Infrared spectroscopy of mass-selected ions in FTICR and QIT mass spectrometers

(1)

HAL Id: hal-00069121

https://hal.archives-ouvertes.fr/hal-00069121

Submitted on 9 Oct 2018

HAL is a multi-disciplinary open access

archive for the deposit and dissemination of sci-entific research documents, whether they are pub-lished or not. The documents may come from teaching and research institutions in France or abroad, or from public or private research centers.

L’archive ouverte pluridisciplinaire HAL, est destinée au dépôt et à la diffusion de documents scientifiques de niveau recherche, publiés ou non, émanant des établissements d’enseignement et de recherche français ou étrangers, des laboratoires publics ou privés.

Infrared spectroscopy of mass-selected ions in FTICR and QIT mass spectrometers

Luke Mac Aleese, Joel Lemaire, Pierre Boissel, Jean-Yves Salpin, Jean-Michel Ortega, Francois Glotin, Philippe Maître

To cite this version:

Luke Mac Aleese, Joel Lemaire, Pierre Boissel, Jean-Yves Salpin, Jean-Michel Ortega, et al.. Infrared spectroscopy of mass-selected ions in FTICR and QIT mass spectrometers. 53rd American Society Mass Spectrometry Conference, 2005, San Antonio, United States. 2005. �hal-00069121�

(2)

Infrared spectroscopy of mass-selected ions in FTICR and

QIT mass spectrometers

(a) _{Laboratoire de Chimie Physique, UMR 8000 CNRS – Université Paris-Sud 11, Faculté des Sciences d’Orsay, bât. 350, 91405 ORSAY Cedex, France.}(b) _{LURE-CLIO, UMR 130 CNRS – Université}

Paris-Sud 11, Faculté des Sciences d’Orsay, bât. 209D, 91405 ORSAY Cedex, France. (c) _{Laboratoire Analyse et Environnement, UMR 8587 CNRS – Université d’Evry Val d’Essone, 91025 Evry Cedex}

An infrared source : the Free Electron Laser CLIO in Orsay

Perspectives : IR spectroscopy of “real world” catalysts and related intermediates

Energy by micropulse (J)

Mean Power

(mW)

CLIO Laser power (3-90 um) + OPOs

CLIO Laser power for various electron energies

CLIO characteristics :

• infrared domain from 100 to 3000 cm

-1

_

_{overview of the « infrared fingerprint » region}

• continuous & rapid tuneability



full spectrum (800-1600cm

-1

_{) in typically 1 hour}

• spectral width around 0.2-0.5 % of central wavenumber (i.e. from  from 8 to 4 cm

-1

₎

• continuous high power over all range (~800mW)

time

40 msec

8 sec

1 psec

16 nsec

=60-70 J

CLIO : a pulsed laser with a particular time structure

MICRA characteristics :

• Mass range 10-1000 amu

• Resolution 70000 @ 130 amu

• Permanent magnet 1.25 Tesla

• Vacuum 5.10-9 mbar

• Dimensions 120 x 80 x 60cm

• Weight 200 kg

Different ion sources :

• Electron impact

• Chemical ionisation

• MALDI

• Laser ablation-ionisation

Irradiation time ~ 500-2000 ms

NdYag 355 nm B

Excitation Detection Excitation

Trapping

IR FEL

MALDI target

matrix

NaCl AA

MICRA ICR cell : an open cell to provide optical acces to the trapped ions

A FT-ICR mass spectrometer : MICRA, the Mobile

FT-ICR Analyzer

An ESI-quadrupole ion trap mass spectrometer :

modified Esquire3000plus Bruker instrument

Ion trap characteristics :

• Mass range 50-3000 m/z

(extended : 200-6000 m/z)

• Resolution 0,15 uma

Ion sources used : electrospray

Modification : two symmetric holes

in the ring electrode

Irradiation time ~ 50-300 ms

Quadrupole ion trap : (1)modified ring

electrode : a hole was built to allow a focused laser beam in, (2)&(3)endcap electrodes

1

CLIO beam

Comparison between IRMPD spectra in ICR and QIT conditions. Test case : protonated Leucine methylester

Results :

Same absorption band position

Same absorption band width : 30-40 cm

-1



same internal energy of the ions

With the RF trap :

“real world” catalysts :

762.9 765.0 765.9 766.9 767.9 768.9 769.9 770.9 771.9 772.9 +MS, 0.0-2.2min (#1-#135) 0 1 2 3 4 7 x10 Intens. 762 764 766 768 770 772 774 m/z P PPh2 S Pd NTf₂ Me2OC Me2OC Ph Ph M = 1048.3

High pressure in the trap : ion molecule reactions in a high

collision rate regime – “real” conditions chemistry.

