OSU RC10 Gas phase measurements and calculations of HCl and Ferrocene Adam Daly and Stephen Kukolich Chemistry Department University of Arizona

OSU RC10 Outline Motivation Calculations Results Conclusions Future Work

OSU RC10 Greenwald, II, Lokshin, B.V. J. Mol. Struc, 222 (1990) 11

OSU RC10 Introduction Shea, J. Kukolich, S J.Chem.Phys

OSU RC10 Introduction Ferrocene C 10 H 10 Fe –Metal – Pi system between Iron and Cyclopentadienyl ligand –Has a wide use in electrochemistry and molecular catalysis of its derivatives. –Easily sublimes at 50˚C at 1 mTorr, air and thermally stable Loosely bound structures –Organometallic/small molecule complexes provide rich computational problems and models for complex long range interaction systems.

OSU RC10 Calculations MP2/6-311+G(d) and DFT Partial Optimizations Using Gaussian 03

OSU RC10 MP2 Results D e = -955cm -1 D e = -965 cm -1 D e = -142 cm -1 A = 1146 MHz B = 628 MHz C = 502 MHz A = 2123 MHz B = 404 MHz C = 404 MHz A = 1136 MHz B = 693 MHz C = 540 MHz

OSU RC10 Experimental Instrumentation –Flygare-Balle PBFTMW spectrometer Pressure Sample injection ~ 1Hz Sample –Freshly sublimed Ferrocene –Anhydrous HCl ~1-5% in Ne at 0.8 to 1.2 atm –Temperature maintained ˚C

OSU RC10 Experimental

OSU RC10 Predicted Spectrum using MP2/Hay-Wadt VDZ (Fe) / 6-31+G (C,H,Cl) Asymmetric top using SPCAT

OSU RC10 Results 91 transitions 4745 – GHz

OSU RC10 A closer look..

OSU RC10 The first fit

OSU RC10 B = (2) MHz eqQ= -53.5(5) MHz s = 4 kHz B = (2) MHz eqQ= -42.1(5) MHz  = 2 kHz Acetylene - HCl Benzene – HCl CClF Legon, A.C., Aldrich, P.D. and Flygare, W.H. J. Chem. Phys. 75, Read, W. G. Campbell, E. J., Henderson, G., Flygare, W. J. J. Am. Chem. Soc. 103, Haubrich, S.T., Roehrig, M.A. Kukolich, S.G., J. Chem. Phys. 93, 121 Experimental Predicted J” K” F” J' K‘ F' Frequency Frequency Difference Experimental Predicted J” K” F” J‘ K‘ F' Frequency Frequency Difference The first fit

OSU RC10 Lines used in the fit The second pattern

OSU RC10 The second substance B~1745 MHz B~872 MHz A = 2123 MHz B = 404 MHz C = 404 MHz

OSU RC could be a J = 2->1 or J= 4->3

OSU RC10 CpCl Pic here Possible Reactions A= 4032 B= 1326 C = 1326 A = 7016 B = 2012 C = 1801 MP2/6-311+G(d) B3LYP/6-311+G(d)

OSU RC10 Summary The data obtained does not support that a a complex is formed from HCl and Ferrocene. There exists a small molecule that is produced when Ferrocene and HCl interact with B( 35 Cl)= and B( 37 Cl)= A second substance is present with symmetric top or near symmetric top with B greater than that predicted from an HCl- Ferrocene complex* Multiple species containing chlorine may be present.

OSU RC10 Future Work Testing with Ruthenocene Mass spectrum of the products of gas phase Ferrocene and HCl (Denton Group at U of A) More Scanning of a possible fit of C 5 H 5 Cl

OSU RC10 Acknowledgements Stephen G. Kukolich Laszlo Sarkozy, Chakree Tanjaroon