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

doi:10.1016/j.jorganchem.2017.10.022

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

Pure And Applied Chemistry

Research output: Contribution to journal › Article › peer-review

13 Citations (Scopus)

34 Downloads (Pure)

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.

Original language	English
Pages (from-to)	101-109
Number of pages	9
Journal	Journal of Organometallic Chemistry
Volume	857
Early online date	21 Oct 2017
DOIs	https://doi.org/10.1016/j.jorganchem.2017.10.022
Publication status	Published - 15 Feb 2018

Keywords

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

Access to Document

10.1016/j.jorganchem.2017.10.022

Rachor-etal-JOC2017-NMR-spectroscopic-study-of-the-adduct-formation-and-reactivity-of-homolepticAccepted author manuscript, 884 KBLicence: CC BY-NC-ND 4.0

Fingerprint

Dive into the research topics of '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.'. Together they form a unique fingerprint.

Avenues of application for cooperative bimetallics
Robertson, S.
Royal Society of Edinburgh
1/10/12 → 30/09/17
Project: Research Fellowship

Cite this

Rachor, S. G., Cleaves, P. A., Robertson, S. D., & Mansell, S. M. (2018). 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. Journal of Organometallic Chemistry, 857, 101-109. https://doi.org/10.1016/j.jorganchem.2017.10.022

@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 = feb,

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",

}

Rachor, SG, Cleaves, PA, Robertson, SD & Mansell, SM 2018, '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.', Journal of Organometallic Chemistry, vol. 857, pp. 101-109. https://doi.org/10.1016/j.jorganchem.2017.10.022

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. / Rachor, Simon G.; Cleaves, Peter A.; Robertson, Stuart D. et al.
In: Journal of Organometallic Chemistry, Vol. 857, 15.02.2018, p. 101-109.

Research output: Contribution to journal › Article › peer-review

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

SN - 0022-328X

VL - 857

SP - 101

EP - 109

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

ER -

Rachor SG, Cleaves PA, Robertson SD, Mansell SM. 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. Journal of Organometallic Chemistry. 2018 Feb 15;857:101-109. Epub 2017 Oct 21. doi: 10.1016/j.jorganchem.2017.10.022