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

Tetramerization of BEB-Doped Phenalenyls to Obtain (BE)₈-[16]Annulenes (E = N, O)

Two (BE)8-[16]annulenes were prepared and fully characterized by experimental and quantum-chemical means (1, E = N; 2, E = O). The 1,8-naphthalenediyl-bridged diborane(6) 3 served as their common starting material, which was treated with [Al(NH3)6]Cl3 to form 1 (91% yield) or with 1,8-naphthalenediboronic acid anhydride to form 2 (93% yield). As a result, the heteroannulenes 1 and 2 are supported by four aromatic “clamps” and may also be viewed as NH- or O-bridged cyclic tetramers of BNB- or BOB-doped phenalenyls. X-ray crystallography on mono-, di-, and tetraadducts 2·thf, 2·py2, and 2·py4 showed that 2 is an oligotopic Lewis acid (thf/py: tetrahydrofuran/pyridine donor). The applicability of 2 also as a Lewis basic ligand in coordination chemistry was demonstrated by the synthesis of the mononuclear Ag+ complex [Ag(py)2(2·py4)]+ and the dinuclear Pb2+ complex 6. During the assembly of 6, the rearrangement of 2 led to the formation of two (BO)9-macrocycles linked by two BOB-phenalenyls to form a nanometer-sized cage with four negatively charged, tetracoordinated B atoms. Both 1 and 2 show several redox waves in the cathodic regions of the cyclic voltammograms. An in-depth assessment of the consequences of electron injection on the aromaticity of 1 and 2 was achieved by electronic structure calculations. 1 and 2 are proposed to exhibit aromatic switching capabilities in the [16]annulene motif.</p

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

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)

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

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

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

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

A Hydride‐Substituted Homoleptic Silylborate: How Similar is it to its Diborane(6)‐Dianion Isostere?

The B‐nucleophilic 9H‐9‐borafluorene dianion reacts with 9‐chloro‐9‐silafluorene to afford air‐ and moisture‐stable silylborate salts M[Ar2(H)B−Si(H)Ar2] (M[HBSiH], M=Li, Na). Li[HBSiH] and Me3SiCl give the B−pyridine adduct Ar2(py)B−Si(H)Ar2 ((py)BSiH) or the chlorosilane Li[Ar2(H)B−Si(Cl)Ar2] (Li[HBSiCl]) in C6H6‐pyridine or THF. In both cases, the first step is H− abstraction at the B center. The resulting free borane subsequently binds a py or thf ligand. While the py adduct is stable at room temperature, the thf adduct undergoes a 1,2‐H shift via the cyclic B(μ‐H)Si intermediate BHSi, which is afterwards attacked at the Si atom by a Cl− ion to give Li[HBSiCl]. DFT calculations were employed to support the proposed reaction mechanism and to characterize the electronic structure of BHSi. Treatment of Li[HBSiCl] with the N‐heterocyclic carbene IMe introduces the neutral donor at the Si atom and leads to Ar2(H)B−Si(IMe)Ar2 (HBSi(IMe)), a donor‐acceptor‐stabilized silylene

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)