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Gas phase measurements and calculations of HCl and Ferrocene

Adam Daly and Stephen KukolichChemistry DepartmentUniversity of Arizona

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Outline

• Motivation

• Calculations

• Results

• Conclusions

• Future Work

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

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Introduction

Shea, J. Kukolich, S J.Chem.Phys. 78 3546

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Introduction

• Ferrocene C10H10Fe– 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.

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Calculations

• MP2/6-311+G(d) and DFT• Partial OptimizationsUsing Gaussian 03

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MP2 Results

De= -955cm-1

De = -965 cm-1

De= -142 cm-1 A = 1146 MHzB = 628 MHzC = 502 MHz

A = 2123 MHzB = 404 MHzC = 404 MHz

A = 1136 MHzB = 693 MHzC = 540 MHz

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Experimental

• Instrumentation– Flygare-Balle PBFTMW spectrometer

• Pressure 10-7

• Sample injection ~ 1Hz

• Sample– Freshly sublimed Ferrocene– Anhydrous HCl ~1-5% in Ne at 0.8 to 1.2 atm– Temperature maintained 35-45 ˚C

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Experimental

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

0.06

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4000 5000 6000 7000 8000 9000 10000 11000 12000

Pred

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d In

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Frequency / MHz

'FERRO35.DAT'

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Results

• 91 transitions • 4745 – 13963 GHz

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A closer look..

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The first fit

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7700 7750 7800 7850

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Frequency / MHz

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B = 3911.410(2) MHzeqQ= -53.5(5) MHzs = 4 kHz

B = 3840.134(2) MHzeqQ= -42.1(5) MHz = 2 kHz

27.11.425.53

)()(

37

35

MHzMHz

CleqQCleqQ

Acetylene - HCl 1.281

Benzene – HCl 1.272

CClF3 1.26843

1 Legon, A.C., Aldrich, P.D. and Flygare, W.H. J. Chem. Phys. 75, 6252 Read, W. G. Campbell, E. J., Henderson, G., Flygare, W. J. J. Am. Chem. Soc. 103, 76703 Haubrich, S.T., Roehrig, M.A. Kukolich, S.G., J. Chem. Phys. 93, 121

Experimental Predicted J” K” F” J' K‘ F' Frequency Frequency Difference1 0 2 0 0 2 7671.850 7671.853 -0.003 1 0 3 0 0 2 7682.375 7682.375 -0.000 1 0 1 0 0 2 7690.796 7690.797 -0.001

Experimental Predicted J” K” F” J‘ K‘ F' Frequency Frequency Difference1 0 2 0 0 2 7812.128 7812.131 -0.003 1 0 3 0 0 2 7825.502 7825.496 0.006 1 0 1 0 0 2 7836.192 7836.195 -0.003

The first fit

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Lines used in the fit

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Frequency / MHz

The second pattern

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The second substance

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Frequency / MHz

B~1745 MHz

B~872 MHz

A = 2123 MHzB = 404 MHzC = 404 MHz

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6981 6981.5 6982 6982.5 6983 6983.5 6984 6984.5 6985

Inte

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Frequency / MHz

'FREQLIST.TXT'

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10472 10472.5 10473 10473.5 10474 10474.5 10475

Inte

nsity

Frequency / MHz

'FREQLIST.TXT'

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13961 13961.5 13962 13962.5 13963 13963.5 13964

Inte

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Frequency / MHz

'FREQLIST.TXT'

6983 could be a J = 2->1or J= 4->3

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CpCl Pic herePossible Reactions

A= 4032B= 1326C = 1326

A = 7016B = 2012C = 1801MP2/6-311+G(d)

B3LYP/6-311+G(d)

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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(35Cl)=3911.4 and B(37Cl)=3840.1.

• 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.

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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 C5H5Cl

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Acknowledgements

•Stephen G. Kukolich•Laszlo Sarkozy, •Chakree Tanjaroon