Copper(I), Silver(I), and Gold(I) Ethylene Complexes of Fluorinated and Boron-Methylated Bis- and Tris(pyridyl)borate Chelators

Brandon T. Watson; Mukundam Vanga; Anurag Noonikara-Poyil; Alvaro Muñoz-Castro; H. V.Rasika Dias

doi:10.1021/acs.inorgchem.2c04009

Copper(I), Silver(I), and Gold(I) Ethylene Complexes of Fluorinated and Boron-Methylated Bis- and Tris(pyridyl)borate Chelators

Brandon T. Watson, Mukundam Vanga, Anurag Noonikara-Poyil, Alvaro Muñoz-Castro, H. V.Rasika Dias^*

^*Corresponding author for this work

University of Texas at Arlington

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

12 Scopus citations

Abstract

Bis- and tris-pyridyl borate ligands containing pyridyl donor arms, a methylated boron cap, and a fluorine-lined coordination pocket have been prepared and utilized in coinage metal chemistry. The tris(pyridyl)borate ligand has been synthesized using a convenient boron source, [NBu₄][MeBF₃]. These N-based ligands permitted the isolation of group 11 metal-ethylene complexes [MeB(6-(CF₃)Py)₃]M(C₂H₄) and [Me₂B(6-(CF₃)Py)₂]M(C₂H₄) (M = Cu, Ag, Au). The gold complexes display the largest coordination-induced upfield shifts of the ethylene ¹³C resonance relative to that of the free ethylene in their NMR spectra, while the silver complexes show the smallest shift. Solid-state structures of five of these metal-ethylene complexes as well as the related free ligands were established by X-ray crystallography. Surprisingly, all three [MeB(6-(CF₃)Py)₃]M(C₂H₄) adopt the rare κ² coordination mode rather than the typical κ³ coordination mode of facial capping tridentate ligands. Computational analyses indicate that κ² coordination mode is favored over the κ³-mode in these coinage metal-ethylene complexes and point to the effects CF₃-substituents have on κ²/κ³-energy difference. The M-C and M-N bond distances of [MeB(6-(CF₃)Py)₃]M(C₂H₄) follow the trend expected based on covalent radii of M(I) ions. The calculated ethylene-M interaction energy of κ²-[MeB(6-(CF₃)Py)₃]M(C₂H₄) indicated that the gold(I) forms the strongest interaction with ethylene. A comparison to the related poly(pyrazolyl)borates is also presented.

Original language	English
Pages (from-to)	1636-1648
Number of pages	13
Journal	Inorganic Chemistry
Volume	62
Issue number	4
DOIs	https://doi.org/10.1021/acs.inorgchem.2c04009
State	Published - 2023

Bibliographical note

Funding Information:
This material is based upon work supported by the National Science Foundation under grant number (CHE-1954456, HVRD). A.M.-C. acknowledge FONDECYT 1221676 grant.

Publisher Copyright:
© 2023 American Chemical Society.

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/acs.inorgchem.2c04009

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@article{9dda7eda29d248f4a0bf2103ca91a685,

title = "Copper(I), Silver(I), and Gold(I) Ethylene Complexes of Fluorinated and Boron-Methylated Bis- and Tris(pyridyl)borate Chelators",

abstract = "Bis- and tris-pyridyl borate ligands containing pyridyl donor arms, a methylated boron cap, and a fluorine-lined coordination pocket have been prepared and utilized in coinage metal chemistry. The tris(pyridyl)borate ligand has been synthesized using a convenient boron source, [NBu4][MeBF3]. These N-based ligands permitted the isolation of group 11 metal-ethylene complexes [MeB(6-(CF3)Py)3]M(C2H4) and [Me2B(6-(CF3)Py)2]M(C2H4) (M = Cu, Ag, Au). The gold complexes display the largest coordination-induced upfield shifts of the ethylene 13C resonance relative to that of the free ethylene in their NMR spectra, while the silver complexes show the smallest shift. Solid-state structures of five of these metal-ethylene complexes as well as the related free ligands were established by X-ray crystallography. Surprisingly, all three [MeB(6-(CF3)Py)3]M(C2H4) adopt the rare κ2 coordination mode rather than the typical κ3 coordination mode of facial capping tridentate ligands. Computational analyses indicate that κ2 coordination mode is favored over the κ3-mode in these coinage metal-ethylene complexes and point to the effects CF3-substituents have on κ2/κ3-energy difference. The M-C and M-N bond distances of [MeB(6-(CF3)Py)3]M(C2H4) follow the trend expected based on covalent radii of M(I) ions. The calculated ethylene-M interaction energy of κ2-[MeB(6-(CF3)Py)3]M(C2H4) indicated that the gold(I) forms the strongest interaction with ethylene. A comparison to the related poly(pyrazolyl)borates is also presented.",

author = "Watson, {Brandon T.} and Mukundam Vanga and Anurag Noonikara-Poyil and Alvaro Mu{\~n}oz-Castro and Dias, {H. V.Rasika}",

note = "Funding Information: This material is based upon work supported by the National Science Foundation under grant number (CHE-1954456, HVRD). A.M.-C. acknowledge FONDECYT 1221676 grant. Publisher Copyright: {\textcopyright} 2023 American Chemical Society.",

year = "2023",

month = jan,

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doi = "10.1021/acs.inorgchem.2c04009",

language = "English",

volume = "62",

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journal = "Inorganic Chemistry",

