NMR spectroscopic study of the adduct formation and reactivity of homoleptic rare earth amides with alkali metal benzyl compounds, and the crystal structures of [Li(TMEDA)2][Nd{N(SiMe3)2}3(CH2Ph)] and [{Li(TMP)}2{Li(Ph)}]2.

Simon G. Rachor, Peter A. Cleaves, Stuart D. Robertson, Stephen M. Mansell

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Abstract

An NMR spectroscopic study has been conducted into the reactivity of alkali metal benzyls [M(CH2Ph)], (M = Li, Na, K) with lanthanide tris(amide) complexes [Ln(N")3] (Ln = Y, Ce, Nd; N" = N(SiMe3)2) and [Ce(TMP)3] (TMP = 2,2,6,6-tetramethylpiperidide). It was found that for [Ln(N")3], benzyl adducts [M][Ln(N")3(CH2Ph)] were initially formed, and the molecular structure for M = Li(TMEDA)2 and Ln = Nd was determined revealing a distorted tetrahedral [Nd(N")3(CH2Ph)] anion. In all cases, these adduct complexes were unstable, intramolecularly deprotonating a methyl arm of a N" ligand via benzyl basicity and eliminating toluene to prepare cyclometallated complexes of the form [M][Ln(N")22-CH2Si(Me)2N(SiMe3)}]. In parallel studies, reactions of [Li(Ph)] with [Ln(N")3] (Ln = Ce, Nd) afforded [Li(N")], whilst for (Ln = Y) adduct formation was observed. [Ce(TMP)3] did not generate any characterisable bimetallic adducts. The reaction of [Li(Ph)] with [Li(TMP)] afforded the hexanuclear [{Li(TMP)}2{Li(μ-Ph)}]2, which features lithium in three different coordination environments.
Original languageEnglish
Pages (from-to)101-109
Number of pages9
JournalJournal of Organometallic Chemistry
Volume857
Early online date21 Oct 2017
DOIs
Publication statusPublished - 15 Feb 2018

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Benzyl Compounds
Alkali metal compounds
alkali metal compounds
Thymidine Monophosphate
Alkali Metals
Alkali metals
Alkalinity
Rare earth elements
Amides
Molecular structure
Rare earths
amides
adducts
Toluene
Lithium
Negative ions
rare earth elements
reactivity
Crystal structure
Ligands

Keywords

  • f-block organometallics
  • metal amide
  • bimetallic
  • benzyl
  • alkali-metal
  • cyclometallate

Cite this

@article{158448e2758d4c55b5c42e663cb7503a,
title = "NMR spectroscopic study of the adduct formation and reactivity of homoleptic rare earth amides with alkali metal benzyl compounds, and the crystal structures of [Li(TMEDA)2][Nd{N(SiMe3)2}3(CH2Ph)] and [{Li(TMP)}2{Li(Ph)}]2.",
abstract = "An NMR spectroscopic study has been conducted into the reactivity of alkali metal benzyls [M(CH2Ph)], (M = Li, Na, K) with lanthanide tris(amide) complexes [Ln(N{"})3] (Ln = Y, Ce, Nd; N{"} = N(SiMe3)2) and [Ce(TMP)3] (TMP = 2,2,6,6-tetramethylpiperidide). It was found that for [Ln(N{"})3], benzyl adducts [M][Ln(N{"})3(CH2Ph)] were initially formed, and the molecular structure for M = Li(TMEDA)2 and Ln = Nd was determined revealing a distorted tetrahedral [Nd(N{"})3(CH2Ph)] anion. In all cases, these adduct complexes were unstable, intramolecularly deprotonating a methyl arm of a N{"} ligand via benzyl basicity and eliminating toluene to prepare cyclometallated complexes of the form [M][Ln(N{"})2{κ2-CH2Si(Me)2N(SiMe3)}]. In parallel studies, reactions of [Li(Ph)] with [Ln(N{"})3] (Ln = Ce, Nd) afforded [Li(N{"})], whilst for (Ln = Y) adduct formation was observed. [Ce(TMP)3] did not generate any characterisable bimetallic adducts. The reaction of [Li(Ph)] with [Li(TMP)] afforded the hexanuclear [{Li(TMP)}2{Li(μ-Ph)}]2, which features lithium in three different coordination environments.",
keywords = "f-block organometallics, metal amide, bimetallic, benzyl, alkali-metal, cyclometallate",
author = "Rachor, {Simon G.} and Cleaves, {Peter A.} and Robertson, {Stuart D.} and Mansell, {Stephen M.}",
year = "2018",
month = "2",
day = "15",
doi = "10.1016/j.jorganchem.2017.10.022",
language = "English",
volume = "857",
pages = "101--109",
journal = "Journal of Organometallic Chemistry",
issn = "0022-328X",

