9) (2002) 1991. (c) C.Z. Li, E. Widjaja and M. Garland, J. Catal. 213(2) (2003) 126. (d) F. Gao, K.P. Ng, C.Z. Li, K.I. Krummel, A.D. Allian and M. Garland, J. Catal. 237 (2006) 49. 2. (a) H.J. Zhang, M. Garland, Y.Z. Zeng and P. Wu, J. Am. Soc. Mass Spectrom., 14 (2003) 1295. (b)F. Gao, A. D. Allian, H.J. Zhang, S.Y. Cheng and M. Garland, J. Catal. 241 (2006) 189. 3. H.J. Zhang, W. Chew and M. Garland, Appl. Spectrosc., 61 (2007) 1366.