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T1 - Copper(I), Silver(I), and Gold(I) Ethylene Complexes of Fluorinated and Boron-Methylated Bis- and Tris(pyridyl)borate Chelators

AU - Watson, Brandon T.

AU - Vanga, Mukundam

AU - Noonikara-Poyil, Anurag

AU - Muñoz-Castro, Alvaro

AU - Dias, H. V.Rasika

N1 - Funding Information: This material is based upon work supported by the National Science Foundation under grant number (CHE-1954456, HVRD). A.M.-C. acknowledge FONDECYT 1221676 grant. Publisher Copyright: © 2023 American Chemical Society.

PY - 2023/1/30

Y1 - 2023/1/30

N2 - Bis- and tris-pyridyl borate ligands containing pyridyl donor arms, a methylated boron cap, and a fluorine-lined coordination pocket have been prepared and utilized in coinage metal chemistry. The tris(pyridyl)borate ligand has been synthesized using a convenient boron source, [NBu4][MeBF3]. These N-based ligands permitted the isolation of group 11 metal-ethylene complexes [MeB(6-(CF3)Py)3]M(C2H4) and [Me2B(6-(CF3)Py)2]M(C2H4) (M = Cu, Ag, Au). The gold complexes display the largest coordination-induced upfield shifts of the ethylene 13C resonance relative to that of the free ethylene in their NMR spectra, while the silver complexes show the smallest shift. Solid-state structures of five of these metal-ethylene complexes as well as the related free ligands were established by X-ray crystallography. Surprisingly, all three [MeB(6-(CF3)Py)3]M(C2H4) adopt the rare κ2 coordination mode rather than the typical κ3 coordination mode of facial capping tridentate ligands. Computational analyses indicate that κ2 coordination mode is favored over the κ3-mode in these coinage metal-ethylene complexes and point to the effects CF3-substituents have on κ2/κ3-energy difference. The M-C and M-N bond distances of [MeB(6-(CF3)Py)3]M(C2H4) follow the trend expected based on covalent radii of M(I) ions. The calculated ethylene-M interaction energy of κ2-[MeB(6-(CF3)Py)3]M(C2H4) indicated that the gold(I) forms the strongest interaction with ethylene. A comparison to the related poly(pyrazolyl)borates is also presented.

AB - Bis- and tris-pyridyl borate ligands containing pyridyl donor arms, a methylated boron cap, and a fluorine-lined coordination pocket have been prepared and utilized in coinage metal chemistry. The tris(pyridyl)borate ligand has been synthesized using a convenient boron source, [NBu4][MeBF3]. These N-based ligands permitted the isolation of group 11 metal-ethylene complexes [MeB(6-(CF3)Py)3]M(C2H4) and [Me2B(6-(CF3)Py)2]M(C2H4) (M = Cu, Ag, Au). The gold complexes display the largest coordination-induced upfield shifts of the ethylene 13C resonance relative to that of the free ethylene in their NMR spectra, while the silver complexes show the smallest shift. Solid-state structures of five of these metal-ethylene complexes as well as the related free ligands were established by X-ray crystallography. Surprisingly, all three [MeB(6-(CF3)Py)3]M(C2H4) adopt the rare κ2 coordination mode rather than the typical κ3 coordination mode of facial capping tridentate ligands. Computational analyses indicate that κ2 coordination mode is favored over the κ3-mode in these coinage metal-ethylene complexes and point to the effects CF3-substituents have on κ2/κ3-energy difference. The M-C and M-N bond distances of [MeB(6-(CF3)Py)3]M(C2H4) follow the trend expected based on covalent radii of M(I) ions. The calculated ethylene-M interaction energy of κ2-[MeB(6-(CF3)Py)3]M(C2H4) indicated that the gold(I) forms the strongest interaction with ethylene. A comparison to the related poly(pyrazolyl)borates is also presented.

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U2 - 10.1021/acs.inorgchem.2c04009

DO - 10.1021/acs.inorgchem.2c04009

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AN - SCOPUS:85146605677

SN - 0020-1669

VL - 62

SP - 1636

EP - 1648

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 4

ER -

Copper(I), Silver(I), and Gold(I) Ethylene Complexes of Fluorinated and Boron-Methylated Bis- and Tris(pyridyl)borate Chelators

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