X-ray and multinuclear NMR study of the mixed aggregate [(Ph2P(O)N(CH2Ph)CH3) · LiOC6H2-2,6-{C(CH3)3}2-4-CH3) · C7H8]2: a model for the directed metalation of phosphinamides

I Fernandez, Robert D Price, P D Bolton, M F Mahon, M G Davidson, F Lopez-Ortiz

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Abstract

The addition of LiBun to a toluene solution of PhP(O)N(CH2Ph)CH3 1 and 2,6-di-tert-butyl-4-methylphenol 5 leads to the formation of the mixed dimer [(Ph2P(O)N(CH2Ph)CH3)(LiOC6H2)-Li-.-2.6-{C(CH3)(3)}(2)-4-(CH3C7H8)-C-.]( 2) 6. The single crystal X-ray structure shows that two lithium aryloxide moieties dimerize giving rise to a Li2O2 core in which each lithium atom is additionally coordinated to a phosphinamide 1 ligand. The multinuclear magnetic resonance study (H-1, Li-7, C-13, P-31) indicates that the solid-state structure is preserved in toluene solution. Complex 6 may be considered as a model for the pre-complexation step preceding the metalation of phosphinamides by an organolithium base.
Original languageEnglish
Pages (from-to)1890-1896
Number of pages7
JournalJournal of Organometallic Chemistry
Volume689
Issue number11
DOIs
Publication statusPublished - 2004

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Biomolecular Nuclear Magnetic Resonance
Toluene
Lithium
toluene
lithium
Nuclear magnetic resonance
X-Rays
methylidyne
X rays
nuclear magnetic resonance
Magnetic resonance
Complexation
Dimers
magnetic resonance
x rays
Magnetic Resonance Spectroscopy
Ligands
dimers
Single crystals
solid state

Cite this

@article{fe6ba8000b174990817042264960f492,
title = "X-ray and multinuclear NMR study of the mixed aggregate [(Ph2P(O)N(CH2Ph)CH3) · LiOC6H2-2,6-{C(CH3)3}2-4-CH3) · C7H8]2: a model for the directed metalation of phosphinamides",
abstract = "The addition of LiBun to a toluene solution of PhP(O)N(CH2Ph)CH3 1 and 2,6-di-tert-butyl-4-methylphenol 5 leads to the formation of the mixed dimer [(Ph2P(O)N(CH2Ph)CH3)(LiOC6H2)-Li-.-2.6-{C(CH3)(3)}(2)-4-(CH3C7H8)-C-.]( 2) 6. The single crystal X-ray structure shows that two lithium aryloxide moieties dimerize giving rise to a Li2O2 core in which each lithium atom is additionally coordinated to a phosphinamide 1 ligand. The multinuclear magnetic resonance study (H-1, Li-7, C-13, P-31) indicates that the solid-state structure is preserved in toluene solution. Complex 6 may be considered as a model for the pre-complexation step preceding the metalation of phosphinamides by an organolithium base.",
author = "I Fernandez and Price, {Robert D} and Bolton, {P D} and Mahon, {M F} and Davidson, {M G} and F Lopez-Ortiz",
note = "ID number: ISI:000221529500005",
year = "2004",
doi = "10.1016/j.jorganchem.2004.03.013",
language = "English",
volume = "689",
pages = "1890--1896",
journal = "Journal of Organometallic Chemistry",
issn = "0022-328X",
publisher = "Elsevier",
number = "11",

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TY - JOUR

T1 - X-ray and multinuclear NMR study of the mixed aggregate [(Ph2P(O)N(CH2Ph)CH3) · LiOC6H2-2,6-{C(CH3)3}2-4-CH3) · C7H8]2: a model for the directed metalation of phosphinamides

AU - Fernandez, I

AU - Price, Robert D

AU - Bolton, P D

AU - Mahon, M F

AU - Davidson, M G

AU - Lopez-Ortiz, F

N1 - ID number: ISI:000221529500005

PY - 2004

Y1 - 2004

N2 - The addition of LiBun to a toluene solution of PhP(O)N(CH2Ph)CH3 1 and 2,6-di-tert-butyl-4-methylphenol 5 leads to the formation of the mixed dimer [(Ph2P(O)N(CH2Ph)CH3)(LiOC6H2)-Li-.-2.6-{C(CH3)(3)}(2)-4-(CH3C7H8)-C-.]( 2) 6. The single crystal X-ray structure shows that two lithium aryloxide moieties dimerize giving rise to a Li2O2 core in which each lithium atom is additionally coordinated to a phosphinamide 1 ligand. The multinuclear magnetic resonance study (H-1, Li-7, C-13, P-31) indicates that the solid-state structure is preserved in toluene solution. Complex 6 may be considered as a model for the pre-complexation step preceding the metalation of phosphinamides by an organolithium base.

AB - The addition of LiBun to a toluene solution of PhP(O)N(CH2Ph)CH3 1 and 2,6-di-tert-butyl-4-methylphenol 5 leads to the formation of the mixed dimer [(Ph2P(O)N(CH2Ph)CH3)(LiOC6H2)-Li-.-2.6-{C(CH3)(3)}(2)-4-(CH3C7H8)-C-.]( 2) 6. The single crystal X-ray structure shows that two lithium aryloxide moieties dimerize giving rise to a Li2O2 core in which each lithium atom is additionally coordinated to a phosphinamide 1 ligand. The multinuclear magnetic resonance study (H-1, Li-7, C-13, P-31) indicates that the solid-state structure is preserved in toluene solution. Complex 6 may be considered as a model for the pre-complexation step preceding the metalation of phosphinamides by an organolithium base.

UR - http://dx.doi.org/10.1016/j.jorganchem.2004.03.013

U2 - 10.1016/j.jorganchem.2004.03.013

DO - 10.1016/j.jorganchem.2004.03.013

M3 - Article

VL - 689

SP - 1890

EP - 1896

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

SN - 0022-328X

IS - 11

ER -