Diselenophosphate-Induced Conversion of an Achiral [Cu20H11{S2P(OiPr)2}9] into a Chiral [Cu20H11{Se2P(OiPr)2}9] Polyhydrido Nanocluster

Rajendra S. Dhayal; Jian Hong Liao; Xiaoping Wang; Yu Chiao Liu; Ming His Chiang; Samia Kahlal; Jean Yves Saillard; C. W. Liu

doi:10.1002/anie.201506736

Diselenophosphate-Induced Conversion of an Achiral [Cu₂₀H₁₁{S₂P(OiPr)₂}₉] into a Chiral [Cu₂₀H₁₁{Se₂P(OiPr)₂}₉] Polyhydrido Nanocluster

Rajendra S. Dhayal, Jian Hong Liao, Xiaoping Wang, Yu Chiao Liu, Ming His Chiang, Samia Kahlal, Jean Yves Saillard, C. W. Liu

Single Crystal Diffraction

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Abstract

A polyhydrido copper nanocluster, [Cu₂₀H₁₁{Se₂P(OiPr)₂}₉] (2_H), which exhibits an intrinsically chiral inorganic core of C₃ symmetry, was synthesized from achiral [Cu₂₀H₁₁{S₂P(OiPr)₂}₉] (1_H) of C_3h symmetry by a ligand-exchange method. The structure has a distorted cuboctahedral Cu₁₃ core, two triangular faces of which are capped along the C₃ axis, one by a Cu₆ cupola and the other by a single Cu atom. The Cu₂₀ framework is further stabilized by 9 diselenophosphate and 11 hydride ligands. The number of hydride, phosphorus, and selenium resonances and their splitting patterns in multinuclear NMR spectra of 2_H indicate that the chiral Cu₂₀H₁₁ core retains its C₃ symmetry in solution. The 11 hydride ligands were located by neutron diffraction experiments and shown to be capping μ₃-H and interstitial μ₅-H ligands (in square-pyramidal and trigonal-bipyramidal cavities), as supported by DFT calculations on [Cu₂₀H₁₁(Se₂PH₂)₉] (2_H′) as a simplified model.

Original language	English
Pages (from-to)	13604-13608
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	54
Issue number	46
DOIs	https://doi.org/10.1002/anie.201506736
State	Published - Nov 1 2015

Keywords

copper
density functional calculations
hydrides
intrinsic chirality
neutron diffraction

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title = "Diselenophosphate-Induced Conversion of an Achiral [Cu20H11{S2P(OiPr)2}9] into a Chiral [Cu20H11{Se2P(OiPr)2}9] Polyhydrido Nanocluster",

abstract = "A polyhydrido copper nanocluster, [Cu20H11{Se2P(OiPr)2}9] (2H), which exhibits an intrinsically chiral inorganic core of C3 symmetry, was synthesized from achiral [Cu20H11{S2P(OiPr)2}9] (1H) of C3h symmetry by a ligand-exchange method. The structure has a distorted cuboctahedral Cu13 core, two triangular faces of which are capped along the C3 axis, one by a Cu6 cupola and the other by a single Cu atom. The Cu20 framework is further stabilized by 9 diselenophosphate and 11 hydride ligands. The number of hydride, phosphorus, and selenium resonances and their splitting patterns in multinuclear NMR spectra of 2H indicate that the chiral Cu20H11 core retains its C3 symmetry in solution. The 11 hydride ligands were located by neutron diffraction experiments and shown to be capping μ3-H and interstitial μ5-H ligands (in square-pyramidal and trigonal-bipyramidal cavities), as supported by DFT calculations on [Cu20H11(Se2PH2)9] (2H′) as a simplified model.",

keywords = "copper, density functional calculations, hydrides, intrinsic chirality, neutron diffraction",

author = "Dhayal, {Rajendra S.} and Liao, {Jian Hong} and Xiaoping Wang and Liu, {Yu Chiao} and Chiang, {Ming His} and Samia Kahlal and Saillard, {Jean Yves} and Liu, {C. W.}",

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year = "2015",

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T1 - Diselenophosphate-Induced Conversion of an Achiral [Cu20H11{S2P(OiPr)2}9] into a Chiral [Cu20H11{Se2P(OiPr)2}9] Polyhydrido Nanocluster

AU - Dhayal, Rajendra S.

AU - Liao, Jian Hong

AU - Wang, Xiaoping

AU - Liu, Yu Chiao

AU - Chiang, Ming His

AU - Kahlal, Samia

AU - Saillard, Jean Yves

AU - Liu, C. W.

PY - 2015/11/1

Y1 - 2015/11/1

N2 - A polyhydrido copper nanocluster, [Cu20H11{Se2P(OiPr)2}9] (2H), which exhibits an intrinsically chiral inorganic core of C3 symmetry, was synthesized from achiral [Cu20H11{S2P(OiPr)2}9] (1H) of C3h symmetry by a ligand-exchange method. The structure has a distorted cuboctahedral Cu13 core, two triangular faces of which are capped along the C3 axis, one by a Cu6 cupola and the other by a single Cu atom. The Cu20 framework is further stabilized by 9 diselenophosphate and 11 hydride ligands. The number of hydride, phosphorus, and selenium resonances and their splitting patterns in multinuclear NMR spectra of 2H indicate that the chiral Cu20H11 core retains its C3 symmetry in solution. The 11 hydride ligands were located by neutron diffraction experiments and shown to be capping μ3-H and interstitial μ5-H ligands (in square-pyramidal and trigonal-bipyramidal cavities), as supported by DFT calculations on [Cu20H11(Se2PH2)9] (2H′) as a simplified model.

AB - A polyhydrido copper nanocluster, [Cu20H11{Se2P(OiPr)2}9] (2H), which exhibits an intrinsically chiral inorganic core of C3 symmetry, was synthesized from achiral [Cu20H11{S2P(OiPr)2}9] (1H) of C3h symmetry by a ligand-exchange method. The structure has a distorted cuboctahedral Cu13 core, two triangular faces of which are capped along the C3 axis, one by a Cu6 cupola and the other by a single Cu atom. The Cu20 framework is further stabilized by 9 diselenophosphate and 11 hydride ligands. The number of hydride, phosphorus, and selenium resonances and their splitting patterns in multinuclear NMR spectra of 2H indicate that the chiral Cu20H11 core retains its C3 symmetry in solution. The 11 hydride ligands were located by neutron diffraction experiments and shown to be capping μ3-H and interstitial μ5-H ligands (in square-pyramidal and trigonal-bipyramidal cavities), as supported by DFT calculations on [Cu20H11(Se2PH2)9] (2H′) as a simplified model.

KW - copper

KW - density functional calculations

KW - hydrides

KW - intrinsic chirality

KW - neutron diffraction

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Diselenophosphate-Induced Conversion of an Achiral [Cu₂₀H₁₁{S₂P(OiPr)₂}₉] into a Chiral [Cu₂₀H₁₁{Se₂P(OiPr)₂}₉] Polyhydrido Nanocluster

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