Sr3[Co(CN)3] and Ba3[Co(CN)3]: Crystal Structure, Chemical Bonding, and Conceptional Considerations of Highly Reduced Metalates

Höhn, Peter; Jach, Franziska; Karabiyik, Baris; Prots, Yurii; Agrestini, S.; Wagner, Frank R.; Ruck, Michael; Tjeng, L. H.; Kniep, Rüdiger

doi:10.1002/anie.201103717

Cited by 19 publications

(51 citation statements)

References 17 publications

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“…Contrary to the well‐known bulk coordination chemistry of Cu, surface‐confinement shrinks the coordination number drastically, typically leading to two‐fold coordination motifs 17a,b. 18 However, cases of three‐fold coordination have been reported both in bulk19 and at surfaces 6b,c. 20 The individual metal atom centers in surface coordination networks are rarely resolved by STM 6a.…”

Section: Methodsmentioning

confidence: 98%

A Surface Coordination Network Based on Copper Adatom Trimers

et al. 2014

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Surface coordination networks formed by coadsorption of metal atoms and organic ligands have interesting properties, for example regarding catalysis and data storage. Surface coordination networks studied to date have typically been based on single metal atom centers. The formation of a novel surface coordination network is now demonstrated that is based on network nodes in the form of clusters consisting of three Cu adatoms. The network forms by deposition of tetrahydroxybenzene (THB) on Cu(111) under UHV conditions. As shown from a combination of scanning tunneling microscopy, X-ray photoelectron spectroscopy, and density functional theory calculations, all four hydroxy groups of THB dehydrogenate upon thermal activation at 440 K. This highly reactive ligand binds to Cu adatom trimers, which are resolved by high-resolution STM. The network creates an ordered array of mono-dispersed metal clusters constituting a two-dimensional analogue of metal-organic frameworks.Metal-organic frameworks (MOFs) have emerged as an important new class of designable nanoporous materials with many potential application areas, not least within gas storage and catalysis. [1] MOFs consist of metal cations interconnected by organic linkers in a crystalline three-dimensional matrix. Motivated by sensing and other interface-related applications, thin-film MOFs have been synthesized by growing or adsorbing MOFs on surfaces. [2] The extreme case of truly two-dimensional, molecular monolayer-thick analogues of MOFs is approached from the complementary direction of surface coordination networks. [3] These structures result from advances in surface supramolecular chemistry under ultrahigh vacuum (UHV) conditions and are synthesized by coadsorbing organic ligands with metal atoms on metal singlecrystal surfaces. Early work in this direction demonstrated formation of metal-organic clusters [4] and networks [5] from coordination between carboxylates and Cu or Fe adatoms. Subsequently, many well-ordered surface coordination networks have been synthesized, [6] notably demonstrating systematic control of network pore size and symmetry from appropriate choice of ligand (size and chemical functionality), metal center, and metal substrate. [7] Bulk MOFs are based on network nodes that in many cases go beyond simple cations, for example, small metal [8] or metal-oxide clusters, such as Zn 4 O clusters in the classic MOF-5. [9] In contrast, surface coordination networks have typically been based on single metal adatom nodes or coordination nodes with two (separated) adatoms. [6c, 10] Achieving more complex network nodes [11] in surface coordination networks is an interesting prospect, as the properties of the network nodes can be key to the functionality of the MOF/surface coordination network, for example, in terms of magnetic properties [10,12] or catalytic activity. [13] Herein we use a combination of scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations to demonstrate the synt...

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Section: Methodsmentioning

confidence: 98%

A Surface Coordination Network Based on Copper Adatom Trimers

et al. 2014

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“…[44] Very recently, [26,45] a completely documented case of reduced cyanide, viz., three CN 6-with trigonal-planar tricyanocobaltate and significantly lengthened C-N bonds of about 1.24 Å relative to the typical [27] 6-demonstrate that the cyanide ligand, while always acknowledged as a π acceptor, [27] can exhibit a hitherto undocumented non-innocent behavior, [26,45] supported by the 18 valence electron configuration for [Co(CN) 3 ] 6-, by the d 10 closed-shell stabilization for Co -I , and by charge compensation through the metal dications. Other super-reduced diatomics like paramagnetic N 2…”

Section: Non-innocent Diatomicsmentioning

confidence: 99%

The Shrinking World of Innocent Ligands: Conventionaland Non‐Conventional Redox‐Active Ligands

2012

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This essay for EurJIC's cluster issue on cooperative and redox non‐innocent ligands introduces the reader to redox‐active ligands, which range from the small archetypical NO+/•/– and O20/•–/2–systems via the classical 1,4‐dihetero‐1,3‐diene chelates (e.g. α‐diimine, dithiolene, or o‐quinone redox series) to π‐conjugated macrocycles. The increased attention paid recently to the redox activity of ligands in coordination chemistry has now prompted wider successful searches, resulting in the establishing of less‐conventional examples such as cyanide, carbon monoxide, thioethers, or acetylacetonate derivatives as non‐innocently behaving ligands. By considering situations with significantly covalent metal–ligand bonding, the cases of metal–oxo, metal–hydrido, and organometallic compounds will also be addressed, with a perspective on how pervasive non‐innocent ligand behavior is. The materials and reactivity potential of redox‐active ligands will be pointed out.

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“…Although not strictly an organometallic ligand, cyanide is often discussed in analogy to isoelectronic CO . However, the sometimes invoked π acceptor character of cyanide is little pronounced, as evident from the rarity of reduced cyanide in metal complexes; one first such recent example is M 3 [Co(CN) 3 ], M = Sr or Ba, with an experimentally and theoretically evidenced 18 VE and d 10 configuration of cobalt(–I) and three CN –1.67 ligands , …”

Section: Organoligand‐based Electron Transfermentioning

confidence: 99%

Sites of Electron Transfer Reactivity in Organometallic Compounds

Kaim

2020

Eur J Inorg Chem

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Three essentially different sites are identified for redox activity in organometallic compounds: The metal, the organometallic (C‐bonded) ligand(s), and potentially noninnocent co‐ligands. Typical reactivity patterns resulting from either of these alternatives will be pointed out by means of representative examples, possibly involving unusual metal oxidation states, carbon‐centered radicals, or ligand redox systems.

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Sr₃[Co(CN)₃] and Ba₃[Co(CN)₃]: Crystal Structure, Chemical Bonding, and Conceptional Considerations of Highly Reduced Metalates

Cited by 19 publications

References 17 publications

A Surface Coordination Network Based on Copper Adatom Trimers

A Surface Coordination Network Based on Copper Adatom Trimers

The Shrinking World of Innocent Ligands: Conventionaland Non‐Conventional Redox‐Active Ligands

Sites of Electron Transfer Reactivity in Organometallic Compounds

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