The reaction of M(CO)3(Ph2PCH2CH2PPh2) (M = Fe, Ru) with parahydrogen: probing the electronic structure of reaction intermediates and the internal rearrangement mechanism for the dihydride products

Daniele Schott, Philip Callaghan, John Dunne, Simon B Duckett, Cyril Godard, Jose M Goicoechea, Jeremy N Harvey, John P Lowe, Roger J Mawby, Georg Mueller, Robin N Perutz, Rinaldo Poli, Michael K Whittlesey

Research output: Contribution to journalArticle

  • 25 Citations

Abstract

The photochem. reaction of Ru(CO)3(dppe) and Fe(CO)3(dppe) (dppe = bis-(1,2-diphenylphosphino)ethane; Ph2PCH2CH2PPh2) with parahydrogen has been studied by in situ-photochem. resulting in NMR spectra of Ru(CO)2(dppe)(H)2 that show significant enhancement of the hydride resonances while normal signals are seen in Fe(CO)2(dppe)(H)2. This effect is assocd. with a singlet electronic state for the key intermediate Ru(CO)2(dppe) while Fe(CO)2(dppe) is a triplet. DFT calcns. reveal electronic ground states consistent with this picture. The fluxionality of Ru(CO)2(dppe)(H)2 and Fe(CO)2(dppe)(H)2 has been examd. by NMR spectroscopy and rationalized by theor. methods which show that two pathways for ligand exchange exist. In the first, the phosphorus and carbonyl centers interchange positions while the two hydride ligands are unaffected. A second pathway involving interchange of all three ligand sets was found at slightly higher energy. The H-H distances in the transition states are consistent with metal-bonded dihydrogen ligands. However, no local min. (intermediate) was found along the rearrangement pathways. Electronic supplementary information (ESI) is available at http://www.rsc.org/suppdata/dt/b4/b407457b/ and contains Cartesian coordinates for all optimized geometries, synthesis and NMR parameters for Fe(CO)2(dppe)(H)2 and rate data for ligand interchange.
LanguageEnglish
Pages3218-3224
Number of pages7
JournalDalton Transactions
Volume20
StatusPublished - 2004

Fingerprint

Reaction intermediates
Carbon Monoxide
Electronic structure
Ligands
Interchanges
Hydrides
Nuclear magnetic resonance
Ethane
Electronic states
Discrete Fourier transforms
Phosphorus
Ground state
Nuclear magnetic resonance spectroscopy
Metals
Hydrogen
Geometry

Keywords

  • Photolysis
  • Transition state structure (probing electronic structure of intermediates in photoreactions of hydrogen with carbonyl-bis(diphenylphosphino)ethane complexes of Fe and Ru)
  • Density functional theory
  • Rearrangement (photochem.
  • Electronic structure
  • Ground state
  • metal carbonyl phenylphosphine complex photoreaction parahydrogen
  • Fluxional rearrangement
  • Excited singlet state
  • internal rearrangement of dihydride products from photochem. reaction of hydrogen with carbonyl-bis(diphenylphosphino)ethane complexes of Fe and Ru)

Cite this

The reaction of M(CO)3(Ph2PCH2CH2PPh2) (M = Fe, Ru) with parahydrogen: probing the electronic structure of reaction intermediates and the internal rearrangement mechanism for the dihydride products. / Schott, Daniele; Callaghan, Philip; Dunne, John; Duckett, Simon B; Godard, Cyril; Goicoechea, Jose M; Harvey, Jeremy N; Lowe, John P; Mawby, Roger J; Mueller, Georg; Perutz, Robin N; Poli, Rinaldo; Whittlesey, Michael K.

In: Dalton Transactions, Vol. 20, 2004, p. 3218-3224.

