Synthesis of Bimetallic Copper-Rich Nanoclusters Encapsulating a Linear Palladium Dihydride Unit

Kiran Kumarvarma Chakrahari; Rhone P.Brocha Silalahi; Tzu Hao Chiu; Xiaoping Wang; Nadia Azrou; Samia Kahlal; Yu Chiao Liu; Ming Hsi Chiang; Jean Yves Saillard; C. W. Liu

doi:10.1002/anie.201814264

Synthesis of Bimetallic Copper-Rich Nanoclusters Encapsulating a Linear Palladium Dihydride Unit

Kiran Kumarvarma Chakrahari, Rhone P.Brocha Silalahi, Tzu Hao Chiu, Xiaoping Wang, Nadia Azrou, Samia Kahlal, Yu Chiao Liu, Ming Hsi Chiang, Jean Yves Saillard, C. W. Liu

Single Crystal Diffraction

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Abstract

The structurally precise Cu-rich hydride nanoclusters [PdCu ₁₄ H ₂ (dtc/dtp) ₆ (C≡CPh) ₆ ] (dtc: di-butyldithiocarbamate (1); dtp: di-isopropyl dithiophosphate (2)) were synthesized from the reaction of polyhydrido copper clusters [Cu ₂₈ H ₁₅ (S ₂ CN ⁿ Bu ₂ ) ₁₂ ] ⁺ or [Cu ₂₀ H ₁₁ {S ₂ P(O ⁱ Pr) ₂ } ₉ ] with phenyl acetylene in the presence of Pd(PPh ₃ ) ₂ Cl ₂ . Their structures and compositions were determined by single-crystal X-ray diffraction and the results supported by ESI-mass spectrometry. Hydride positions in 1 were confirmed by single-crystal neutron diffraction. Each hydride is connected to one Pd ⁰ and four Cu ^I atoms in slightly distorted trigonalbipyramidal geometry. The anatomies of clusters 1 and 2 are very similar and DFT calculations allow rationalizing the interactions between the encapsulated [PdH ₂ ] ²⁻ unit and its Cu ₁₄ bicapped icosahedral cage. As a result, Pd has the highest coordination number (14) so far recorded.

Original language	English
Pages (from-to)	4943-4947
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	58
Issue number	15
DOIs	https://doi.org/10.1002/anie.201814264
State	Published - Apr 1 2019

Funding

This work was supported by the Ministry of Science and Technology in Taiwan (MOST 108-2923-M-259-001), the France-Taiwan ANR-MOST 2018 program (project Nano-alloys) and the GENCI French national computer resource center (grant A0030807367). Single crystal neutron diffraction performed on TOPAZ used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory, under Contract No. DE-AC05-00OR22725 with UT-Battelle, LLC. This work was supported by the Ministry of Science and Technology in Taiwan (MOST 108-2923-M-259-001), the France-Taiwan ANR-MOST 2018 program (project Nanoalloys) and the GENCI French national computer resource center (grant A0030807367). Single crystal neutron diffraction performed on TOPAZ used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory, under Contract No. DE-AC05-00OR22725 with UT-Battelle, LLC.

Keywords

copper
hydrides
nanoclusters
neutron diffraction
palladium

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title = "Synthesis of Bimetallic Copper-Rich Nanoclusters Encapsulating a Linear Palladium Dihydride Unit",

abstract = " The structurally precise Cu-rich hydride nanoclusters [PdCu 14 H 2 (dtc/dtp) 6 (C≡CPh) 6 ] (dtc: di-butyldithiocarbamate (1); dtp: di-isopropyl dithiophosphate (2)) were synthesized from the reaction of polyhydrido copper clusters [Cu 28 H 15 (S 2 CN n Bu 2 ) 12 ] + or [Cu 20 H 11 \{S 2 P(O i Pr) 2 \} 9 ] with phenyl acetylene in the presence of Pd(PPh 3 ) 2 Cl 2 . Their structures and compositions were determined by single-crystal X-ray diffraction and the results supported by ESI-mass spectrometry. Hydride positions in 1 were confirmed by single-crystal neutron diffraction. Each hydride is connected to one Pd 0 and four Cu I atoms in slightly distorted trigonalbipyramidal geometry. The anatomies of clusters 1 and 2 are very similar and DFT calculations allow rationalizing the interactions between the encapsulated [PdH 2 ] 2− unit and its Cu 14 bicapped icosahedral cage. As a result, Pd has the highest coordination number (14) so far recorded.",

