Copper Hydride Clusters with Cu9 and Cu13 Frameworks, Showing a Potential for Hydrogen Storage via Fluxional Exchange between Face-Capping and Interstitial Hydrides

IF 4.7 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Pub Date : 2025-09-22 DOI:10.1021/acs.inorgchem.5c03167

Takayuki Nakajima, Madoka Shimada, Yurika Komura, Seina Sakabe, Kanako Nakamae, Kento Iwai, Tomoaki Tanase

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Abstract

Using meso-Ph₂PCH₂P(Ph)(CH₂)₃P(Ph)CH₂PPh₂ (meso-dpmppp), new copper hydride clusters, [Cu₉H₇(meso-dpmppp)₃]X₂ (X = PF₆ (1a), BF₄ (1b), and BPh₄ (1c)), were synthesized and characterized to have a 4,4,4-tricapped trigonal prism (TTP) Cu₉ core. 1a,b was converted by treatment with LiBH₄ to [Cu₉H₈(meso-dpmppp)₃]X (X = PF₆ (2a), BF₄ (2b)), which accommodates an additional hydride while retaining the TTP Cu₉ core. In contrast to the static property of the eight face-capping hydrides of 2, five of the seven hydrides in 1 exhibited the fluxional behavior, which could be frozen at −80 °C into four face-capping and one interstitial hydrides. The Cu₉ core of 1b could be expanded by treating with Ph₂SiH₂ and [Cu(MeCN)₄]BF₄ to give the centered icosahedral (CIH) Cu₁₃ core of [Cu₁₃H₁₀(meso-dpmppp)₃(MeCN)₃](BF₄)₃ (3). The similar CIH cluster of [Cu₁₃H₁₀(meso-dpmppmNBn)₃(MeCN)₃](BF₄)₃ (4) was also synthesized using meso-Ph₂PCH₂P(Ph)CH₂N(CH₂C₆H₅)CH₂P(Ph)CH₂PPh₂ (meso-dpmppmNBn). Treatment of 1a with H₂ (1 atm) in the presence of DBU (1,8-diazabicyclo[5.4.0]-7-undecene) gave 2a quantitatively, and 2a reacted easily with 1 equiv of TfOH or PhOH to be converted back to 1a with concomitant H₂ formation, suggesting a potential for hydrogen storage through the fluxional exchange between face-capping and interstitial hydrides around the TTP scaffold.

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具有Cu9和Cu13框架的铜氢化物簇，通过表面盖层和间隙氢化物之间的交换显示出储氢的潜力

利用meso-Ph2PCH2P(Ph)(CH2)3P(Ph)CH2PPh2 （meso-dpmppp）合成了新的氢化铜簇[Cu9H7(meso-dpmppp)3]X2 (X = PF6 (1a), BF4 (1b), BPh4 (1c))，并对其具有4,4,4三向三角棱镜（TTP） Cu9核进行了表征。1a，b经LiBH4处理转化为[Cu9H8(meso-dpmppp)3]X (X = PF6 (2a), BF4 (2b))，在保留TTP Cu9核心的同时容纳了一个额外的氢化物。与2中的8个面盖氢化物的静态特性相反，1中的7个氢化物中有5个表现出流动行为，可以在- 80℃下冷冻成4个面盖氢化物和1个间隙氢化物。在Ph2SiH2和[Cu(MeCN)4]BF4的作用下，1b的Cu9核可以扩展，得到[Cu13H10(meso-dpmppp)3(MeCN)3](BF4)3(3)的中心二十面体（CIH） Cu13核。用meso-Ph2PCH2P(Ph)CH2N(CH2C6H5)CH2P(Ph)CH2PPh2 （meso-dpmppmNBn）合成了类似的CIH簇[Cu13H10(meso-dpmppmNBn)3(MeCN)3](BF4)3(4)。在DBU（1,8-重氮双环[5.4.0]-7-十一烯）存在的情况下，用H2 （1atm）处理1a，可以定量地得到2a， 2a很容易与1等量的TfOH或phh反应，转化回1a，同时形成H2，这表明通过TTP支架周围的面盖和间隙氢化物之间的通量交换，可能存在储氢的潜力。

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来源期刊

Inorganic Chemistry 化学-无机化学与核化学

CiteScore

7.60

自引率

13.00%

发文量

1960

审稿时长

1.9 months

期刊介绍： Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.