Synthesis and Characterisation of Novel Bis(diphenylphosphane oxide)methanidoytterbium(III) Complexes

Shalini Rangarajan; Owen A. Beaumont; Maravanji S. Balakrishna; Glen B. Deacon; Victoria L. Blair

doi:10.3390/molecules27227704

Synthesis and Characterisation of Novel Bis(diphenylphosphane oxide)methanidoytterbium(III) Complexes

Shalini Rangarajan
, Owen A. Beaumont
, Maravanji S. Balakrishna
, Glen B. Deacon
, Victoria L. Blair

School of Chemistry

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

2 Citations (Scopus)

Abstract

Reaction of [YbCp₂(dme)] (Cp = cyclopentadienyl, dme = 1,2 dimethoxyethane) with bis(diphenylphosphano)methane dioxide (H₂dppmO₂) leads to deprotonation of the ligand H₂dppmO₂ and oxidation of ytterbium, forming an extremely air-sensitive product, [Yb^III(HdppmO₂)₃] (1), a six-coordinate complex with three chelating (OPCHPO) HdppmO₂ ligands. Complex 1 was also obtained by a redox transmetallation/protolysis synthesis from metallic ytterbium, Hg(C₆F₅)_2, and H₂dppmO₂. In a further preparation, the reaction of [Yb(C₆F₅)₂] with H₂dppmO₂, not only yielded compound 1, but also gave a remarkable tetranuclear cage, [Yb₄(µ-HdppmO₂)₆(µ-F)₆] (2) containing two [Yb(µ-F)]₂ rhombic units linked by two fluoride ligands and the tetranuclear unit is encapsulated by six bridging HdppmO₂ donors. The fluoride ligands of the cage result from C-F activation of pentafluorobenzene and concomitant formation of p-H₂C₆F₄ and m-H₂C₆F₄, the last being an unexpected product.

Original language	English
Article number	7704
Number of pages	14
Journal	Molecules
Volume	27
Issue number	22
DOIs	https://doi.org/10.3390/molecules27227704
Publication status	Published - Nov 2022

Keywords

C-F activation
fluoride cage
methanide
phosphine oxide
ytterbium

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10.3390/molecules27227704Licence: CC BY

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@article{359a509d9afc43128a30b53fdda921ff,

title = "Synthesis and Characterisation of Novel Bis(diphenylphosphane oxide)methanidoytterbium(III) Complexes",

abstract = "Reaction of [YbCp2(dme)] (Cp = cyclopentadienyl, dme = 1,2 dimethoxyethane) with bis(diphenylphosphano)methane dioxide (H2dppmO2) leads to deprotonation of the ligand H2dppmO2 and oxidation of ytterbium, forming an extremely air-sensitive product, [YbIII(HdppmO2)3] (1), a six-coordinate complex with three chelating (OPCHPO) HdppmO2 ligands. Complex 1 was also obtained by a redox transmetallation/protolysis synthesis from metallic ytterbium, Hg(C6F5)2, and H2dppmO2. In a further preparation, the reaction of [Yb(C6F5)2] with H2dppmO2, not only yielded compound 1, but also gave a remarkable tetranuclear cage, [Yb4(µ-HdppmO2)6(µ-F)6] (2) containing two [Yb(µ-F)]2 rhombic units linked by two fluoride ligands and the tetranuclear unit is encapsulated by six bridging HdppmO2 donors. The fluoride ligands of the cage result from C-F activation of pentafluorobenzene and concomitant formation of p-H2C6F4 and m-H2C6F4, the last being an unexpected product.",

keywords = "C-F activation, fluoride cage, methanide, phosphine oxide, ytterbium",

author = "Shalini Rangarajan and Beaumont, \{Owen A.\} and Balakrishna, \{Maravanji S.\} and Deacon, \{Glen B.\} and Blair, \{Victoria L.\}",

note = "Funding Information: G.B.D. and V.L.B. gratefully acknowledges the Australian Research Council (ARC) for funding, DP190100798 and FT200100918 respectively. Funding Information: We are grateful to the Faculty of Science, Monash University for providing the required facility for carrying out the work. S.R. gratefully acknowledges the Indian Institute of Technology Bombay-Monash Academy for the financial support. We thank Alasdair McKay for assisting us in NMR spectroscopic measurements, Craig Forsyth and Zhifang Gou for X-ray crystallography assistance and Reshma Jose for computational studies. Publisher Copyright: {\textcopyright} 2022 by the authors.",

year = "2022",

month = nov,

doi = "10.3390/molecules27227704",

language = "English",

volume = "27",

journal = "Molecules",

issn = "1420-3049",

publisher = "MDPI AG",

number = "22",

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TY - JOUR

T1 - Synthesis and Characterisation of Novel Bis(diphenylphosphane oxide)methanidoytterbium(III) Complexes

AU - Rangarajan, Shalini

AU - Beaumont, Owen A.

