Group 11 <i>m</i>-Terphenyl Complexes Featuring Metallophilic Interactions

Liu, Yu; Taylor, Laurence J.; Argent, Stephen P.; McMaster, Jonathan; Kays, Deborah L.

doi:10.1021/acs.inorgchem.0c03623

Cited by 9 publications

(7 citation statements)

References 95 publications

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“…The longer Cu–S bond lengths in 1 and 2 are consistent with the increased bulkiness of the ligands . The Cu--Cu distances in complexes 1 and 2 are 2.452(2) Å and 2.410(7) Å, respectively, which are greater than the sum of the covalent radii (2.24 Å) of the two Cu atoms, which does not establish metal–metal bonding, but are within the sum of the van der Waals radii (2.8 Å), suggesting the presence of a correlation-dispersion interaction. − Additionally, the Cu--Cu distances in both complexes are comparable to those in some previously reported copper(I) complexes, , and these Cu--Cu distances, in conjunction with computational studies, , concluded that the Cu--Cu separations in 1 and 2 do not indicate the presence of Cu–Cu bonds. Moreover, it is noteworthy that the Cu--Cu distance of 2 is slightly longer than that of 1 , which produces higher dispersion energy due to the increased numbers of isopropyl groups.…”

Section: Resultsmentioning

confidence: 82%

Dimeric Copper and Lithium Thiolates: Comparison of Copper Thiolates with Their Lithium Congeners

et al. 2021

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The direct reactions of the large terphenyl thiols HSAr iPr4 (Ar iPr4 = −C 6 H 3 -2,6-(C 6 H 3 -2,6-iPr 2 ) 2 ) and HSAr iPr6 (Ar iPr6 = −C 6 H 3 -2,6-(C 6 H 2 -2,4,6-iPr 3 ) 2 ) with stoichiometric amounts of mesitylcopper(I) in THF at ca. 80 °C afforded the first well-characterized dimeric copper thiolato species {CuSAr iPr4 } 2 (1) and {CuSAr iPr6 } 2 (2) with elimination of mesitylene. The complexes 1 and 2 were characterized by NMR and electronic spectroscopy as well as by X-ray crystallography. They have dimeric Cu 2 S 2 core structures in which the two copper atoms are bridged by the sulfurs from the thiolato ligands and feature short Cu--Cu distances near 2.4 Å as well as a weak copper-flanking aryl ring interaction from a terphenyl substituent. The structures of the planar Cu 2 S 2 cores bear a resemblance to the Cu A site in nitrous oxide reductase in which two cysteines also bridge two copper atoms. The related dimeric Li 2 S 2 structural motif was also observed in the lithium congeners {LiSAr iPr4 } 2 (3) and {LiSAr iPr6 } 2 (4) which were synthesized directly from the thiols and n-BuLi in hexanes. However, despite the very similar effective ionic radii of the Li + (0.59 Å) and Cu + (0.60 Å) ions, the Li--Li structures display very much longer (by more than ca. 0.5 Å) separations than the corresponding Cu--Cu distances in 1 and 2, which may be due to weaker dispersion interactions.

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Section: Resultsmentioning

confidence: 82%

Dimeric Copper and Lithium Thiolates: Comparison of Copper Thiolates with Their Lithium Congeners

et al. 2021

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“…The ligand–metal delocalization indices fit well with other reported metal–ligand delocalization indices. For example, in dimeric copper and silver m -terphenyl complexes with comparable metal coordination geometries and short metal–metal distances, the delocalization indices between each metal and the bridging carbon atom of the m -terphenyl ligand were found to be in the range 0.51–0.61 . For the bridged C 2v isomer of Co 2 (CO) 8 , the delocalization indices between the cobalt centers and the bridging CO were found to have an average value of around 0.82 …”

