Isolation and Structural Elucidation of 15-Nuclear Copper Dihydride Clusters: An Intermediate in the Formation of a Two-Electron Copper Superatom

Kiran Kumarvarma Chakrahari; Jingping Liao; Rhone P.Brocha Silalahi; Tzu Hao Chiu; Jian Hong Liao; Xiaoping Wang; Samia Kahlal; Jean Yves Saillard; C. W. Liu

doi:10.1002/smll.202002544

Isolation and Structural Elucidation of 15-Nuclear Copper Dihydride Clusters: An Intermediate in the Formation of a Two-Electron Copper Superatom

Kiran Kumarvarma Chakrahari, Jingping Liao, Rhone P.Brocha Silalahi, Tzu Hao Chiu, Jian Hong Liao, Xiaoping Wang, Samia Kahlal, Jean Yves Saillard, C. W. Liu

Single Crystal Diffraction

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

37 Scopus citations

Abstract

Highly reactive copper-dihydride clusters, [Cu₁₅(H)₂(S₂CNR₂)₆(C₂Ph)₆](PF₆) {R = ⁿBu (1_H), ⁿPr (2_H), ⁱBu (3_H)}, are isolated during the reaction of [Cu₂₈H₁₅{S₂CNⁿBu₂}₁₂](PF₆) with ten equivalents of phenylacetylene. They are found to be intermediates in the formation of the earlier reported two-electron superatom [Cu₁₃(S₂CNR₂)₆(C₂Ph)₄]⁺. Better yields are obtained by reacting dithiocarbamate sodium salts, [Cu(CH₃CN)₄](PF₆), BH₄⁻ and phenylacetylene. The presence of two hydrides in the isolated clusters is confirmed by the synthesis and characterization of its deuteride analogue [Cu₁₅(D)₂(S₂CNR₂)₆(C₂Ph)₆]⁺, and a single-crystal neutron structure of 2_H. Structural characterization of 1_H reveals a new bicapped icosahedral copper(I) cage encapsulating a linear copper dihydride (CuH₂)⁻ unit. Reaction of 3_H with Au(I) salts yields a highly luminescent [AuCu₁₂(S₂CNⁱBu₂)₆(C₂Ph)₄]⁺ cluster.

Original language	English
Article number	2002544
Journal	Small
Volume	17
Issue number	27
DOIs	https://doi.org/10.1002/smll.202002544
State	Published - Jul 8 2021

Funding

K.K.C. and J.L. contributed equally to this work. This work was supported by the Ministry of Science and Technology of Taiwan (MOST 109-2113-M-259-008, 108-2923-M-259-001), and the France-Taiwan ANR-MOST program (project Nanoalloys). K.K.C. would like to thank SERB for financial support (SRG/2019/001618). The Grand Equipement de Calcul Intensif (GENCI) is acknowledged for computing resources (Project A0050807367). Single-crystal neutron diffraction used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. This manuscript has been authored by UT-Battelle, LLC, under contract DE-AC05-00OR22725 with the US Department of Energy (DOE). K.K.C. and J.L. contributed equally to this work. This work was supported by the Ministry of Science and Technology of Taiwan (MOST 109‐2113‐M‐259‐008, 108‐2923‐M‐259‐001), and the France‐Taiwan ANR‐MOST program (project Nanoalloys). K.K.C. would like to thank SERB for financial support (SRG/2019/001618). The Grand Equipement de Calcul Intensif (GENCI) is acknowledged for computing resources (Project A0050807367). Single‐crystal neutron diffraction used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. This manuscript has been authored by UT‐Battelle, LLC, under contract DE‐AC05‐00OR22725 with the US Department of Energy (DOE).

Keywords

copper
hydride
nanoclusters
neutron diffraction

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title = "Isolation and Structural Elucidation of 15-Nuclear Copper Dihydride Clusters: An Intermediate in the Formation of a Two-Electron Copper Superatom",

