Stereochemically non-rigid transition metal complexes of2,6-bis[(1-phenylimino)ethyl]pyridine (BIP)Part 2. Dynamic NMR studies of fac-[ReX(CO)3(BIP)](X = C1, Br, or I).Crystal structure of fac-[ReBr(CO)3(BIP)]

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

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Abstract

The complexes fac-[ReX(CO)3(BIP)] (X = CI, 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 ligand exists in three conformational forms, namely E,E- andboth distal and proximal E,Z-isomers. 2D-EXSY NMR has been used to measure 1,4-metallotropic shifts of the ReX(CO) 3 moietybetween equivalent E,E forms, E,Z-isomerisation of the pendant imine function and restricted C-C rotation of the pendant arm of theBIP ligand. Activation energies AG * (298.15 K) for all these processes are of comparable magnitude, in the range 79-88 kJmol-J, andare essentially halogen independent. Restricted rotation of the phenyl ring attached to the Re-coordinated nitrogen was also detected withAG * = 67.3 + 0.2 kJ mol- i. A crystal structure of fac-[ReBr(CO)3(BIP)] confirms the E-conformation of the pendant imine functionwith its N atom cis to the pyridyl nitrogen.
LanguageEnglish
Pages171-183
JournalJournal of Organometallic Chemistry
Volume538
Publication statusPublished - 1997

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Coordination Complexes
Carbon Monoxide
Transition metals
Imines
Crystal structure
Nuclear magnetic resonance
Ligands
Nitrogen
Halogens
Isomerization
Isomers
Conformations
Activation energy
Atoms
pyridine

Cite this

@article{be21b687b20b46f6805ead6e148e8e7b,
title = "Stereochemically non-rigid transition metal complexes of2,6-bis[(1-phenylimino)ethyl]pyridine (BIP)Part 2. Dynamic NMR studies of fac-[ReX(CO)3(BIP)](X = C1, Br, or I).Crystal structure of fac-[ReBr(CO)3(BIP)]",
abstract = "The complexes fac-[ReX(CO)3(BIP)] (X = CI, 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 ligand exists in three conformational forms, namely E,E- andboth distal and proximal E,Z-isomers. 2D-EXSY NMR has been used to measure 1,4-metallotropic shifts of the ReX(CO) 3 moietybetween equivalent E,E forms, E,Z-isomerisation of the pendant imine function and restricted C-C rotation of the pendant arm of theBIP ligand. Activation energies AG * (298.15 K) for all these processes are of comparable magnitude, in the range 79-88 kJmol-J, andare essentially halogen independent. Restricted rotation of the phenyl ring attached to the Re-coordinated nitrogen was also detected withAG * = 67.3 + 0.2 kJ mol- i. A crystal structure of fac-[ReBr(CO)3(BIP)] confirms the E-conformation of the pendant imine functionwith its N atom cis to the pyridyl nitrogen.",
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 = "1997",
language = "English",
volume = "538",
pages = "171--183",
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 2. Dynamic NMR studies of fac-[ReX(CO)3(BIP)](X = C1, Br, or I).Crystal structure of fac-[ReBr(CO)3(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 - 1997

Y1 - 1997

N2 - The complexes fac-[ReX(CO)3(BIP)] (X = CI, 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 ligand exists in three conformational forms, namely E,E- andboth distal and proximal E,Z-isomers. 2D-EXSY NMR has been used to measure 1,4-metallotropic shifts of the ReX(CO) 3 moietybetween equivalent E,E forms, E,Z-isomerisation of the pendant imine function and restricted C-C rotation of the pendant arm of theBIP ligand. Activation energies AG * (298.15 K) for all these processes are of comparable magnitude, in the range 79-88 kJmol-J, andare essentially halogen independent. Restricted rotation of the phenyl ring attached to the Re-coordinated nitrogen was also detected withAG * = 67.3 + 0.2 kJ mol- i. A crystal structure of fac-[ReBr(CO)3(BIP)] confirms the E-conformation of the pendant imine functionwith its N atom cis to the pyridyl nitrogen.

AB - The complexes fac-[ReX(CO)3(BIP)] (X = CI, 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 ligand exists in three conformational forms, namely E,E- andboth distal and proximal E,Z-isomers. 2D-EXSY NMR has been used to measure 1,4-metallotropic shifts of the ReX(CO) 3 moietybetween equivalent E,E forms, E,Z-isomerisation of the pendant imine function and restricted C-C rotation of the pendant arm of theBIP ligand. Activation energies AG * (298.15 K) for all these processes are of comparable magnitude, in the range 79-88 kJmol-J, andare essentially halogen independent. Restricted rotation of the phenyl ring attached to the Re-coordinated nitrogen was also detected withAG * = 67.3 + 0.2 kJ mol- i. A crystal structure of fac-[ReBr(CO)3(BIP)] confirms the E-conformation of the pendant imine functionwith its N atom cis to the pyridyl nitrogen.

M3 - Article

VL - 538

SP - 171

EP - 183

JO - Journal of Organometallic Chemistry

T2 - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

SN - 0022-328X

ER -