Our 1

rst

_{target : functionalization of a secondary amine}

N

H

O

+ 2

_OH

_O

N

70° C

THF

24h

100%

P PPh2 S Pd Me2OC Me2OC Ph Ph 0 .4 0 .8 1 .2 1 .6 2 0 4 00 8 00 1 2 00 8 00 1 4 00 2 0 00 1 46 8 72 8    72 5 1 47 9    2 04 8 - 2 09 0 C O s t r. 2 03 8 - 2 09 3 1 03 4 1 04 0 97 5 98 0 89 5 89 4 C a lc . In t . ( k m /m o l) IR M P D Y ie ld 0 0 .2 0 .4 0 .6 0 4 0 0 8 0 0 1 2 0 0 1 6 0 0 8 0 0 1 4 0 0 2 0 0 0 1 4 5 2    8 2 4    8 1 4 1 4 7 2 2 0 5 7 - 2 0 9 8 C O s t r. 2 0 6 2 - 2 1 0 4 C a lc . I n t . ( k m /m o l) I R M P D Y ie ld 0 0 . 3 0 . 6 0 8 0 1 6 0 6 0 0 1 0 0 0 1 4 0 0 1 8 0 0 M n ( B z )+   1 4 6 4 7 4 4    7 3 8 1 4 7 1 C a l c . I n t . ( k m / m o l ) I R M P D Y i e ld 0 0 .6 1 .2 0 4 0 8 0 6 0 0 1 0 0 0 1 4 0 0 1 8 0 0 M n ( B z ) 2 + 1 4 3 7    8 1 3    ( s h . 8 3 3 ) 8 1 4 1 4 5 2 9 1 1   9 1 4 C a lc . I n t . ( k m /m o l ) I R M P D

Y ie ld

Probing the spin state

Probing the coordination mode

Bz coordination change (

6

-> 

4

_{) upon CO}

addition to an 18-electron complex

IRMPD spectroscopy also provides a good tool for probing the coordination mode of benzene. Heteroleptic Mn+_(Bz)(CO) n

complexes have also been studied. Mn+_(Bz)(CO)

3 is another

example of 18-electron complex, and the magnitudes of the

blue-shift of ₁₁ and red-shift of ₁₉ are similar to the ones observed for

Mn+_(Bz)

2.

Upon addition of CO to Mn+_(Bz)(CO)

3, Mn+(Bz)(CO)4 was

generated. Three additional bands were observed at 985, 975

and 1034 cm-1 _{for Mn}+_(Bz)(CO)

4, and the positions of 11 and 19

suggest that the Mn+_{-benzene interaction is weaker than in}

Mn+_(Bz)(CO)

3. The IRMPD spectrum of Mn+(Bz)(CO)4 is in very

good agreement with the calculated IR spectrum of the isomer

presenting an 4 _{coordination of benzene.}

Metal

+

_{-Benzene complexes}

As shown in the recent work of Duncan’s group (J.

Am. Chem. Soc. 2004 126 10981 and references

therein), the magnitude of the shifts of the vibrational bands of benzene provide a clear diagnostic of the

Metal+_{-benzene bonding scheme. The larger is the}

interaction, the larger are :

- the blue-shift of ₁₁ (out-of-plane H bend, 673 cm -1 _in

Bz),

- the red-shift of ₁₉ (in plane C ring distortion, 1486

cm-1 _{in Bz).}

With this respect, our study of Mn+ _{complexes is}

interesting. Within the first row transition metal M+

complexes, the mono- and di-benzene complexes display the smallest and largest shifts respectively :

- the first benzene is weakly bound to Mn+ _{in its}

7_S(s1_d5_{) G.State,}

- the Mn+_{-benzene interaction is large in the}

18-electron Mn+_(Bz)

2 Complex.

Luke Mac Aleese

(a)

_{, Joel Lemaire}

(a)

_{, Pierre Boissel}

(a)

_{, Jean-Yves Salpin}

(c)

_{, Jean-Michel Ortega}

(b)

_,

François Glotin

(b)

_{, Philippe Maître}

(a)

Laboratoire de Chimie Physique, Laboratoire pour l’Utilisation du Rayonnement Electromagnétique, CNRS & Université Paris-Sud 11, ORSAY, France

Laboratoire Analyse et Environnement, CNRS & Université d’Evry Val d’Essone, EVRY, France

ALYXAN (Startup company for developping portable ICR analyzers)

http://www.alyxan.com/ - michel.heninger@lcp.u-psud.fr

Ion formation / irradiation :

- MALDI in -cyano matrix

- UV 355 (3rd harmonic of Nd-YAG) - ~20 mJ/pulse

- Electrospray in water - Concentration : 10-5 _mol/L

ICR

QIT

0 0.2 0.4 0.6 0.8 1 -0.15 -0.1 -0.05 0 0.05 0.1 0.15 1000 1200 1400 1600 1800 2000

protonated leucine methylester

ICR

QIT

laser frequency (cm-1)

Infrared spectra of several protonated amino methyl esters and the related

homo and hetero proton bound dimers were studied at CLIO in the FT-ICR

mass spectrometer MICRA, and their infrared spectra were obtained after

irradiation with the free electron laser “CLIO” beam.

Leucine methyl ester crystal were compressed with a-cyano matrix into a

small pellet and placed in MICRA. After desoption, ionisation, selection and

relaxation, an IR spectrum was taken : ICR-IRMPD spectrum of protonated

leucine methyl ester is represented by the red line here.

Leucine methyl ester cristal was dissolved in water and electrosprayed in

the quadrupole ion trap Bruker : after isolation of the protonated species,

they were irradiated for a few milliseconds. The QIT-IRMPD spectrum of

protonated leucine methyl ester is represented in blue.

Pd (II) L L Pd( ) L L Pd( ) L L Pd( ) L L Pd( ) L L RNH2 H₂O Pd (0) L L R NH H + R NH H H N H R OH H HO O H H