Metal-Deficient Supramolecule based on fivefold-symmetric Building Blocks. Ein Supermolekül mit minimaler Metallbesetzung basierend auf einem fünffach-symmetrischen Baustein

An unprecedented cationic supramolecule [(Cp '' Fe(eta(5)-P-5))(12){CuNCMe}(8)](8+) 2.66 nm in diameter was selectively isolated as a salt of the weakly coordinating anion [Al{OC(CF3)(3)}(4)](-) for the first time and characterized by X-ray structure analysis, PXRD, NMR spectroscopy, and mass spectrometry. Its metal-deficient core contains the lowest possible number of Cu atoms to connect 12 pentaphosphaferrocene units, providing a supramolecule with fullerene topology which, topologically, also represents the simplest homologue in the family of metal-deficient pentaphosphaferrocene-based supramolecules [{Cp(R)Fe(eta(5)-P-5)}(12)(CuX)(20-n)]. The 12 vacant metal sites between the cyclo-P-5 rings, the largest number attained to date, make this compound a facile precursor for potential inner and outer modifications of the core as well as for functionalization via the substitution of labile acetonitrile ligands

catena-Poly[[bis­[1-(2-hydroxy­ethyl)-1H-tetra­zole-κN 4]copper(II)]-di-μ-chlorido]: a powder study

The crystal structure of the title polymeric complex, [CuCl2(C3H6N4O)2]n, was obtained by the Rietveld refinement from laboratory X-ray powder diffraction data collected at room temperature. The unique CuII ion lies on an inversion center and is in a slightly distorted octa­hedral coordination environment. In the hydroxy­ethyl group, all H atoms, the O atom and its attached C atom are disordered over two positions; the site occupancy factors are ca 0.6 and 0.4. The OH group is involved in an intra­molecular O—H⋯N hydrogen bond

Synthesis and Reactivity of a Cyclooctatetraene‐Like Polyphosphorus Ligand Complex [Cyclo‐P 8 ]

The thermolysis of Cp′′′Ta(CO)4 with white phosphorus (P4) gives access to [{Cp′′′Ta}2(μ,η2 : 2 : 2 : 2 : 1 : 1-P8)] (A), representing the first complex containing a cyclooctatetraene-like (COT) cyclo-P8 ligand. While ring sizes of n >6 have remained elusive for cyclo-Pn structural motifs, the choice of the transition metal, co-ligand and reaction conditions allowed the isolation of A. Reactivity investigations reveal its versatile coordination behaviour as well as its redox properties. Oxidation leads to dimerization to afford [{Cp′′′Ta}4(μ4,η2 : 2 : 2 : 2 : 2 : 2 : 2 : 2 : 1 : 1 : 1 : 1-P16)][TEF]2 (4, TEF=[Al(OC{CF3}3)4]−). Reduction, however, leads to the fission of one P−P bond in A followed by rapid dimerization to form [K@[2.2.2]cryptand]2[{Cp′′′Ta}4(μ4,η2 : 2 : 2 : 2 : 2 : 2 : 2 : 2 : 1 : 1 : 1 : 1-P16)] (5), which features an unprecedented chain-type P16 ligand. Lastly, A serves as a P2 synthon, via ring contraction to the triple-decker complex [{Cp′′′Ta}2(μ,η6 : 6-P6)] (B)

Synthese und Reaktivität eines Cyclooctatetraen‐artigen Polyphosphor‐Ligandkomplexes [Cyclo‐P₈]

Die Thermolyse von Cp′′′Ta(CO)4 mit weißem Phosphor (P4) eröffnet den Zugang zu [{Cp′′′Ta}2(μ,η2 : 2 : 2 : 2 : 1 : 1-P8)] (A), der erste Komplex, der einen cyclooctatetraen-artigen (COT) cyclo-P8-Liganden enthält. Während sich Ringgrößen von n >6 für cyclo-Pn-Strukturmotive bisher nicht realisieren ließen, konnte A abhängig von der Wahl des Übergangsmetalls, des Coliganden und der Reaktionsbedingungen isoliert werden. Untersuchungen zur Reaktivität zeigen sein vielseitiges Koordinationsverhalten und seine Redoxeigenschaften. Während die Oxidation zur Dimerisierung führt und [{Cp′′′Ta}4(μ4,η2 : 2 : 2 : 2 : 2 : 2 : 2 : 2 : 1 : 1 : 1 : 1-P16)][TEF]2 (4, TEF=[Al(OC{CF3}3)4]−) ergibt, führt die Reduktion dagegen zur Spaltung einer P−P-Bindung in A mit anschließender schneller Dimerisierung und Bildung von [K@[2.2.2]Kryptand]2[{Cp′′′Ta}4(μ4,η2 : 2 : 2 : 2 : 2 : 2 : 2 : 2 : 1 : 1 : 1 : 1-P16)] (5), welches einen beispiellosen kettenartigen P16-Liganden aufweist. Letztlich dient A als ein P2-Synthon, welches über eine Ringkontraktion zum Triple-Decker-Komplex [{Cp′′′Ta}2(μ,η6 : 6-P6)] (B) reagiert

