Monomeric β‐Diketiminato Group 13 Metal Dipnictogenide Complexes with Two Terminal EH2 (E = P, As) Groups

Bin Li, Suzanne Bauer, Manfred Scheer, Alexey Timoshkin, Michael Seidl

Research output

Abstract

The pnictogenyl group 13 compounds (Dipp2Nacnac)M[E(SiMe3)2]Cl and (Dipp2Nacnac)M(EH2)2 (Dipp2Nacnac = HC[C(Me)N(Ar)]2, Ar = 2,6‐iPr2C6H3; M = Al, Ga, In; E = P, As) were successfully synthesized. The salt metathesis between (Dipp2Nacnac)MCl2 and LiE(SiMe3)2 only led to mono‐ substituted compounds (Dipp2Nacnac)M[E(SiMe3)2]Cl [E = P, M = Ga(1), In (2); E = As, M = Ga (3), In (4)], regardless of the stoichiometric ratios used. In contrast to the steric effect of the SiMe3 groups in 1‐4, the reactions of the corresponding halides with LiPH2•DME (or KAsH2) facilely yielded the dipnictogenide compounds (Dipp2Nacnac)M(EH2)2 (E = P, M = Al (5), Ga (6), In (7); E = As, M = Al (8), Ga (9)), avoiding the use of flammable and toxic PH3 and AsH3 for their synthesis. The compounds 5‐9 are the first examples of monomeric group 13 diphosphanides and diarsanides in which the metal center is bound to two terminal PH2 and AsH2 groups, respectively. In contrast to the successful synthesis of the indium diphosphanide (Dipp2Nacnac)In(PH2)2, the reaction of (Dipp2Nacnac)InCl2 with KAsH2 led to an indium mirror due to the instability of the target product.
Original languageEnglish
JournalChemistry - A European Journal
Volume25
DOIs
Publication statusPublished - 29 Aug 2019

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Indium
Coordination Complexes
Metal complexes
Poisons
Mirrors
Salts
Metals
N,N-diethyl-2-(1-pyridyl)ethylamine
arsine

Cite this

@article{6a55fc8c31344c6b93614447cf3d68ad,
title = "Monomeric β‐Diketiminato Group 13 Metal Dipnictogenide Complexes with Two Terminal EH2 (E = P, As) Groups",
abstract = "The pnictogenyl group 13 compounds (Dipp2Nacnac)M[E(SiMe3)2]Cl and (Dipp2Nacnac)M(EH2)2 (Dipp2Nacnac = HC[C(Me)N(Ar)]2, Ar = 2,6‐iPr2C6H3; M = Al, Ga, In; E = P, As) were successfully synthesized. The salt metathesis between (Dipp2Nacnac)MCl2 and LiE(SiMe3)2 only led to mono‐ substituted compounds (Dipp2Nacnac)M[E(SiMe3)2]Cl [E = P, M = Ga(1), In (2); E = As, M = Ga (3), In (4)], regardless of the stoichiometric ratios used. In contrast to the steric effect of the SiMe3 groups in 1‐4, the reactions of the corresponding halides with LiPH2•DME (or KAsH2) facilely yielded the dipnictogenide compounds (Dipp2Nacnac)M(EH2)2 (E = P, M = Al (5), Ga (6), In (7); E = As, M = Al (8), Ga (9)), avoiding the use of flammable and toxic PH3 and AsH3 for their synthesis. The compounds 5‐9 are the first examples of monomeric group 13 diphosphanides and diarsanides in which the metal center is bound to two terminal PH2 and AsH2 groups, respectively. In contrast to the successful synthesis of the indium diphosphanide (Dipp2Nacnac)In(PH2)2, the reaction of (Dipp2Nacnac)InCl2 with KAsH2 led to an indium mirror due to the instability of the target product.",
author = "Bin Li and Suzanne Bauer and Manfred Scheer and Alexey Timoshkin and Michael Seidl",
year = "2019",
month = "8",
day = "29",
doi = "https://doi.org/10.1002/chem.201903887",
language = "English",
volume = "25",
journal = "Chemistry - A European Journal",
issn = "0947-6539",
publisher = "Wiley-Blackwell",