keywords = "copper, hydrides, nanoclusters, neutron diffraction, palladium",

author = "Chakrahari, \{Kiran Kumarvarma\} and Silalahi, \{Rhone P.Brocha\} and Chiu, \{Tzu Hao\} and Xiaoping Wang and Nadia Azrou and Samia Kahlal and Liu, \{Yu Chiao\} and Chiang, \{Ming Hsi\} and Saillard, \{Jean Yves\} and Liu, \{C. W.\}",

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year = "2019",

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doi = "10.1002/anie.201814264",

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AU - Chakrahari, Kiran Kumarvarma

AU - Silalahi, Rhone P.Brocha

AU - Chiu, Tzu Hao

AU - Wang, Xiaoping

AU - Azrou, Nadia

AU - Kahlal, Samia

AU - Liu, Yu Chiao

AU - Chiang, Ming Hsi

AU - Saillard, Jean Yves

AU - Liu, C. W.

PY - 2019/4/1

Y1 - 2019/4/1

N2 - The structurally precise Cu-rich hydride nanoclusters [PdCu 14 H 2 (dtc/dtp) 6 (C≡CPh) 6 ] (dtc: di-butyldithiocarbamate (1); dtp: di-isopropyl dithiophosphate (2)) were synthesized from the reaction of polyhydrido copper clusters [Cu 28 H 15 (S 2 CN n Bu 2 ) 12 ] + or [Cu 20 H 11 {S 2 P(O i Pr) 2 } 9 ] with phenyl acetylene in the presence of Pd(PPh 3 ) 2 Cl 2 . Their structures and compositions were determined by single-crystal X-ray diffraction and the results supported by ESI-mass spectrometry. Hydride positions in 1 were confirmed by single-crystal neutron diffraction. Each hydride is connected to one Pd 0 and four Cu I atoms in slightly distorted trigonalbipyramidal geometry. The anatomies of clusters 1 and 2 are very similar and DFT calculations allow rationalizing the interactions between the encapsulated [PdH 2 ] 2− unit and its Cu 14 bicapped icosahedral cage. As a result, Pd has the highest coordination number (14) so far recorded.

AB - The structurally precise Cu-rich hydride nanoclusters [PdCu 14 H 2 (dtc/dtp) 6 (C≡CPh) 6 ] (dtc: di-butyldithiocarbamate (1); dtp: di-isopropyl dithiophosphate (2)) were synthesized from the reaction of polyhydrido copper clusters [Cu 28 H 15 (S 2 CN n Bu 2 ) 12 ] + or [Cu 20 H 11 {S 2 P(O i Pr) 2 } 9 ] with phenyl acetylene in the presence of Pd(PPh 3 ) 2 Cl 2 . Their structures and compositions were determined by single-crystal X-ray diffraction and the results supported by ESI-mass spectrometry. Hydride positions in 1 were confirmed by single-crystal neutron diffraction. Each hydride is connected to one Pd 0 and four Cu I atoms in slightly distorted trigonalbipyramidal geometry. The anatomies of clusters 1 and 2 are very similar and DFT calculations allow rationalizing the interactions between the encapsulated [PdH 2 ] 2− unit and its Cu 14 bicapped icosahedral cage. As a result, Pd has the highest coordination number (14) so far recorded.

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Synthesis of Bimetallic Copper-Rich Nanoclusters Encapsulating a Linear Palladium Dihydride Unit

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