Stereochemically non-rigid transition metal complexes of2,6-bis[1-(phenylimino)ethyl]pyridine (BIP). Part 3. Dynamic NMRstudies of fac-[PtXMe3(BIP)] (X C1, Br, or I). Crystal structure offac-[PtIMe3(BIP)]

KG Orrell, AG Osborne, V Sik, Mateus Webba da Silva, MB Hursthouse, DE Hibbs, KM Abdul Malik, NG Vassilev

Research output: Contribution to journalArticle

Abstract

The complexes fac-[PtXMe3(BIP)] (X Cl,Br or I;BIP 2,6-bis[1-(phenylimino)ethyl]pyridine) have been synthesised andcharacterised as involving BIP as a bidentate chelate ligand. In solution the metal-bound ligand exists in four conformationalforms, namely distal and proximal E,E and E,Z-isomers. 2D-EXSY NMR has been used to measure 1,4-metallotropic shifts ofthe PtXMe3 moiety between equivalent distal E,E forms, E,Z isomerisation of the pendant imine function and restricted C Crotation of the pendant arm of the BIP ligand. Activation energies, DG" (298.15 K), for all these processes are in the range 67–96kJ mol 1 and are essentially halogen independent. A crystal structure of fac-[PtIMe3(BIP)] shows that the pendant imine functionis in the E-conformation and is rotated at an angle of 80.1° to the plane of the pyridine.
LanguageEnglish
Pages35-47
JournalJournal of Organometallic Chemistry
Volume555
Publication statusPublished - 1998

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Coordination Complexes
Transition metals
Imines
Crystal structure
Ligands
Halogens
Isomerization
Isomers
Conformations
Activation energy
Metals
Nuclear magnetic resonance
pyridine

Cite this

@article{d965ffe5d75645eab5fb03557ce304f6,
title = "Stereochemically non-rigid transition metal complexes of2,6-bis[1-(phenylimino)ethyl]pyridine (BIP). Part 3. Dynamic NMRstudies of fac-[PtXMe3(BIP)] (X C1, Br, or I). Crystal structure offac-[PtIMe3(BIP)]",
abstract = "The complexes fac-[PtXMe3(BIP)] (X Cl,Br or I;BIP 2,6-bis[1-(phenylimino)ethyl]pyridine) have been synthesised andcharacterised as involving BIP as a bidentate chelate ligand. In solution the metal-bound ligand exists in four conformationalforms, namely distal and proximal E,E and E,Z-isomers. 2D-EXSY NMR has been used to measure 1,4-metallotropic shifts ofthe PtXMe3 moiety between equivalent distal E,E forms, E,Z isomerisation of the pendant imine function and restricted C Crotation of the pendant arm of the BIP ligand. Activation energies, DG{"} (298.15 K), for all these processes are in the range 67–96kJ mol 1 and are essentially halogen independent. A crystal structure of fac-[PtIMe3(BIP)] shows that the pendant imine functionis in the E-conformation and is rotated at an angle of 80.1° to the plane of the pyridine.",
author = "KG Orrell and AG Osborne and V Sik and {Webba da Silva}, Mateus and MB Hursthouse and DE Hibbs and {Abdul Malik}, KM and NG Vassilev",
year = "1998",
language = "English",
volume = "555",
pages = "35--47",

}

Stereochemically non-rigid transition metal complexes of2,6-bis[1-(phenylimino)ethyl]pyridine (BIP). Part 3. Dynamic NMRstudies of fac-[PtXMe3(BIP)] (X C1, Br, or I). Crystal structure offac-[PtIMe3(BIP)]. / Orrell, KG; Osborne, AG; Sik, V; Webba da Silva, Mateus; Hursthouse, MB; Hibbs, DE; Abdul Malik, KM; Vassilev, NG.

Vol. 555, 1998, p. 35-47.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Stereochemically non-rigid transition metal complexes of2,6-bis[1-(phenylimino)ethyl]pyridine (BIP). Part 3. Dynamic NMRstudies of fac-[PtXMe3(BIP)] (X C1, Br, or I). Crystal structure offac-[PtIMe3(BIP)]

AU - Orrell, KG

AU - Osborne, AG

AU - Sik, V

AU - Webba da Silva, Mateus

AU - Hursthouse, MB

AU - Hibbs, DE

AU - Abdul Malik, KM

AU - Vassilev, NG

PY - 1998

Y1 - 1998

N2 - The complexes fac-[PtXMe3(BIP)] (X Cl,Br or I;BIP 2,6-bis[1-(phenylimino)ethyl]pyridine) have been synthesised andcharacterised as involving BIP as a bidentate chelate ligand. In solution the metal-bound ligand exists in four conformationalforms, namely distal and proximal E,E and E,Z-isomers. 2D-EXSY NMR has been used to measure 1,4-metallotropic shifts ofthe PtXMe3 moiety between equivalent distal E,E forms, E,Z isomerisation of the pendant imine function and restricted C Crotation of the pendant arm of the BIP ligand. Activation energies, DG" (298.15 K), for all these processes are in the range 67–96kJ mol 1 and are essentially halogen independent. A crystal structure of fac-[PtIMe3(BIP)] shows that the pendant imine functionis in the E-conformation and is rotated at an angle of 80.1° to the plane of the pyridine.

AB - The complexes fac-[PtXMe3(BIP)] (X Cl,Br or I;BIP 2,6-bis[1-(phenylimino)ethyl]pyridine) have been synthesised andcharacterised as involving BIP as a bidentate chelate ligand. In solution the metal-bound ligand exists in four conformationalforms, namely distal and proximal E,E and E,Z-isomers. 2D-EXSY NMR has been used to measure 1,4-metallotropic shifts ofthe PtXMe3 moiety between equivalent distal E,E forms, E,Z isomerisation of the pendant imine function and restricted C Crotation of the pendant arm of the BIP ligand. Activation energies, DG" (298.15 K), for all these processes are in the range 67–96kJ mol 1 and are essentially halogen independent. A crystal structure of fac-[PtIMe3(BIP)] shows that the pendant imine functionis in the E-conformation and is rotated at an angle of 80.1° to the plane of the pyridine.

M3 - Article

VL - 555

SP - 35

EP - 47

ER -