}

TY - JOUR

T1 - Monomeric β‐Diketiminato Group 13 Metal Dipnictogenide Complexes with Two Terminal EH2 (E = P, As) Groups

AU - Li, Bin

AU - Bauer, Suzanne

AU - Scheer, Manfred

AU - Timoshkin, Alexey

AU - Seidl, Michael

PY - 2019/8/29

Y1 - 2019/8/29

N2 - The pnictogenyl group 13 compounds (Dipp2Nacnac)M[E(SiMe3)2]Cl and (Dipp2Nacnac)M(EH2)2 (Dipp2Nacnac = HC[C(Me)N(Ar)]2, Ar = 2,6‐iPr2C6H3; M = Al, Ga, In; E = P, As) were successfully synthesized. The salt metathesis between (Dipp2Nacnac)MCl2 and LiE(SiMe3)2 only led to mono‐ substituted compounds (Dipp2Nacnac)M[E(SiMe3)2]Cl [E = P, M = Ga(1), In (2); E = As, M = Ga (3), In (4)], regardless of the stoichiometric ratios used. In contrast to the steric effect of the SiMe3 groups in 1‐4, the reactions of the corresponding halides with LiPH2•DME (or KAsH2) facilely yielded the dipnictogenide compounds (Dipp2Nacnac)M(EH2)2 (E = P, M = Al (5), Ga (6), In (7); E = As, M = Al (8), Ga (9)), avoiding the use of flammable and toxic PH3 and AsH3 for their synthesis. The compounds 5‐9 are the first examples of monomeric group 13 diphosphanides and diarsanides in which the metal center is bound to two terminal PH2 and AsH2 groups, respectively. In contrast to the successful synthesis of the indium diphosphanide (Dipp2Nacnac)In(PH2)2, the reaction of (Dipp2Nacnac)InCl2 with KAsH2 led to an indium mirror due to the instability of the target product.

AB - The pnictogenyl group 13 compounds (Dipp2Nacnac)M[E(SiMe3)2]Cl and (Dipp2Nacnac)M(EH2)2 (Dipp2Nacnac = HC[C(Me)N(Ar)]2, Ar = 2,6‐iPr2C6H3; M = Al, Ga, In; E = P, As) were successfully synthesized. The salt metathesis between (Dipp2Nacnac)MCl2 and LiE(SiMe3)2 only led to mono‐ substituted compounds (Dipp2Nacnac)M[E(SiMe3)2]Cl [E = P, M = Ga(1), In (2); E = As, M = Ga (3), In (4)], regardless of the stoichiometric ratios used. In contrast to the steric effect of the SiMe3 groups in 1‐4, the reactions of the corresponding halides with LiPH2•DME (or KAsH2) facilely yielded the dipnictogenide compounds (Dipp2Nacnac)M(EH2)2 (E = P, M = Al (5), Ga (6), In (7); E = As, M = Al (8), Ga (9)), avoiding the use of flammable and toxic PH3 and AsH3 for their synthesis. The compounds 5‐9 are the first examples of monomeric group 13 diphosphanides and diarsanides in which the metal center is bound to two terminal PH2 and AsH2 groups, respectively. In contrast to the successful synthesis of the indium diphosphanide (Dipp2Nacnac)In(PH2)2, the reaction of (Dipp2Nacnac)InCl2 with KAsH2 led to an indium mirror due to the instability of the target product.

UR - https://onlinelibrary.wiley.com/doi/pdf/10.1002/chem.201903887

U2 - https://doi.org/10.1002/chem.201903887

DO - https://doi.org/10.1002/chem.201903887

M3 - Article

VL - 25

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

ER -