Reactivities of Interstitial Hydrides in a Cu11 Template: En Route to Bimetallic Clusters

Rhone P.Brocha Silalahi; Qi Wang; Jian Hong Liao; Tzu Hao Chiu; Ying Yann Wu; Xiaoping Wang; Samia Kahlal; Jean Yves Saillard; C. W. Liu

doi:10.1002/anie.202113266

Reactivities of Interstitial Hydrides in a Cu₁₁ Template: En Route to Bimetallic Clusters

Rhone P.Brocha Silalahi, Qi Wang, Jian Hong Liao, Tzu Hao Chiu, Ying Yann Wu, Xiaoping Wang, Samia Kahlal, Jean Yves Saillard, C. W. Liu

Single Crystal Diffraction

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

28 Scopus citations

Abstract

In sharp contrast to surface hydrides, reactivities of interstitial hydrides are difficult to explore. When treated with a metal ion (Cu⁺, Ag⁺, and Au⁺), the stable Cu^I dihydride template [Cu₁₁H₂{S₂P(OⁱPr)₂}₆(C≡CPh)₃] (H₂Cu₁₁) generates surprisingly three very different compounds, namely [CuH₂Cu₁₁{S₂P(OⁱPr)₂}₆(C≡CPh)₃]⁺ (1), [AgH₂Cu₁₄{S₂P(OⁱPr)₂}₆((C≡CPh)₆]⁺ (2), and [AuCu₁₁{S₂P(OⁱPr)₂}₆(C≡CPh)₃Cl] (3). Compounds 1 and 2 are both M^I species and maintain the same number of hydride ligands as their H₂Cu₁₁ precursor. Neutron diffraction revealed the first time a trigonal-pyramidal hydride coordination mode in the AgCu₃ environment of 2. 3 has no hydride and exhibits a mixed-valent [AuCu₁₁]¹⁰⁺ metal core, making it a two-electron superatom.

Original language	English
Article number	e202113266
Journal	Angewandte Chemie - International Edition
Volume	61
Issue number	2
DOIs	https://doi.org/10.1002/anie.202113266
State	Published - Jan 10 2022

Funding

This work was supported by the Ministry of Science and Technology of Taiwan (MOST, Grant No. 109‐2113‐M‐259‐008), the France‐Taiwan ANR‐MOST program (project Nanoalloys) and the GENCI computing resource (grant A0090807367). Q.W. thanks the China Scholarship Council for a Ph.D. grant. The single‐crystal neutron diffraction measurements performed on TOPAZ used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. This work was supported by the Ministry of Science and Technology of Taiwan (MOST, Grant No. 109-2113-M-259-008), the France-Taiwan ANR-MOST program (project Nanoalloys) and the GENCI computing resource (grant A0090807367). Q.W. thanks the China Scholarship Council for a Ph.D. grant. The single-crystal neutron diffraction measurements performed on TOPAZ used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory.

Funders	Funder number
ANR-MOST
France‐Taiwan ANR‐MOST program
Office of Science
Oak Ridge National Laboratory
China Scholarship Council
Ministry of Science and Technology, Taiwan	109‐2113‐M‐259‐008
Grand Équipement National De Calcul Intensif	A0090807367

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title = "Reactivities of Interstitial Hydrides in a Cu11 Template: En Route to Bimetallic Clusters",

abstract = "In sharp contrast to surface hydrides, reactivities of interstitial hydrides are difficult to explore. When treated with a metal ion (Cu+, Ag+, and Au+), the stable CuI dihydride template [Cu11H2{S2P(OiPr)2}6(C≡CPh)3] (H2Cu11) generates surprisingly three very different compounds, namely [CuH2Cu11{S2P(OiPr)2}6(C≡CPh)3]+ (1), [AgH2Cu14{S2P(OiPr)2}6((C≡CPh)6]+ (2), and [AuCu11{S2P(OiPr)2}6(C≡CPh)3Cl] (3). Compounds 1 and 2 are both MI species and maintain the same number of hydride ligands as their H2Cu11 precursor. Neutron diffraction revealed the first time a trigonal-pyramidal hydride coordination mode in the AgCu3 environment of 2. 3 has no hydride and exhibits a mixed-valent [AuCu11]10+ metal core, making it a two-electron superatom.",

author = "Silalahi, {Rhone P.Brocha} and Qi Wang and Liao, {Jian Hong} and Chiu, {Tzu Hao} and Wu, {Ying Yann} and Xiaoping Wang and Samia Kahlal and Saillard, {Jean Yves} and Liu, {C. W.}",

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doi = "10.1002/anie.202113266",

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AU - Silalahi, Rhone P.Brocha

AU - Wang, Qi

AU - Liao, Jian Hong

AU - Chiu, Tzu Hao

AU - Wu, Ying Yann

AU - Wang, Xiaoping

AU - Kahlal, Samia

AU - Saillard, Jean Yves

AU - Liu, C. W.

PY - 2022/1/10

Y1 - 2022/1/10

N2 - In sharp contrast to surface hydrides, reactivities of interstitial hydrides are difficult to explore. When treated with a metal ion (Cu+, Ag+, and Au+), the stable CuI dihydride template [Cu11H2{S2P(OiPr)2}6(C≡CPh)3] (H2Cu11) generates surprisingly three very different compounds, namely [CuH2Cu11{S2P(OiPr)2}6(C≡CPh)3]+ (1), [AgH2Cu14{S2P(OiPr)2}6((C≡CPh)6]+ (2), and [AuCu11{S2P(OiPr)2}6(C≡CPh)3Cl] (3). Compounds 1 and 2 are both MI species and maintain the same number of hydride ligands as their H2Cu11 precursor. Neutron diffraction revealed the first time a trigonal-pyramidal hydride coordination mode in the AgCu3 environment of 2. 3 has no hydride and exhibits a mixed-valent [AuCu11]10+ metal core, making it a two-electron superatom.

AB - In sharp contrast to surface hydrides, reactivities of interstitial hydrides are difficult to explore. When treated with a metal ion (Cu+, Ag+, and Au+), the stable CuI dihydride template [Cu11H2{S2P(OiPr)2}6(C≡CPh)3] (H2Cu11) generates surprisingly three very different compounds, namely [CuH2Cu11{S2P(OiPr)2}6(C≡CPh)3]+ (1), [AgH2Cu14{S2P(OiPr)2}6((C≡CPh)6]+ (2), and [AuCu11{S2P(OiPr)2}6(C≡CPh)3Cl] (3). Compounds 1 and 2 are both MI species and maintain the same number of hydride ligands as their H2Cu11 precursor. Neutron diffraction revealed the first time a trigonal-pyramidal hydride coordination mode in the AgCu3 environment of 2. 3 has no hydride and exhibits a mixed-valent [AuCu11]10+ metal core, making it a two-electron superatom.

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Reactivities of Interstitial Hydrides in a Cu₁₁ Template: En Route to Bimetallic Clusters

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