Across the Dimensions: A Three‐Component Self‐Assembly of Pentaphosphaferrocene‐based Coordination Polymers

Pentaphosphaferrocenes [CpRFe(η5-P5)] (Cp*=η5-C5Me5) (A), Cp’’=η5-C5H3tBu2-1,3 (B)) are excellent building blocks for polymeric assemblies in supramolecular chemistry in combination with coinage metal salts of weakly coordinating anions such as AgSbF6. Adding rigid aromatic dinitriles ortho/meta/para-(NC)2C6H4 in a one-pot reaction between [CpRFe(η5-P5)] and AgSbF6 leads to various coordination polymers (CPs) by a three-component self-assembly. The sterical demand of the differently substituted cyclopentadiene ligands as well as the rigid constitution of the isomeric dinitriles (NC)2C6H4 play a key role in the formation of the isolated CPs. All CPs were characterized by NMR spectroscopy, mass spectrometry, elemental analysis, and single-crystal X-ray diffraction

Synthesis, molecular and electronic structure of an incomplete cuboidal Re3S4 cluster with an anusual quadruplet ground state

A Re(IV) cluster complex [Re3(μ3-S)(μ-S)3(dppe)3Br3]+ with nine cluster skeletal electrons (CSE) and a quadruplet ground state has been prepared by treatment of [Re3S7Br6]Br with 1,2-bis(diphenylphosphino)ethane (dppe) in MeCN

Organometallic-Organic Hybrid Polymers Assembled from Pentaphosphaferrocene, Bipyridyl Linkers, and Cul Ions

A multicomponent approach of the P-n ligand complex [Cp*Fe((5)-P-5)] (1: Cp* = (5)-C5Me5) with the ditopic organic linkers 4,4-bipyridine (2) or trans-1,2-di(pyridine-4-yl)ethene (3) in the presence of Cu-I salts of the anions [BF4](-) and [PF6](-) or the coordinating anion Br-, leads to the formation of four novel organometallic-organic hybrid polymers: the cationic 1D polymeric compounds [Cu-4{Cp*Fe(mu(3),(5:1:1)-P-5)}(2)(mu,(1:1)-C10H8N2)(4)(CH3CN)(4)](n)[BF4](4n) (4) and [Cu-4{Cp*Fe(mu(3),(5:1:1)-P-5)}(2)(mu,(1:1)-C10H8N2)(4)(CH3CN)(4)](n)[PF6](4n) (5) as well as the unique neutral threefold 2D 2D interpenetrated networks [Cu2Cl2{Cp*Fe(mu(3),(5:1:1)-P-5)}(mu,(1:1)-C12H10N2)](n) (6) and [Cu2Br2{Cp*Fe(mu(3),(5:1:1)-P-5)}(mu,(1:1)-C10H8N2)](n) (7)

The Missing Parent Compound [(C 5 H 5 )Fe(η 5 ‐P 5 )]: Synthesis, Characterization, Coordination Behavior and Encapsulation

