Copolymerization of Fe4Cu2C(CO)12 moieties with bidentate N-ligands: synthesis and crystal structure of the [Fe4Cu2(μ6-C)(CO)12(μ-bipy)]4·8THF square tetramer and the infinite [Fe4Cu2(μ6-C)(CO)12(μ-L–L)]∞ zigzag chains

Abstract

Substitution of the acetonitrile ligands in Fe(4)Cu(2)C(CO)(12)(MeCN)(2) with bidentate L-L ligands, such as 4,4'-bipyridine (bipy), pyrazine (pyz) or p-dicyanobenzene (p-DCB), gives rise to either infinite [Fe(4)Cu(2)(micro(6)-C)(CO)(12)(micro-L-L)](infinity) zigzag chain polymers or to [Fe(4)Cu(2)(micro(6)-C)(CO)(12)(micro-L-L)](4).8THF square oligomers, as a function of the crystallization solvent.

Chains and Nanochannels Self‐Assembled from Carbido Clusters, Silver Ions and Heterocyclic Ligands – Crystal Structures of the 1D Coordination Polymers [{AgOC4H8{Rh6C(CO)15}AgOC4H8}pyz]∞ and [bipy{Ag2Ru6C(CO)16}(bipy)2{Ag2Ru6C(CO)16}·2C4H8O]∞

“…Concentrated THF solutions of the clusters were then layered with toluene solutions of different bifunctional linear heterocyclic ligands (such as pyrazine and 4,4Ј-bipyridine), aiming to the self-assembly of infinite chains. The same reactions were performed with [Cu(NCMe) 4 ]BF 4 , with identical workup. The materials obtained, insoluble in most organic solvents, were all characterized by elemental analysis and ATR solid-state IR spectroscopy.…”

“…These units are sometimes mentioned as clusters, [2] even if no direct bonds exist between the metal atoms. To the contrary, the structures based on "true" metal clusters are less common, the most recent examples being the polymers of [TeFe 3 (CO) 9 Cu 2 ], [3] [Fe 4 Cu 2 C(CO) 12 ] [4] and [(C 5 Me 5 ) 2 Mo 2 S 4 Cu 2 ] [5] (formed with bridging bifunctional ligands). Other clusterderived polymers exploit inorganic ligands {as bridging halides in [Pt 9 (CO) 18 (CdCl 2 ) 2 ] 2- [6] or [Pd 3 (C 7 H 7 ) 2 Cl 2 ] [7] } metal-metal bonds {as in the superwire [{AgRu 6 C-(CO) 16 } -] ϱ [8] }, or hydrogen bonds {as found in the arrays of [Re 6 (µ 3 -Se) 8 ] 2+ clusters with nicotinamide [9] }.…”

Functionalization, Modification, and Transformation of Platinum Chini Clusters

“…The [Pt 9 (CO) 18 (µ 3 ‐CdCl 2 ) 2 ] 2– adduct self‐assembles upon crystallization into 1‐D {[Pt 9 (CO) 18 (µ 3 ‐CdCl 2 ) 2 ] 2– } ∞ superwires via formation of µ 3 ‐Cd 2 Cl 4 bridges (Figure ). Oligomerization and polymerization of metal carbonyl clusters via interaction with metal cations or Lewis acids is not uncommon and may be exploited for the self‐assembly of molecular nanomaterials , , , . Recently, the possibility to construct ternary E‐M‐Cu‐CO (M = Ru, Fe) complexes or polymers on reacting chalcogenide carbonyl clusters with CuX (X = Cl, Br, I) has been reviewed, showing potential applications in areas of semiconductors and catalysis.…”

Structural variations, electrochemical properties and computational studies on monomeric and dimeric Fe–Cu carbide clusters, forming copper-based staple arrays

“…Accordingly, the reaction of [Fe 4 C(CO) 12 (CuNCMe) 2 ] with pyrazine, in the absence of Ag + , yielded zigzag chains of [{Fe 4 C(CO) 12 Cu 2 }(pyz)] • . 8 In order to test a more general method for the preparation of [Fe 4 C(CO) 12 Cu-L]clusters and to prepare a monomeric compound, to be used as a reference for electrochemical studies, we reacted [Fe 4 C(CO) 12 ] 2-, [Cu(NCMe) 4 ] + and pyridine in THF at room temperature and obtained [Fe 4 C(CO) 12 Cu-py] -(5). The reaction is straightforward, fast and selective but its apparent simplicity is outweighed by the complexity of the synthesis of [Fe 4 C(CO) 12 ] 2-, which is prepared from [Fe 6 C(CO) 16 ] 2by a three step sequence of reactions, including oxidation, protonation and reduction.…”

“…Similarly, having synthesized two Fe-Cu heterometallic clusters, [Fe 5 C(CO) 14 (CuCl)] 2and [Fe 4 C(CO) 12 (CuCl) 2 ] 2-, 7 we exploited the reactivity of the latter for the formation of coordination polymers with bifunctional N-donors, such as pyrazine or 4,4¢-dipyridine. 8 In order to obtain different supramolecular assemblies, we employed other bifunctional ligands (not necessarily linear) and were able to construct some dimeric structures; however, besides the anticipated ligand substitution, we also observed structural rearrangements of the metal core, caused by loss/gain of copper ions. When copper atoms are incorporated in the cluster, they form Cu 3 (m-S 2 CNEt 2 ) 2 and Cu 3 (m-pz) 2 units, reminiscent of the staples found in gold nanoparticles.…”