Heavier group 13 metal(I) heterocycles stabilized by sterically demanding diiminophosphinates: a structurally characterized monomer-dimer pair for gallium

Andrew L. Hawley; C. André Ohlin; Lea Fohlmeister; Andreas Stasch

doi:10.1002/chem.201604495

Heavier group 13 metal(I) heterocycles stabilized by sterically demanding diiminophosphinates: a structurally characterized monomer-dimer pair for gallium

Andrew L. Hawley, C. André Ohlin, Lea Fohlmeister, Andreas Stasch

School of Chemistry

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Abstract

We have synthesized and characterized the monomeric diiminophosphinate-stabilized group 13 metal(I) complexes [^DipLE:], ^DipL = Ph₂P(NDip)₂, Dip = 2,6-iPr₂C₆H₃; E = Ga (1), In (2) and Tl (3). In addition, we structurally characterized the dimeric complex [(^DipLGa)²], 1₂. Similar synthetic attempts using ^MesL = Ph₂P(NMes)₂, Mes = 2,4,6-Me₃C₆H₂ afforded product mixtures from which the mixed oxidation state species [(^MesL)₃Ga₄I₃] 4 was isolated. [^DipLGa:] 1 is converted with dry air to the gallium(III) oxide species [(^DipLGaO)₂] 5. Density Functional Theory studies on [^DipLE:] and [(^DipLE)₂], E = Al-Tl, shed light on the bonding in these compounds and show that the newly formed E-E bonding interactions can be described as weak single σ-bond with no significant π-bonding contribution for E = Al, Ga. A large contribution to the dimer binding enthalpies results from London dispersion forces.

Original language	English
Pages (from-to)	447-455
Number of pages	9
Journal	Chemistry - A European Journal
Volume	23
Issue number	2
Early online date	2 Dec 2016
DOIs	https://doi.org/10.1002/chem.201604495
Publication status	Published - 5 Jan 2017

Keywords

Group 13 elements
Low valent main group compounds
Metal-metal interactions
N-ligands
O-O activation

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10.1002/chem.201604495

CEJ_Stasch_GaGa_PURE
© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. This work has been 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://doi.org/10.1002/chem.201604495
Accepted author manuscript, 8.2 MB

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title = "Heavier group 13 metal(I) heterocycles stabilized by sterically demanding diiminophosphinates: a structurally characterized monomer-dimer pair for gallium",

abstract = "We have synthesized and characterized the monomeric diiminophosphinate-stabilized group 13 metal(I) complexes [DipLE:], DipL = Ph2P(NDip)2, Dip = 2,6-iPr2C6H3; E = Ga (1), In (2) and Tl (3). In addition, we structurally characterized the dimeric complex [(DipLGa)2], 12. Similar synthetic attempts using MesL = Ph2P(NMes)2, Mes = 2,4,6-Me3C6H2 afforded product mixtures from which the mixed oxidation state species [(MesL)3Ga4I3] 4 was isolated. [DipLGa:] 1 is converted with dry air to the gallium(III) oxide species [(DipLGaO)2] 5. Density Functional Theory studies on [DipLE:] and [(DipLE)2], E = Al-Tl, shed light on the bonding in these compounds and show that the newly formed E-E bonding interactions can be described as weak single σ-bond with no significant π-bonding contribution for E = Al, Ga. A large contribution to the dimer binding enthalpies results from London dispersion forces.",

keywords = "Group 13 elements, Low valent main group compounds, Metal-metal interactions, N-ligands, O-O activation",

author = "Hawley, {Andrew L.} and Ohlin, {C. Andr{\'e}} and Lea Fohlmeister and Andreas Stasch",

note = "A. S. is grateful to the Australian Research Council for support and a fellowship. C. A. O. thanks the Australian Research Council for Discovery Project grants DP11015530 and DP130100483.",

year = "2017",

month = jan,

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doi = "10.1002/chem.201604495",

language = "English",

volume = "23",

pages = "447--455",

journal = "Chemistry - A European Journal",

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T2 - a structurally characterized monomer-dimer pair for gallium

AU - Hawley, Andrew L.

AU - Ohlin, C. André

AU - Fohlmeister, Lea

AU - Stasch, Andreas

N1 - A. S. is grateful to the Australian Research Council for support and a fellowship. C. A. O. thanks the Australian Research Council for Discovery Project grants DP11015530 and DP130100483.

PY - 2017/1/5

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N2 - We have synthesized and characterized the monomeric diiminophosphinate-stabilized group 13 metal(I) complexes [DipLE:], DipL = Ph2P(NDip)2, Dip = 2,6-iPr2C6H3; E = Ga (1), In (2) and Tl (3). In addition, we structurally characterized the dimeric complex [(DipLGa)2], 12. Similar synthetic attempts using MesL = Ph2P(NMes)2, Mes = 2,4,6-Me3C6H2 afforded product mixtures from which the mixed oxidation state species [(MesL)3Ga4I3] 4 was isolated. [DipLGa:] 1 is converted with dry air to the gallium(III) oxide species [(DipLGaO)2] 5. Density Functional Theory studies on [DipLE:] and [(DipLE)2], E = Al-Tl, shed light on the bonding in these compounds and show that the newly formed E-E bonding interactions can be described as weak single σ-bond with no significant π-bonding contribution for E = Al, Ga. A large contribution to the dimer binding enthalpies results from London dispersion forces.

AB - We have synthesized and characterized the monomeric diiminophosphinate-stabilized group 13 metal(I) complexes [DipLE:], DipL = Ph2P(NDip)2, Dip = 2,6-iPr2C6H3; E = Ga (1), In (2) and Tl (3). In addition, we structurally characterized the dimeric complex [(DipLGa)2], 12. Similar synthetic attempts using MesL = Ph2P(NMes)2, Mes = 2,4,6-Me3C6H2 afforded product mixtures from which the mixed oxidation state species [(MesL)3Ga4I3] 4 was isolated. [DipLGa:] 1 is converted with dry air to the gallium(III) oxide species [(DipLGaO)2] 5. Density Functional Theory studies on [DipLE:] and [(DipLE)2], E = Al-Tl, shed light on the bonding in these compounds and show that the newly formed E-E bonding interactions can be described as weak single σ-bond with no significant π-bonding contribution for E = Al, Ga. A large contribution to the dimer binding enthalpies results from London dispersion forces.

KW - Group 13 elements

KW - Low valent main group compounds

KW - Metal-metal interactions

KW - N-ligands

KW - O-O activation

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VL - 23

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JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

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Heavier group 13 metal(I) heterocycles stabilized by sterically demanding diiminophosphinates: a structurally characterized monomer-dimer pair for gallium

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Heavier group 13 metal(I) heterocycles stabilized by sterically demanding diiminophosphinates: a structurally characterized monomer-dimer pair for gallium

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Keywords

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Heavier group 13 metal(I) heterocycles stabilized by sterically demanding diiminophosphinates (dataset)

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