The so far missing parent compound of the large family of pentaphosphaferrocenes [CpFe(η5-P5)] (1 b) was synthesized by the thermolysis of [CpFe(CO)2]2 with P4 using the very high-boiling solvent diisopropylbenzene. It was comprehensively characterized by, inter alia, NMR spectroscopy, single crystal X-ray structure analysis, cyclic voltammetry and DFT computations. Moreover, its coordination behavior towards CuI halides was explored, revealing the unprecedented 2D polymeric networks [{CpFe(η5:1:1:1:1-P5)}Cu2(μ-X)2]n (2 a: X=Cl, 2 b: X=Br) and [{CpFe(η5:1:1-P5)}Cu(μ-I)]n (3) and even the first cyclo-P5-containing 3D coordination polymer [{CpFe(η5:1:1-P5)}Cu(μ-I)]n (4). The sandwich complex 1 b can also be incorporated in nano-sized supramolecules based on [Cp*Fe(η5-P5)] (1 a) and CuX (X=Cl, Br, I): [CpFe(η5-P5)]@[{Cp*Fe(η5-P5)}12(CuX)20-n] (5 a: X=Cl, n=2.4; 5 b: X=Br, n=2.4; 5 c: X=I, n=0.95). Thereby, the formation of the CuI-containing fullerene-like sphere 5 c is found for the first time

Tuning the dimensionality of organometallic-organic hybrid polymers assembled from [Cp₂Mo₂(CO)₄(η²-P₂)], rigid bipyridyl linkers and Ag ions

The reactions of the P₂ ligand complex [Cp₂Mo₂(CO)₄(η²-P₂)] (Cp = C₅H₅, 1) with Ag[Al{OC(CF₃)₃}₄] (Ag[TEF]) in the presence of the rigid bipyridyl linkers 1,2-di(pyridin-4-yl)ethyne (3), 4,4′-bis(pyridin-4-ylethynyl)-1,1′-biphenyl (4) and 4,4′-bipyridine (5) possessing various lengths are studied. The reaction with the longer linkers (3 and 4) leads to the formation of the 1D organometallic–organic hybrid polymers [{Cp₂Mo₂(CO)₄(μ₄,η¹˸¹˸²˸²-P₂)}₂{Cp₂Mo₂(CO)₄(μ₃,η¹˸²˸²-P₂)}₂(μ,η¹˸¹-C₁₂H₈N₂)Ag₂]n[TEF]₂n (6) and [{Cp₂Mo₂(CO)₄(μ₄,η¹˸¹˸²˸²-P₂)}₂{Cp₂Mo₂(CO)₄(μ₃,η¹˸²˸²-P₂)}₂(μ,η¹˸¹-C₂₆H₁₆N₂)Ag₂]n[TEF]₂n (7) in high selectivity. A similar reaction with the short linker 5 affords a mixture of the 2D hybrid polymers [{Cp₂Mo₂(CO)₄(μ₄,η¹˸²˸²˸²-P₂)}₂(μ,η¹˸¹-C₁₃H₁₄N₂)Ag₂]n[TEF]₂n (8) and the 3D hybrid network [{Cp₂Mo₂(CO)₄(μ₄,η¹˸¹˸²:²-P₂)}₂(μ,η¹˸¹-C10H8N₂)Ag]n[TEF]₂n (9). However, a selective synthesis of 8 or 9 is possible when the reaction is performed at 0 °C and 60 °C, respectively

Iodination of cyclo-E5-Complexes (E = P, As). Die Iodierung von cyclo‐E5‐Komplexen (E=P, As)

In a high-yield one-pot synthesis, the reactions of [Cp*M(eta(5)-P-5)] (M=Fe (1), Ru (2)) with I(2)resulted in the selective formation of [Cp*MP6I6](+)salts (3,4). The products comprise unprecedented all-cistripodal triphosphino-cyclotriphosphine ligands. The iodination of [Cp*Fe(eta(5)-As-5)] (6) gave, in addition to [Fe(CH3CN)(6)](2+)salts of the rare [As6I8](2-)(in7) and [As4I14](2-)(in8) anions, the first di-cationic Fe-As triple decker complex [(Cp*Fe)(2)(mu,eta(5:5)-As-5)][As6I8] (9). In contrast, the iodination of [Cp*Ru(eta(5)-As-5)] (10) did not result in the full cleavage of the M-As bonds. Instead, a number of dinuclear complexes were obtained: [(Cp*Ru)(2)(mu,eta(5:5)-As-5)][As6I8](0.5)(11) represents the first Ru-As(5)triple decker complex, thus completing the series of monocationic complexes [(Cp(R)M)(2)(mu,eta(5:5)-E-5)](+)(M=Fe, Ru; E=P, As). [(Cp*Ru)(2)As8I6] (12) crystallizes as a racemic mixture of both enantiomers, while [(Cp*Ru)(2)As4I4] (13) crystallizes as a symmetric and an asymmetric isomer and features a unique tetramer of {AsI} arsinidene units as a middle deck