Nature of the Short Rh-Li Contact between Lithium and the Rhodium ω-Alkenyl Complex [Rh(CH2CMe2CH2CH═CH2)2]-

Sumeng Liu; Brett A. Smith; Justin K. Kirkland; Konstantinos D. Vogiatzis; Gregory S. Girolami

doi:10.1021/acs.inorgchem.1c00737

Nature of the Short Rh-Li Contact between Lithium and the Rhodium ω-Alkenyl Complex [Rh(CH₂CMe₂CH₂CH═CH₂)₂]^-

Sumeng Liu, Brett A. Smith, Justin K. Kirkland, Konstantinos D. Vogiatzis, Gregory S. Girolami

Chemical Sciences Division

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

2 Scopus citations

Abstract

We describe the preparation of the cis-bis(η1,η2-2,2-dimethylpent-4-en-1-yl)rhodate(I) anion, cis-[Rh(CH2CMe2CH2CH═CH2)2]-, and the interaction of this species with Li+ both in solution and in the solid state. For the lithium(diethyl ether) salt [Li(Et2O)][Rh(CH2CMe2CH2CH═CH2)2], VT-NMR and 1H{7Li} NOE NMR studies in toluene-d8 show that the Li+ cation is in close proximity to the dz2 orbital of rhodium. In the solid-state structure of the lithium(12-crown-4) salt [Li(12-crown-4)2][Li{Rh(CH2CMe2CH2CH═CH2)2}2], one lithium atom is surrounded by two [Rh(CH2CMe2CH2CH═CH2)2]- anions, and in this assembly there are two unusually short Rh-Li distances of 2.48 Å. DFT calculations, natural energy decomposition, and ETS-NOCV analysis suggest that there is a weak dative interaction between the 4dz2 orbitals on the Rh centers and the 2pz orbital of the Li+ cation. The charge-transfer term between Rh and Li+ contributes only about the 1/5 of the total interaction energy, however, and the principal driving force for the proximity of Rh and Li in compounds 1 and 2 is that Li+ is electrostatically attracted to negative charges on the dialkylrhodiate anions.

Original language	English
Pages (from-to)	8790-8801
Number of pages	12
Journal	Inorganic Chemistry
Volume	60
Issue number	12
DOIs	https://doi.org/10.1021/acs.inorgchem.1c00737
State	Published - Jun 21 2021

Funding

National Science Foundation under grants CHE 1954745 and CHE 1665191 (to G.S.G.) and CHE-1800237 (to K.D.V.). G.S.G. thanks the National Science Foundation (grants CHE 16-65191 and CHE 19-54745) for supporting this research. B.A.S., J.K.K., and K.D.V. gratefully acknowledge the National Science Foundation (CHE-1800237) for financially supporting this work and the Advanced Computer Facility (ACF) of the University of Tennessee for computational resources.

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title = "Nature of the Short Rh-Li Contact between Lithium and the Rhodium ω-Alkenyl Complex [Rh(CH2CMe2CH2CH═CH2)2]-",

abstract = "We describe the preparation of the cis-bis(η1,η2-2,2-dimethylpent-4-en-1-yl)rhodate(I) anion, cis-[Rh(CH2CMe2CH2CH═CH2)2]-, and the interaction of this species with Li+ both in solution and in the solid state. For the lithium(diethyl ether) salt [Li(Et2O)][Rh(CH2CMe2CH2CH═CH2)2], VT-NMR and 1H{7Li} NOE NMR studies in toluene-d8 show that the Li+ cation is in close proximity to the dz2 orbital of rhodium. In the solid-state structure of the lithium(12-crown-4) salt [Li(12-crown-4)2][Li{Rh(CH2CMe2CH2CH═CH2)2}2], one lithium atom is surrounded by two [Rh(CH2CMe2CH2CH═CH2)2]- anions, and in this assembly there are two unusually short Rh-Li distances of 2.48 {\AA}. DFT calculations, natural energy decomposition, and ETS-NOCV analysis suggest that there is a weak dative interaction between the 4dz2 orbitals on the Rh centers and the 2pz orbital of the Li+ cation. The charge-transfer term between Rh and Li+ contributes only about the 1/5 of the total interaction energy, however, and the principal driving force for the proximity of Rh and Li in compounds 1 and 2 is that Li+ is electrostatically attracted to negative charges on the dialkylrhodiate anions.",

author = "Sumeng Liu and Smith, {Brett A.} and Kirkland, {Justin K.} and Vogiatzis, {Konstantinos D.} and Girolami, {Gregory S.}",

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AU - Liu, Sumeng

AU - Smith, Brett A.

AU - Kirkland, Justin K.

AU - Vogiatzis, Konstantinos D.

AU - Girolami, Gregory S.

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AB - We describe the preparation of the cis-bis(η1,η2-2,2-dimethylpent-4-en-1-yl)rhodate(I) anion, cis-[Rh(CH2CMe2CH2CH═CH2)2]-, and the interaction of this species with Li+ both in solution and in the solid state. For the lithium(diethyl ether) salt [Li(Et2O)][Rh(CH2CMe2CH2CH═CH2)2], VT-NMR and 1H{7Li} NOE NMR studies in toluene-d8 show that the Li+ cation is in close proximity to the dz2 orbital of rhodium. In the solid-state structure of the lithium(12-crown-4) salt [Li(12-crown-4)2][Li{Rh(CH2CMe2CH2CH═CH2)2}2], one lithium atom is surrounded by two [Rh(CH2CMe2CH2CH═CH2)2]- anions, and in this assembly there are two unusually short Rh-Li distances of 2.48 Å. DFT calculations, natural energy decomposition, and ETS-NOCV analysis suggest that there is a weak dative interaction between the 4dz2 orbitals on the Rh centers and the 2pz orbital of the Li+ cation. The charge-transfer term between Rh and Li+ contributes only about the 1/5 of the total interaction energy, however, and the principal driving force for the proximity of Rh and Li in compounds 1 and 2 is that Li+ is electrostatically attracted to negative charges on the dialkylrhodiate anions.

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Nature of the Short Rh-Li Contact between Lithium and the Rhodium ω-Alkenyl Complex [Rh(CH₂CMe₂CH₂CH═CH₂)₂]^-

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