Research output: Contribution to journalArticle

Schott, D, Callaghan, P, Dunne, J, Duckett, SB, Godard, C, Goicoechea, JM, Harvey, JN, Lowe, JP, Mawby, RJ, Mueller, G, Perutz, RN, Poli, R & Whittlesey, MK 2004, 'The reaction of M(CO)3(Ph2PCH2CH2PPh2) (M = Fe, Ru) with parahydrogen: probing the electronic structure of reaction intermediates and the internal rearrangement mechanism for the dihydride products' Dalton Transactions, vol. 20, pp. 3218-3224.
Schott, Daniele ; Callaghan, Philip ; Dunne, John ; Duckett, Simon B ; Godard, Cyril ; Goicoechea, Jose M ; Harvey, Jeremy N ; Lowe, John P ; Mawby, Roger J ; Mueller, Georg ; Perutz, Robin N ; Poli, Rinaldo ; Whittlesey, Michael K. / The reaction of M(CO)3(Ph2PCH2CH2PPh2) (M = Fe, Ru) with parahydrogen: probing the electronic structure of reaction intermediates and the internal rearrangement mechanism for the dihydride products. In: Dalton Transactions. 2004 ; Vol. 20. pp. 3218-3224
@article{ff571d329e6842318c6793dd349c2dd0,
title = "The reaction of M(CO)3(Ph2PCH2CH2PPh2) (M = Fe, Ru) with parahydrogen: probing the electronic structure of reaction intermediates and the internal rearrangement mechanism for the dihydride products",
abstract = "The photochem. reaction of Ru(CO)3(dppe) and Fe(CO)3(dppe) (dppe = bis-(1,2-diphenylphosphino)ethane; Ph2PCH2CH2PPh2) with parahydrogen has been studied by in situ-photochem. resulting in NMR spectra of Ru(CO)2(dppe)(H)2 that show significant enhancement of the hydride resonances while normal signals are seen in Fe(CO)2(dppe)(H)2. This effect is assocd. with a singlet electronic state for the key intermediate Ru(CO)2(dppe) while Fe(CO)2(dppe) is a triplet. DFT calcns. reveal electronic ground states consistent with this picture. The fluxionality of Ru(CO)2(dppe)(H)2 and Fe(CO)2(dppe)(H)2 has been examd. by NMR spectroscopy and rationalized by theor. methods which show that two pathways for ligand exchange exist. In the first, the phosphorus and carbonyl centers interchange positions while the two hydride ligands are unaffected. A second pathway involving interchange of all three ligand sets was found at slightly higher energy. The H-H distances in the transition states are consistent with metal-bonded dihydrogen ligands. However, no local min. (intermediate) was found along the rearrangement pathways. Electronic supplementary information (ESI) is available at http://www.rsc.org/suppdata/dt/b4/b407457b/ and contains Cartesian coordinates for all optimized geometries, synthesis and NMR parameters for Fe(CO)2(dppe)(H)2 and rate data for ligand interchange.",
keywords = "Photolysis, Transition state structure (probing electronic structure of intermediates in photoreactions of hydrogen with carbonyl-bis(diphenylphosphino)ethane complexes of Fe and Ru), Density functional theory, Rearrangement (photochem., Electronic structure, Ground state, metal carbonyl phenylphosphine complex photoreaction parahydrogen, Fluxional rearrangement, Excited singlet state, internal rearrangement of dihydride products from photochem. reaction of hydrogen with carbonyl-bis(diphenylphosphino)ethane complexes of Fe and Ru)",
author = "Daniele Schott and Philip Callaghan and John Dunne and Duckett, {Simon B} and Cyril Godard and Goicoechea, {Jose M} and Harvey, {Jeremy N} and Lowe, {John P} and Mawby, {Roger J} and Georg Mueller and Perutz, {Robin N} and Rinaldo Poli and Whittlesey, {Michael K}",
year = "2004",
language = "English",
volume = "20",
pages = "3218--3224",
journal = "Dalton Transactions",
issn = "1477-9226",
publisher = "Royal Society of Chemistry",

}

TY - JOUR

T1 - The reaction of M(CO)3(Ph2PCH2CH2PPh2) (M = Fe, Ru) with parahydrogen: probing the electronic structure of reaction intermediates and the internal rearrangement mechanism for the dihydride products

