Stereochemically non-rigid transition metal complexes of2,6-bis[(1-phenylimino) ethyl]pyridine (BIP)Part 1. Dynamic NMR studies of[M( C6F 5) 2(BIP)] (M = Pd II or Pt II)

KG Orrell, AG Osborne, V Sik, Mateus Webba da Silva

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Abstract

The complexes [M(C6Fs)2(BIP)] (M = Pd n or Pt n, BIP = 2,6-bis[(1-phenylimino)ethyl]pyridine) have been synthesised and characterisedas involving BIP as a bidentate chelate ligand. In solution they undergo 1,4 metallotropic shifts of the M(C~Fs) z moiety, E,Zisomerisation of the pendant imine bond, and restricted C-C rotation of the pendant portion of the BIP ligand. 1H and 9F dynamic NMRstudies yielded activation energies for these three types of fluxion. AG* (298 K) values for the three processes were 89.6, 86.6 and47.4kJmol 1 respectively for the Pt rt complex. Values for the Pd II complex were significantly lower in magnitude, namely 71.6, 70.4and 41.8 kJ mol- 1 respectively.
LanguageEnglish
Pages235-246
JournalJournal of Organometallic Chemistry
Volume530
Publication statusPublished - 1997

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Coordination Complexes
Transition metals
Nuclear magnetic resonance
Ligands
Imines
Activation energy
pyridine

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@article{f8501ab4860e4171be867a63a18441ec,
title = "Stereochemically non-rigid transition metal complexes of2,6-bis[(1-phenylimino) ethyl]pyridine (BIP)Part 1. Dynamic NMR studies of[M( C6F 5) 2(BIP)] (M = Pd II or Pt II)",
abstract = "The complexes [M(C6Fs)2(BIP)] (M = Pd n or Pt n, BIP = 2,6-bis[(1-phenylimino)ethyl]pyridine) have been synthesised and characterisedas involving BIP as a bidentate chelate ligand. In solution they undergo 1,4 metallotropic shifts of the M(C~Fs) z moiety, E,Zisomerisation of the pendant imine bond, and restricted C-C rotation of the pendant portion of the BIP ligand. 1H and 9F dynamic NMRstudies yielded activation energies for these three types of fluxion. AG* (298 K) values for the three processes were 89.6, 86.6 and47.4kJmol 1 respectively for the Pt rt complex. Values for the Pd II complex were significantly lower in magnitude, namely 71.6, 70.4and 41.8 kJ mol- 1 respectively.",
author = "KG Orrell and AG Osborne and V Sik and {Webba da Silva}, Mateus",
year = "1997",
language = "English",
volume = "530",
pages = "235--246",
journal = "Journal of Organometallic Chemistry",
issn = "0022-328X",
publisher = "Elsevier",

}

TY - JOUR

T1 - Stereochemically non-rigid transition metal complexes of2,6-bis[(1-phenylimino) ethyl]pyridine (BIP)Part 1. Dynamic NMR studies of[M( C6F 5) 2(BIP)] (M = Pd II or Pt II)

AU - Orrell, KG

AU - Osborne, AG

AU - Sik, V

AU - Webba da Silva, Mateus

PY - 1997

Y1 - 1997

N2 - The complexes [M(C6Fs)2(BIP)] (M = Pd n or Pt n, BIP = 2,6-bis[(1-phenylimino)ethyl]pyridine) have been synthesised and characterisedas involving BIP as a bidentate chelate ligand. In solution they undergo 1,4 metallotropic shifts of the M(C~Fs) z moiety, E,Zisomerisation of the pendant imine bond, and restricted C-C rotation of the pendant portion of the BIP ligand. 1H and 9F dynamic NMRstudies yielded activation energies for these three types of fluxion. AG* (298 K) values for the three processes were 89.6, 86.6 and47.4kJmol 1 respectively for the Pt rt complex. Values for the Pd II complex were significantly lower in magnitude, namely 71.6, 70.4and 41.8 kJ mol- 1 respectively.

AB - The complexes [M(C6Fs)2(BIP)] (M = Pd n or Pt n, BIP = 2,6-bis[(1-phenylimino)ethyl]pyridine) have been synthesised and characterisedas involving BIP as a bidentate chelate ligand. In solution they undergo 1,4 metallotropic shifts of the M(C~Fs) z moiety, E,Zisomerisation of the pendant imine bond, and restricted C-C rotation of the pendant portion of the BIP ligand. 1H and 9F dynamic NMRstudies yielded activation energies for these three types of fluxion. AG* (298 K) values for the three processes were 89.6, 86.6 and47.4kJmol 1 respectively for the Pt rt complex. Values for the Pd II complex were significantly lower in magnitude, namely 71.6, 70.4and 41.8 kJ mol- 1 respectively.

M3 - Article

VL - 530

SP - 235

EP - 246

JO - Journal of Organometallic Chemistry

T2 - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

SN - 0022-328X

ER -