Fine tunable metal assemblies constrained by multidentate phosphine ligands

Tanase, Tomoaki; Nakamae, Kanako; Ura, Yasuyuki; Nakajima, Takayuki

doi:10.1016/j.ccr.2022.214581

Cited by 14 publications

(9 citation statements)

References 266 publications

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“…Nevertheless, it should be stated that relatively large number of heterometallic di-and trinuclear complexes have been already reported. 1,8,17 Peng and co-workers have recently developed pentanuclear mixed-metal chains by using a tripyridyldiamide ligand (H 2 tpda); heating H 2 tpda in naphthalene with Ru 2 (OAc) 4 Cl and Ni(OAc) 2 •4H 2 O in a 4 : 2 : 1 ratio in the presence of NaNCS afforded the NiRu 2 Ni 2 string, [NiRu 2 Ni 2 (tpda) 4 (NCS) 2 ] (50), which was purified by silica-gel column chromatography in 35% yield (Scheme 6 and Fig. 7a).…”

Section: Heterometallic Molecular Metal Chainsmentioning

confidence: 99%

“…Nevertheless, it should be stated that relatively large number of heterometallic di- and trinuclear complexes have been already reported. 1,8,17…”

Section: Heterometallic Molecular Metal Chainsmentioning

confidence: 99%

“…These phosphines contain PCP and PNP units and well organize a variety of metal units, including the rigid-rod Pt 6 , Pt 2 Pd 2 Pt 2 , and Pd 8 metal chains, flexible M 4 metal chains and {Au 2 MCu} 2 rings (M = Au, Ag, Cu), and cage-type Cu 9 H 7 and Cu 16 H 14 copper hydride clusters and small-size Cu 2 H, Cu 3 H, Cu 4 H 2 , Cu 4 H 3 , and Cu 8 H 6 complexes. [15][16][17] Especially, meso-and racdpmppm have proven very effective to support Pd 8 chains of [Pd 8 (meso-or rac-dpmppm) 4 ] 4+ , [18][19][20][21] that showed interesting self-assembling dynamic behaviours in the solution states, leading to 1D coordination polymers, 20 metal-chain-wired Bucky balls, 22 and electrochemical H 2 formation. 23 While selfassembly of organic and inorganic components has widely been well accepted as a powerful and promising synthetic strategy to create nano-scaled molecular architectures and devices, [24][25][26][27] synthetic attempts with the concept on the molecular metal chains have hardly been performed despite that it may be desired to bring about a significant breakthrough to expand the length of metal chains to nano-scale.…”

Section: Introductionmentioning

confidence: 99%

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Aiming for dynamic behaviours of molecular metal chains

et al. 2023

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Section: Heterometallic Molecular Metal Chainsmentioning

confidence: 99%

“…Nevertheless, it should be stated that relatively large number of heterometallic di- and trinuclear complexes have been already reported. 1,8,17…”

Section: Heterometallic Molecular Metal Chainsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Aiming for dynamic behaviours of molecular metal chains

et al. 2023

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“…Recent studies have revealed that array-based clusters with chainlike units are promising candidates to expose more active sites. − The rationale behind this proposal relies on the fact that more metal atoms of array-based clusters are located on the surface; namely, much fewer active sites are encapsulated in the core (Figure b). Herein, we report the facial synthesis, structure, and catalytic performance of a new array-based [Cu 8 (Tf-dpf) 4 (NO 3 ) 2 ](NO 3 ) 2 nanocluster (abbreviated as the Cu 8 array hereafter).…”

Section: Introductionmentioning

confidence: 99%

Array-Based Clusters of Copper with Largely Exposed Metal Sites for Promoting Catalysis

Xu,

Liu,

Sun

et al. 2023

Chem. Mater.

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Most ligand-stabilized metal nanoclusters feature a core–shell or polyhedron-derived metal framework, in which the metal active sites would be blocked by either metal–ligand interfacial shells or surface passive units. We report, in this work, a strategy of largely exposing metal sites and thus promoting catalysis via constructing metal nanoclusters with array-based geometry. Exampled here are a pair of Cu8 clusters with polyhedron-derived ([Cu8(RS)6(PPh3)4(MeCN)4H]+, where RS is 3,5-bis(trifluoromethyl)benzenethiol) and array-based ([Cu8(Tf-dpf)4(NO3)2](NO3)2, Tf-dpf is N,N′-di(5-trifluoromethyl-2-pyridyl) formamidinate) structure, respectively. In sharp contrast to the cubic Cu8 cluster whose metal core has been totally covered by ligands, the array-based analogue displays largely uncoordinated metal sites. As a result, the array-based Cu8 cluster exhibits significantly enhanced activity in catalytic hydrogenation reactions in comparison to the cubic one. In addition, the array-based Cu8 cluster shows excellent catalytic performance in the “aldehyde–acetylene–amine” A3-coupling reaction for the synthesis of propargylamines. The reaction can be converted almost perfectly with a rather low amount of cluster, which further reflects its potential catalytic application.

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“…The protecting ligands are crucial to the clusters and influence their stabilities, crystallographic stacking, electronic structures, and properties. Longer multidentate ligands were effective in the extension of aligned metal strings. − Koshevoy and co-workers demonstrated that by extension of the spacer of the diphosphine ligands the size of a gold–silver cluster was increased . Whether elongation of the ligand will directly lead to linear extension of a cluster remains to be further explored.…”

Section: Introductionmentioning

confidence: 99%

Elongation of a Trigonal-Prismatic Copper Cluster by Diphosphine Ligands with Longer Spacers

et al. 2022

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A pair of alkynyl–diphosphine-coprotected copper(I) clusters, namely, [Cu6(4-MeO-PhCC)5(dppe)3](ClO4) [Cu 6 ; dppe = 1,2-bis(diphenylphosphino)ethane] and [Cu11(H)(4-MeO-PhCC)8(dpppe)3](ClO4)2 [Cu 11 ; dpppe = 1,5-bis(diphenylphosphino)pentane], featuring trigonal-prismatic frameworks have been synthesized by a reduction method. Their molecular structures are determined by X-ray crystallography and characterized by multiple techniques. The length of the spacer of the diphosphine ligand can directly affect the aspect ratio of the clusters. Cu 6 with dppe as ligands has a trigonal-prismatic core. The longer alkyl spacer of dpppe helps to elongate the trigonal-prismatic framework to form Cu 11 , with its trigonal-prismatic framework encapsulating a Cu5H unit. Electrospray ionization mass spectrometry, 2H NMR, and liberations of hydrogen further verify the presence of a hydride in the cluster. Density functional theory calculations help to locate the position of the hydride and understand the electronic structures of the clusters. Cu 11 is the first alkynyl–phosphine-coprotected copper hydride cluster. These two clusters show distinct luminescence properties. The compact Cu 6 is phosphorescent upon radiation, while the longer Cu 11 with more flexibility is nonluminous. This work enriches the family of copper hydrides and demonstrates the ligand effects in the extension of the length and structural complexity of clusters.

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Fine tunable metal assemblies constrained by multidentate phosphine ligands

Cited by 14 publications

References 266 publications

Aiming for dynamic behaviours of molecular metal chains

Aiming for dynamic behaviours of molecular metal chains

Array-Based Clusters of Copper with Largely Exposed Metal Sites for Promoting Catalysis

Elongation of a Trigonal-Prismatic Copper Cluster by Diphosphine Ligands with Longer Spacers

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