AU - Schott,Daniele

AU - Callaghan,Philip

AU - Dunne,John

AU - Duckett,Simon B

AU - Godard,Cyril

AU - Goicoechea,Jose M

AU - Harvey,Jeremy N

AU - Lowe,John P

AU - Mawby,Roger J

AU - Mueller,Georg

AU - Perutz,Robin N

AU - Poli,Rinaldo

AU - Whittlesey,Michael K

PY - 2004

Y1 - 2004

N2 - The photochem. reaction of Ru(CO)3(dppe) and Fe(CO)3(dppe) (dppe = bis-(1,2-diphenylphosphino)ethane; Ph2PCH2CH2PPh2) with parahydrogen has been studied by in situ-photochem. resulting in NMR spectra of Ru(CO)2(dppe)(H)2 that show significant enhancement of the hydride resonances while normal signals are seen in Fe(CO)2(dppe)(H)2. This effect is assocd. with a singlet electronic state for the key intermediate Ru(CO)2(dppe) while Fe(CO)2(dppe) is a triplet. DFT calcns. reveal electronic ground states consistent with this picture. The fluxionality of Ru(CO)2(dppe)(H)2 and Fe(CO)2(dppe)(H)2 has been examd. by NMR spectroscopy and rationalized by theor. methods which show that two pathways for ligand exchange exist. In the first, the phosphorus and carbonyl centers interchange positions while the two hydride ligands are unaffected. A second pathway involving interchange of all three ligand sets was found at slightly higher energy. The H-H distances in the transition states are consistent with metal-bonded dihydrogen ligands. However, no local min. (intermediate) was found along the rearrangement pathways. Electronic supplementary information (ESI) is available at http://www.rsc.org/suppdata/dt/b4/b407457b/ and contains Cartesian coordinates for all optimized geometries, synthesis and NMR parameters for Fe(CO)2(dppe)(H)2 and rate data for ligand interchange.

AB - The photochem. reaction of Ru(CO)3(dppe) and Fe(CO)3(dppe) (dppe = bis-(1,2-diphenylphosphino)ethane; Ph2PCH2CH2PPh2) with parahydrogen has been studied by in situ-photochem. resulting in NMR spectra of Ru(CO)2(dppe)(H)2 that show significant enhancement of the hydride resonances while normal signals are seen in Fe(CO)2(dppe)(H)2. This effect is assocd. with a singlet electronic state for the key intermediate Ru(CO)2(dppe) while Fe(CO)2(dppe) is a triplet. DFT calcns. reveal electronic ground states consistent with this picture. The fluxionality of Ru(CO)2(dppe)(H)2 and Fe(CO)2(dppe)(H)2 has been examd. by NMR spectroscopy and rationalized by theor. methods which show that two pathways for ligand exchange exist. In the first, the phosphorus and carbonyl centers interchange positions while the two hydride ligands are unaffected. A second pathway involving interchange of all three ligand sets was found at slightly higher energy. The H-H distances in the transition states are consistent with metal-bonded dihydrogen ligands. However, no local min. (intermediate) was found along the rearrangement pathways. Electronic supplementary information (ESI) is available at http://www.rsc.org/suppdata/dt/b4/b407457b/ and contains Cartesian coordinates for all optimized geometries, synthesis and NMR parameters for Fe(CO)2(dppe)(H)2 and rate data for ligand interchange.

KW - Photolysis

KW - Transition state structure (probing electronic structure of intermediates in photoreactions of hydrogen with carbonyl-bis(diphenylphosphino)ethane complexes of Fe and Ru)

KW - Density functional theory

KW - Rearrangement (photochem.

KW - Electronic structure

KW - Ground state

KW - metal carbonyl phenylphosphine complex photoreaction parahydrogen

KW - Fluxional rearrangement

KW - Excited singlet state

KW - internal rearrangement of dihydride products from photochem. reaction of hydrogen with carbonyl-bis(diphenylphosphino)ethane complexes of Fe and Ru)

M3 - Article

VL - 20

SP - 3218

EP - 3224

JO - Dalton Transactions

T2 - Dalton Transactions

JF - Dalton Transactions

SN - 1477-9226

ER -