Expected and unexpected reactivities of homoleptic LiNacNac and heteroleptic NacNacMg(TMP) β-diketiminates towards various small unsaturated organic molecules

Richard M. Gauld; Jennifer R. Lynch; Alan R. Kennedy; Jim Barker; Jacqueline Reid; Robert E. Mulvey

doi:10.1021/acs.inorgchem.1c00549

Expected and unexpected reactivities of homoleptic LiNacNac and heteroleptic NacNacMg(TMP) β-diketiminates towards various small unsaturated organic molecules

Richard M. Gauld, Jennifer R. Lynch, Alan R. Kennedy, Jim Barker, Jacqueline Reid, Robert E. Mulvey

Pure And Applied Chemistry

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

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Abstract

Homoleptic LiNacNac forms simple donor-acceptor complexes with N,N′-dicyclohexylcarbodiimide (CyN= C= NCy), triphenylphosphine oxide (Ph3P= O), and benzophenone (Ph2CO). These crystallographically characterized compounds could be regarded as model intermediates en route to reducing the N= C, P= O, and C= O bonds of unsaturated substrates. Heteroleptic NacNacMg(TMP) intriguingly functions as a TMP nucleophile both with t-BuNCO and t-BuNCS, producing a urea or thiourea derivative respectively attached to Mg, though the NacNac ligand in the former reaction also engages noninnocently with a second t-BuNCO molecule via insertion at the reactive NacNac backbone γ-carbon site.

Original language	English
Pages (from-to)	6057-6064
Number of pages	8
Journal	Inorganic Chemistry
Volume	60
Issue number	8
Early online date	8 Apr 2021
DOIs	https://doi.org/10.1021/acs.inorgchem.1c00549
Publication status	Published - 19 Apr 2021

Keywords

NacNac ligand
LiNacNac
organic ligands

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10.1021/acs.inorgchem.1c00549Licence: CC BY 4.0

Mulvey-etal-IC-2021-Expected-and-unexpected-reactivities-of-homoleptic-LiNacNacFinal published version, 1.81 MBLicence: CC BY 4.0

Doctoral Training Partnership 2020-2021 University of Strathclyde | Lynch, Jennifer
Mulvey, R. (Principal Investigator), Robertson, S. (Co-investigator) & Lynch, J. (Research Co-investigator)
EPSRC (Engineering and Physical Sciences Research Council)
1/10/20 → 17/04/24
Project: Research Studentship - Internally Allocated
Doctoral Training Partnership (DTP 2016-2017 University of Strathclyde) | Gauld, Richard Mackay
Mulvey, R. (Principal Investigator), Hevia, E. (Co-investigator) & Gauld, R. M. (Research Co-investigator)
EPSRC (Engineering and Physical Sciences Research Council)
1/10/16 → 23/06/20
Project: Research Studentship - Internally Allocated

Data for: "Expected and unexpected reactivities of homoleptic LiNacNac and heteroleptic NacNacMg(TMP) β-diketiminates towards various small unsaturated organic molecules"
Lynch, J. (Creator), Gauld, R. M. (Creator), Mulvey, R. (Creator), Kennedy, A. (Creator), Barker, J. (Creator) & Reid, J. (Creator), University of Strathclyde, 1 Apr 2021
DOI: 10.15129/a79e0465-457a-40cd-81f6-fd2b90df2a3d
Dataset

Cite this

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title = "Expected and unexpected reactivities of homoleptic LiNacNac and heteroleptic NacNacMg(TMP) β-diketiminates towards various small unsaturated organic molecules",

abstract = "Homoleptic LiNacNac forms simple donor-acceptor complexes with N,N′-dicyclohexylcarbodiimide (CyN= C= NCy), triphenylphosphine oxide (Ph3P= O), and benzophenone (Ph2CO). These crystallographically characterized compounds could be regarded as model intermediates en route to reducing the N= C, P= O, and C= O bonds of unsaturated substrates. Heteroleptic NacNacMg(TMP) intriguingly functions as a TMP nucleophile both with t-BuNCO and t-BuNCS, producing a urea or thiourea derivative respectively attached to Mg, though the NacNac ligand in the former reaction also engages noninnocently with a second t-BuNCO molecule via insertion at the reactive NacNac backbone γ-carbon site.",

keywords = "NacNac ligand, LiNacNac, organic ligands",

author = "Gauld, {Richard M.} and Lynch, {Jennifer R.} and Kennedy, {Alan R.} and Jim Barker and Jacqueline Reid and Mulvey, {Robert E.}",

year = "2021",

month = apr,

day = "19",

doi = "10.1021/acs.inorgchem.1c00549",

language = "English",

volume = "60",

pages = "6057--6064",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "8",

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TY - JOUR

T1 - Expected and unexpected reactivities of homoleptic LiNacNac and heteroleptic NacNacMg(TMP) β-diketiminates towards various small unsaturated organic molecules

AU - Gauld, Richard M.

AU - Lynch, Jennifer R.

AU - Kennedy, Alan R.

AU - Barker, Jim

AU - Reid, Jacqueline

AU - Mulvey, Robert E.

PY - 2021/4/19

Y1 - 2021/4/19

N2 - Homoleptic LiNacNac forms simple donor-acceptor complexes with N,N′-dicyclohexylcarbodiimide (CyN= C= NCy), triphenylphosphine oxide (Ph3P= O), and benzophenone (Ph2CO). These crystallographically characterized compounds could be regarded as model intermediates en route to reducing the N= C, P= O, and C= O bonds of unsaturated substrates. Heteroleptic NacNacMg(TMP) intriguingly functions as a TMP nucleophile both with t-BuNCO and t-BuNCS, producing a urea or thiourea derivative respectively attached to Mg, though the NacNac ligand in the former reaction also engages noninnocently with a second t-BuNCO molecule via insertion at the reactive NacNac backbone γ-carbon site.

AB - Homoleptic LiNacNac forms simple donor-acceptor complexes with N,N′-dicyclohexylcarbodiimide (CyN= C= NCy), triphenylphosphine oxide (Ph3P= O), and benzophenone (Ph2CO). These crystallographically characterized compounds could be regarded as model intermediates en route to reducing the N= C, P= O, and C= O bonds of unsaturated substrates. Heteroleptic NacNacMg(TMP) intriguingly functions as a TMP nucleophile both with t-BuNCO and t-BuNCS, producing a urea or thiourea derivative respectively attached to Mg, though the NacNac ligand in the former reaction also engages noninnocently with a second t-BuNCO molecule via insertion at the reactive NacNac backbone γ-carbon site.

KW - NacNac ligand

KW - LiNacNac

KW - organic ligands

U2 - 10.1021/acs.inorgchem.1c00549

DO - 10.1021/acs.inorgchem.1c00549

M3 - Article

SN - 0020-1669

VL - 60

SP - 6057

EP - 6064

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 8

ER -

Expected and unexpected reactivities of homoleptic LiNacNac and heteroleptic NacNacMg(TMP) β-diketiminates towards various small unsaturated organic molecules

Abstract

Keywords

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Projects

Doctoral Training Partnership 2020-2021 University of Strathclyde | Lynch, Jennifer

Doctoral Training Partnership (DTP 2016-2017 University of Strathclyde) | Gauld, Richard Mackay

Datasets

Data for: "Expected and unexpected reactivities of homoleptic LiNacNac and heteroleptic NacNacMg(TMP) β-diketiminates towards various small unsaturated organic molecules"

Cite this