Section: Resultsmentioning

confidence: 99%

Electron Density Analysis of Metal–Metal Bonding in a Ni₄Cluster Featuring Ferromagnetic Exchange

et al. 2022

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We present a combined experimental and theoretical study of the nature of the proposed metal−metal bonding in the tetranuclear cluster Ni 4 (NP t Bu 3 ) 4 , which features four nickel(I) centers engaged in strong ferromagnetic coupling. High-resolution single-crystal synchrotron X-ray diffraction data collected at 25 K provide an accurate geometrical structure and a multipole model electron density description. Topological analysis of the electron density in the Ni 4 N 4 core using the quantum theory of atoms in molecules clearly identifies the bonding as an eight-membered ring of type [Ni−N−] 4 without direct Ni−Ni bonding, and this result is generally corroborated by an analysis of the energy density distribution. In contrast, the calculated bond delocalization index of ∼0.6 between neighboring Ni atoms is larger than what has been found for other bridged metal−metal bonds and implies direct Ni−Ni bonding. Similar support for the presence of direct Ni−Ni bonding is found in the interacting quantum atom approach, an energy decomposition scheme, which suggests the presence of stabilizing Ni−Ni bonding interactions with an exchange-correlation energy contribution approximately 50% of that of the Ni−N interactions. Altogether, while the direct interactions between neighboring Ni centers are too weak and sterically constrained to bear the signature of a topological bond critical point, other continuous measures clearly indicate significant Ni−Ni bonding. These metal−metal bonding interactions likely mediate direct ferromagnetic exchange, giving rise to the high-spin ground state of the molecule.

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“…This suggests that the aromaticity of the mesityl ligand is disrupted by metal coordination and the complexes retain their dimeric structures in solution. In contrast to the silver m-terphenyl complex [(2,6-Mes 2 C 6 H 3 )Ag] 2 , 13 only broad, unresolved 1 J CAg splitting patterns were observed for the Z 2 -bound carbon atoms in [2-Ag] 2 . More conclusive evidence that complexes [2-Cu] 2 and [2-Ag] 2 remain dimeric in solution was provided by diffusion-ordered spectroscopy (DOSY) measurements in benzene solution.…”

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confidence: 82%

“…To classify the coordination environment of the metal ions in the dimers, we performed the same NBO analysis on the isostructural m-terphenyl complexes published by Kays. 13 As for the metallophilic interactions, the complexes have slightly higher WBIs: 0.261 for [(2,6-Mes 2 C 6 H 3 )Cu] 2 and 0.398 for [(2,6-Mes 2 C 6 H 3 )Ag] 2 . The gold derivative has an AuÁ Á ÁAu bond order of 0.291 and thus, unlike for the nitrogen-bonded complexes, does not exhibit the strongest metal-metal interaction in the series.…”

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confidence: 98%

“…11 Despite the widespread use of m -terphenyl ligands to stabilize unique bonding types between metal centers, corresponding complexes with possible metallophilic bonding interactions are comparatively rare, 12 and it was only recently that the group of Kays unambiguously identified such interactions in a series of binuclear d 10 metal complexes. 13 Due to the remarkable similarities with our systems, spectroscopic, structural and theoretical comparisons are made.…”

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confidence: 99%

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Coinage metal complexes of BN analogues of m-terphenyl ligands

Lamprecht¹,

Lindl²,

Endres³

et al. 2023

Chem. Commun.

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Group 11 m-Terphenyl Complexes Featuring Metallophilic Interactions

Abstract: A series of group 11 m-terphenyl complexes have been synthesized via a metathesis reaction from the iron(II) complexes (2,6

Cited by 9 publications

References 95 publications

Dimeric Copper and Lithium Thiolates: Comparison of Copper Thiolates with Their Lithium Congeners

Dimeric Copper and Lithium Thiolates: Comparison of Copper Thiolates with Their Lithium Congeners

Electron Density Analysis of Metal–Metal Bonding in a Ni₄Cluster Featuring Ferromagnetic Exchange

Coinage metal complexes of BN analogues of m-terphenyl ligands

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Group 11 m-Terphenyl Complexes Featuring Metallophilic Interactions

Abstract: A series of group 11 m-terphenyl complexes have been synthesized via a metathesis reaction from the iron(II) complexes (2,6

Cited by 9 publications

References 95 publications

Dimeric Copper and Lithium Thiolates: Comparison of Copper Thiolates with Their Lithium Congeners

Dimeric Copper and Lithium Thiolates: Comparison of Copper Thiolates with Their Lithium Congeners

Electron Density Analysis of Metal–Metal Bonding in a Ni4Cluster Featuring Ferromagnetic Exchange

Coinage metal complexes of BN analogues of m-terphenyl ligands

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Electron Density Analysis of Metal–Metal Bonding in a Ni₄Cluster Featuring Ferromagnetic Exchange