Ring-shaped phosphinoamido-magnesium-hydride complexes: syntheses, structures, reactivity, and catalysis

Lea Fohlmeister; Andreas Stasch

doi:10.1002/chem.201601623

Ring-shaped phosphinoamido-magnesium-hydride complexes: syntheses, structures, reactivity, and catalysis

Lea Fohlmeister, Andreas Stasch

School of Chemistry

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

Abstract

A series of magnesium(II) complexes bearing the sterically demanding phosphinoamide ligand, L⁻=Ph₂PNDip⁻, Dip=2,6-diisopropylphenyl, including heteroleptic magnesium alkyl and hydride complexes are described. The ligand geometry enforces various novel ring and cluster geometries for the heteroleptic compounds. We have studied the stoichiometric reactivity of [(LMgH)₄] towards unsaturated substrates, and investigated catalytic hydroborations and hydrosilylations of ketones and pyridines. We found that hydroborations of two ketones with pinacolborane using various Mg precatalysts is very rapid at room temperature with very low catalyst loadings, and ketone hydrosilylation using phenylsilane is rapid at 70 °C. Our studies point to an insertion/σ-bond metathesis catalytic cycle of an in situ formed “MgH₂” active species.

Original language	English
Pages (from-to)	10235–10246
Journal	Chemistry - A European Journal
Volume	22
Issue number	29
Early online date	8 Jun 2016
DOIs	https://doi.org/10.1002/chem.201601623
Publication status	Published - 11 Jul 2016

Keywords

Hydrides
Hydroboration
Hydromagnesiation
Hydrosilylation
Magnesium

Access to Document

10.1002/chem.201601623

Main text_manuscriptNEW
© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. This work is made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at https://dx.doi.org/10.1002/chem.201601623
Accepted author manuscript, 4.42 MB
Supp_Inf_NEW
© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. This work is made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at https://dx.doi.org/10.1002/chem.201601623
Accepted author manuscript, 3.06 MB

Cite this

@article{a2ed0c27128e4778ae589fc48dfa1f3b,

title = "Ring-shaped phosphinoamido-magnesium-hydride complexes: syntheses, structures, reactivity, and catalysis",

abstract = "A series of magnesium(II) complexes bearing the sterically demanding phosphinoamide ligand, L−=Ph2PNDip−, Dip=2,6-diisopropylphenyl, including heteroleptic magnesium alkyl and hydride complexes are described. The ligand geometry enforces various novel ring and cluster geometries for the heteroleptic compounds. We have studied the stoichiometric reactivity of [(LMgH)4] towards unsaturated substrates, and investigated catalytic hydroborations and hydrosilylations of ketones and pyridines. We found that hydroborations of two ketones with pinacolborane using various Mg precatalysts is very rapid at room temperature with very low catalyst loadings, and ketone hydrosilylation using phenylsilane is rapid at 70 °C. Our studies point to an insertion/σ-bond metathesis catalytic cycle of an in situ formed “MgH2” active species.",

keywords = "Hydrides, Hydroboration, Hydromagnesiation, Hydrosilylation, Magnesium",

author = "Lea Fohlmeister and Andreas Stasch",

note = "A.S. is grateful to the Australian Research Council for project support and a fellowship.",

year = "2016",

month = jul,

day = "11",

doi = "10.1002/chem.201601623",

language = "English",

volume = "22",

pages = "10235–10246",

journal = "Chemistry - A European Journal",

issn = "1521-3765",

publisher = "John Wiley & Sons, Ltd",

number = "29",

}

TY - JOUR

T1 - Ring-shaped phosphinoamido-magnesium-hydride complexes

T2 - syntheses, structures, reactivity, and catalysis

AU - Fohlmeister, Lea

AU - Stasch, Andreas

N1 - A.S. is grateful to the Australian Research Council for project support and a fellowship.

PY - 2016/7/11

Y1 - 2016/7/11

N2 - A series of magnesium(II) complexes bearing the sterically demanding phosphinoamide ligand, L−=Ph2PNDip−, Dip=2,6-diisopropylphenyl, including heteroleptic magnesium alkyl and hydride complexes are described. The ligand geometry enforces various novel ring and cluster geometries for the heteroleptic compounds. We have studied the stoichiometric reactivity of [(LMgH)4] towards unsaturated substrates, and investigated catalytic hydroborations and hydrosilylations of ketones and pyridines. We found that hydroborations of two ketones with pinacolborane using various Mg precatalysts is very rapid at room temperature with very low catalyst loadings, and ketone hydrosilylation using phenylsilane is rapid at 70 °C. Our studies point to an insertion/σ-bond metathesis catalytic cycle of an in situ formed “MgH2” active species.

AB - A series of magnesium(II) complexes bearing the sterically demanding phosphinoamide ligand, L−=Ph2PNDip−, Dip=2,6-diisopropylphenyl, including heteroleptic magnesium alkyl and hydride complexes are described. The ligand geometry enforces various novel ring and cluster geometries for the heteroleptic compounds. We have studied the stoichiometric reactivity of [(LMgH)4] towards unsaturated substrates, and investigated catalytic hydroborations and hydrosilylations of ketones and pyridines. We found that hydroborations of two ketones with pinacolborane using various Mg precatalysts is very rapid at room temperature with very low catalyst loadings, and ketone hydrosilylation using phenylsilane is rapid at 70 °C. Our studies point to an insertion/σ-bond metathesis catalytic cycle of an in situ formed “MgH2” active species.

KW - Hydrides

KW - Hydroboration

KW - Hydromagnesiation

KW - Hydrosilylation

KW - Magnesium

UR - http://onlinelibrary.wiley.com/wol1/doi/10.1002/chem.201601623/suppinfo

U2 - 10.1002/chem.201601623

DO - 10.1002/chem.201601623

M3 - Article

SN - 1521-3765

VL - 22

SP - 10235

EP - 10246

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 29

ER -

Ring-shaped phosphinoamido-magnesium-hydride complexes: syntheses, structures, reactivity, and catalysis

Abstract

Keywords

Access to Document

Other files and links

Fingerprint