AU - Balakrishna, Maravanji S.

AU - Deacon, Glen B.

AU - Blair, Victoria L.

N1 - Funding Information: G.B.D. and V.L.B. gratefully acknowledges the Australian Research Council (ARC) for funding, DP190100798 and FT200100918 respectively. Funding Information: We are grateful to the Faculty of Science, Monash University for providing the required facility for carrying out the work. S.R. gratefully acknowledges the Indian Institute of Technology Bombay-Monash Academy for the financial support. We thank Alasdair McKay for assisting us in NMR spectroscopic measurements, Craig Forsyth and Zhifang Gou for X-ray crystallography assistance and Reshma Jose for computational studies. Publisher Copyright: © 2022 by the authors.

PY - 2022/11

Y1 - 2022/11

N2 - Reaction of [YbCp2(dme)] (Cp = cyclopentadienyl, dme = 1,2 dimethoxyethane) with bis(diphenylphosphano)methane dioxide (H2dppmO2) leads to deprotonation of the ligand H2dppmO2 and oxidation of ytterbium, forming an extremely air-sensitive product, [YbIII(HdppmO2)3] (1), a six-coordinate complex with three chelating (OPCHPO) HdppmO2 ligands. Complex 1 was also obtained by a redox transmetallation/protolysis synthesis from metallic ytterbium, Hg(C6F5)2, and H2dppmO2. In a further preparation, the reaction of [Yb(C6F5)2] with H2dppmO2, not only yielded compound 1, but also gave a remarkable tetranuclear cage, [Yb4(µ-HdppmO2)6(µ-F)6] (2) containing two [Yb(µ-F)]2 rhombic units linked by two fluoride ligands and the tetranuclear unit is encapsulated by six bridging HdppmO2 donors. The fluoride ligands of the cage result from C-F activation of pentafluorobenzene and concomitant formation of p-H2C6F4 and m-H2C6F4, the last being an unexpected product.

AB - Reaction of [YbCp2(dme)] (Cp = cyclopentadienyl, dme = 1,2 dimethoxyethane) with bis(diphenylphosphano)methane dioxide (H2dppmO2) leads to deprotonation of the ligand H2dppmO2 and oxidation of ytterbium, forming an extremely air-sensitive product, [YbIII(HdppmO2)3] (1), a six-coordinate complex with three chelating (OPCHPO) HdppmO2 ligands. Complex 1 was also obtained by a redox transmetallation/protolysis synthesis from metallic ytterbium, Hg(C6F5)2, and H2dppmO2. In a further preparation, the reaction of [Yb(C6F5)2] with H2dppmO2, not only yielded compound 1, but also gave a remarkable tetranuclear cage, [Yb4(µ-HdppmO2)6(µ-F)6] (2) containing two [Yb(µ-F)]2 rhombic units linked by two fluoride ligands and the tetranuclear unit is encapsulated by six bridging HdppmO2 donors. The fluoride ligands of the cage result from C-F activation of pentafluorobenzene and concomitant formation of p-H2C6F4 and m-H2C6F4, the last being an unexpected product.

KW - C-F activation

KW - fluoride cage

KW - methanide

KW - phosphine oxide

KW - ytterbium

UR - https://www.scopus.com/pages/publications/85142604741

U2 - 10.3390/molecules27227704

DO - 10.3390/molecules27227704

M3 - Article

C2 - 36431801

AN - SCOPUS:85142604741

SN - 1420-3049

VL - 27

JO - Molecules

JF - Molecules

IS - 22

M1 - 7704

ER -

Synthesis and Characterisation of Novel Bis(diphenylphosphane oxide)methanidoytterbium(III) Complexes

Abstract

Keywords

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Synthesis, Synergy and Sustainability: Development of active-metal reagents

CTREC: Challenging targets in rare earth metal-organic chemistry

Cite this

Synthesis and Characterisation of Novel Bis(diphenylphosphane oxide)methanidoytterbium(III) Complexes

Abstract

Keywords

Access to Document

Other files and links

Projects

Synthesis, Synergy and Sustainability: Development of active-metal reagents

CTREC: Challenging targets in rare earth metal-organic chemistry

Cite this