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TY - JOUR

T1 - NMR spectroscopic study of the adduct formation and reactivity of homoleptic rare earth amides with alkali metal benzyl compounds, and the crystal structures of [Li(TMEDA)2][Nd{N(SiMe3)2}3(CH2Ph)] and [{Li(TMP)}2{Li(Ph)}]2.

AU - Rachor, Simon G.

AU - Cleaves, Peter A.

AU - Robertson, Stuart D.

AU - Mansell, Stephen M.

PY - 2018/2/15

Y1 - 2018/2/15

N2 - An NMR spectroscopic study has been conducted into the reactivity of alkali metal benzyls [M(CH2Ph)], (M = Li, Na, K) with lanthanide tris(amide) complexes [Ln(N")3] (Ln = Y, Ce, Nd; N" = N(SiMe3)2) and [Ce(TMP)3] (TMP = 2,2,6,6-tetramethylpiperidide). It was found that for [Ln(N")3], benzyl adducts [M][Ln(N")3(CH2Ph)] were initially formed, and the molecular structure for M = Li(TMEDA)2 and Ln = Nd was determined revealing a distorted tetrahedral [Nd(N")3(CH2Ph)] anion. In all cases, these adduct complexes were unstable, intramolecularly deprotonating a methyl arm of a N" ligand via benzyl basicity and eliminating toluene to prepare cyclometallated complexes of the form [M][Ln(N")2{κ2-CH2Si(Me)2N(SiMe3)}]. In parallel studies, reactions of [Li(Ph)] with [Ln(N")3] (Ln = Ce, Nd) afforded [Li(N")], whilst for (Ln = Y) adduct formation was observed. [Ce(TMP)3] did not generate any characterisable bimetallic adducts. The reaction of [Li(Ph)] with [Li(TMP)] afforded the hexanuclear [{Li(TMP)}2{Li(μ-Ph)}]2, which features lithium in three different coordination environments.

AB - An NMR spectroscopic study has been conducted into the reactivity of alkali metal benzyls [M(CH2Ph)], (M = Li, Na, K) with lanthanide tris(amide) complexes [Ln(N")3] (Ln = Y, Ce, Nd; N" = N(SiMe3)2) and [Ce(TMP)3] (TMP = 2,2,6,6-tetramethylpiperidide). It was found that for [Ln(N")3], benzyl adducts [M][Ln(N")3(CH2Ph)] were initially formed, and the molecular structure for M = Li(TMEDA)2 and Ln = Nd was determined revealing a distorted tetrahedral [Nd(N")3(CH2Ph)] anion. In all cases, these adduct complexes were unstable, intramolecularly deprotonating a methyl arm of a N" ligand via benzyl basicity and eliminating toluene to prepare cyclometallated complexes of the form [M][Ln(N")2{κ2-CH2Si(Me)2N(SiMe3)}]. In parallel studies, reactions of [Li(Ph)] with [Ln(N")3] (Ln = Ce, Nd) afforded [Li(N")], whilst for (Ln = Y) adduct formation was observed. [Ce(TMP)3] did not generate any characterisable bimetallic adducts. The reaction of [Li(Ph)] with [Li(TMP)] afforded the hexanuclear [{Li(TMP)}2{Li(μ-Ph)}]2, which features lithium in three different coordination environments.

KW - f-block organometallics

KW - metal amide

KW - bimetallic

KW - benzyl

KW - alkali-metal

KW - cyclometallate

UR - http://www.sciencedirect.com/science/journal/0022328X?sdc=1

U2 - 10.1016/j.jorganchem.2017.10.022

DO - 10.1016/j.jorganchem.2017.10.022

M3 - Article

VL - 857

SP - 101

EP - 109

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

SN - 0022-328X

ER -