abstract = "Highly reactive copper-dihydride clusters, [Cu15(H)2(S2CNR2)6(C2Ph)6](PF6) \{R = nBu (1H), nPr (2H), iBu (3H)\}, are isolated during the reaction of [Cu28H15\{S2CNnBu2\}12](PF6) with ten equivalents of phenylacetylene. They are found to be intermediates in the formation of the earlier reported two-electron superatom [Cu13(S2CNR2)6(C2Ph)4]+. Better yields are obtained by reacting dithiocarbamate sodium salts, [Cu(CH3CN)4](PF6), BH4− and phenylacetylene. The presence of two hydrides in the isolated clusters is confirmed by the synthesis and characterization of its deuteride analogue [Cu15(D)2(S2CNR2)6(C2Ph)6]+, and a single-crystal neutron structure of 2H. Structural characterization of 1H reveals a new bicapped icosahedral copper(I) cage encapsulating a linear copper dihydride (CuH2)− unit. Reaction of 3H with Au(I) salts yields a highly luminescent [AuCu12(S2CNiBu2)6(C2Ph)4]+ cluster.",

keywords = "copper, hydride, nanoclusters, neutron diffraction",

author = "Chakrahari, \{Kiran Kumarvarma\} and Jingping Liao and Silalahi, \{Rhone P.Brocha\} and Chiu, \{Tzu Hao\} and Liao, \{Jian Hong\} and Xiaoping Wang and Samia Kahlal and Saillard, \{Jean Yves\} and Liu, \{C. W.\}",

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doi = "10.1002/smll.202002544",

language = "English",

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T2 - An Intermediate in the Formation of a Two-Electron Copper Superatom

AU - Chakrahari, Kiran Kumarvarma

AU - Liao, Jingping

AU - Silalahi, Rhone P.Brocha

AU - Chiu, Tzu Hao

AU - Liao, Jian Hong

AU - Wang, Xiaoping

AU - Kahlal, Samia

AU - Saillard, Jean Yves

AU - Liu, C. W.

PY - 2021/7/8

Y1 - 2021/7/8

N2 - Highly reactive copper-dihydride clusters, [Cu15(H)2(S2CNR2)6(C2Ph)6](PF6) {R = nBu (1H), nPr (2H), iBu (3H)}, are isolated during the reaction of [Cu28H15{S2CNnBu2}12](PF6) with ten equivalents of phenylacetylene. They are found to be intermediates in the formation of the earlier reported two-electron superatom [Cu13(S2CNR2)6(C2Ph)4]+. Better yields are obtained by reacting dithiocarbamate sodium salts, [Cu(CH3CN)4](PF6), BH4− and phenylacetylene. The presence of two hydrides in the isolated clusters is confirmed by the synthesis and characterization of its deuteride analogue [Cu15(D)2(S2CNR2)6(C2Ph)6]+, and a single-crystal neutron structure of 2H. Structural characterization of 1H reveals a new bicapped icosahedral copper(I) cage encapsulating a linear copper dihydride (CuH2)− unit. Reaction of 3H with Au(I) salts yields a highly luminescent [AuCu12(S2CNiBu2)6(C2Ph)4]+ cluster.

AB - Highly reactive copper-dihydride clusters, [Cu15(H)2(S2CNR2)6(C2Ph)6](PF6) {R = nBu (1H), nPr (2H), iBu (3H)}, are isolated during the reaction of [Cu28H15{S2CNnBu2}12](PF6) with ten equivalents of phenylacetylene. They are found to be intermediates in the formation of the earlier reported two-electron superatom [Cu13(S2CNR2)6(C2Ph)4]+. Better yields are obtained by reacting dithiocarbamate sodium salts, [Cu(CH3CN)4](PF6), BH4− and phenylacetylene. The presence of two hydrides in the isolated clusters is confirmed by the synthesis and characterization of its deuteride analogue [Cu15(D)2(S2CNR2)6(C2Ph)6]+, and a single-crystal neutron structure of 2H. Structural characterization of 1H reveals a new bicapped icosahedral copper(I) cage encapsulating a linear copper dihydride (CuH2)− unit. Reaction of 3H with Au(I) salts yields a highly luminescent [AuCu12(S2CNiBu2)6(C2Ph)4]+ cluster.

KW - copper

KW - hydride

KW - nanoclusters

KW - neutron diffraction

UR - https://www.scopus.com/pages/publications/85094135050

U2 - 10.1002/smll.202002544

DO - 10.1002/smll.202002544

M3 - Article

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AN - SCOPUS:85094135050

SN - 1613-6810

VL - 17

JO - Small

JF - Small

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M1 - 2002544

ER -

Isolation and Structural Elucidation of 15-Nuclear Copper Dihydride Clusters: An Intermediate in the Formation of a Two-Electron Copper Superatom

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