Synthesis and Characterization of a Copper Dinitrogen Complex Supported by a Weakly Coordinating Anion.

We report the synthesis and full characterization of the copper dinitrogen complex [(η-N)Cu{Al(OR)}] 2 (R=C(CF)) prepared by a cascade metathesis reaction of Ag[Al(OR)] with CuI-excess in iso-perfluorohexane (i-pfh) under N atmosphere. Title compound 2 features an extraordinarily high N stretching frequency at 2313/2314 cm (IR/Raman) and was characterized by single-crystal and powder X-ray diffractometry. Quantum chemical charge displacement analysis based on natural orbitals of chemical valence (CD-NOCV) indicates that the copper-dinitrogen interaction is still governed by weak π-backdonation, but is significantly reduced compared to all literature-known transition metal dinitrogen complexes.

Towards hydrogen-rich ionic (NH)(BHNHBHNHBH) and related molecular NHBHNHBHNHBH.

Attempts of the synthesis of ionic (NH)(BHNHBHNHBH) a metathetical approach resulted in a mixture of the target compound and partly dehydrogenated molecular NHBHNHBHNHBH product. The mixed specimen was characterised by NMR and vibrational spectroscopies, and the cocrystal structure was analyzed from powder X-ray diffraction data supported by theoretical density functional theory calculations. The compound crystallises in a 2/ unit cell with the lattice parameters of = 13.

Stabilization of Potent Co(II)-based Lewis Acids with Weakly Basic Ligands.

Pairing cations with weakly coordinating anions (WCAs) often renders them highly Lewis-acidic and extremely reactive. Although these features are often desirable, excessive reactivity of a cation may lead to decomposition of solvents or WCAs, hindering isolation, storage and practical use of such species. In an attempt to mitigate the problem, we introduce a series of readily available novel Co(II)-WCA salts with the metal center stabilized by weakly bound ligands: SO , halogenated acetonitriles and nitromethane with comprehensive characterization including structural, magnetic and spectral (IR) properties as well as thermal stability assessment.

Extending the chemistry of weakly basic ligands: solvates of Ag and Cu stabilized by [Al{OC(CF)}] anion as model examples in the screening of useful weakly interacting solvents.

Weakly Coordinating Anions (WCAs) facilitate the formation of exotic "naked" cationic species. However, the feasibility of the respective synthesis approaches may be limited by the basicity of the solvent utilized, as the latter is one of the most important factors determining the solvation ability. In this work, we focus on a series of novel complexes of Ag(i) and Cu(i) with weakly basic ligands such as CHCl, ClCCN and SO stabilized by perfluorinated alkoxyaluminate, Al[(OR)], R = C(CF).

Building blocks for the chemistry of perfluorinated alkoxyaluminates [Al{OC(CF)}]: simplified preparation and characterization of Li-Cs, Ag, NH, NH and NH salts.

Advanced weakly coordinating anions (WCAs) significantly facilitate synthesis of various exotic chemical compounds and novel, potentially useful materials. One of such anions - [Al{OC(CF)}], denoted [Al(OR)], appears particularly convenient, as it can be easily prepared from the commercially available alanates and HOC(CF). Here we present a thorough characterization of a series of solvent-free M[Al(OR)] salts, M = Li-Cs, Ag, NH, NH and NH, and related compounds of monovalent cations, which are crucial starting materials for further work with these species.

Completing the triad: synthesis and full characterization of homoleptic and heteroleptic carbonyl and nitrosyl complexes of the group VI metals.

Oxidation of M(CO) (M = Cr, Mo, W) with the synergistic oxidative system Ag[WCA]/0.5 I yields the fully characterized metalloradical salts [M(CO)]˙[WCA] (weakly coordinating anion WCA = [F-{Al(OR)}], R = C(CF)). The new metalloradical cations with M = Mo and W showcase a similar structural fluxionality as the previously reported [Cr(CO)]˙.

A Stable Crystalline Copper(I)-N O Complex Stabilized as the Salt of a Weakly Coordinating Anion.

Nitrous oxide is considered a poor ligand, and therefore only a handful of well-defined metal-N O complexes are known. Oxidation of copper powder with an extreme oxidant, [Ag I ][An] ([An] =[Al(OC(CF ) ) ] ) in perfluorinated hexane leads to Cu [An], the first auxiliary ligand-free Cu salt of the perfluorinated alkoxyaluminate anion. The compound is capable of forming a stable and crystalline complex with nitrous oxide, Cu(N O)[An], where the Cu-N O bond is by far the strongest among all other molecular metal-N O complexes known.

Homoleptic Gold Acetonitrile Complexes with Medium to Very Weakly Coordinating Counterions: Effect on Aurophilicity?

A series of gold acetonitrile complexes [Au(NCMe) ] [WCA] with weakly coordinating counterions (WCAs) was synthesized by the reaction of elemental gold and nitrosyl salts [NO] [WCA] in acetonitrile ([WCA] =[GaCl ] , [B(CF ) ] , [Al(OR ) ] ; R =C(CF ) ). In the crystal structures, the [Au(NCMe) ] units appeared as monomers, dimers, or chains. A clear correlation between the aurophilicity and the coordinating ability of counterions was observed, with more strongly coordinating WCAs leading to stronger aurophilic contacts (distances, C-N stretching frequencies of [Au(NCMe) ] units).

Coordination Chemistry of Diiodine and Implications for the Oxidation Capacity of the Synergistic Ag(+) /X2 (X=Cl, Br, I) System.

The synergistic Ag(+) /X2 system (X=Cl, Br, I) is a very strong, but ill-defined oxidant-more powerful than X2 or Ag(+) alone. Intermediates for its action may include [Agm (X2 )n ](m+) complexes. Here, we report on an unexpectedly variable coordination chemistry of diiodine towards this direction: (A)Ag-I2 -Ag(A), [Ag2 (I2 )4 ](2+) (A(-) )2 and [Ag2 (I2 )6 ](2+) (A(-) )2 ⋅(I2 )x≈0.

Silver Complexes of Dihalogen Molecules.

The perfluorohexane-soluble and donor-free silver compound Ag(A) (A=Al(OR(F) )4 ; R(F) =C(CF3 )3 ) prepared using a facile novel route has unprecedented capabilities to form unusual and weakly bound complexes. Here, we report on the three dihalogen-silver complexes Ag(Cl2 )A, Ag(Br2 )A, and Ag(I2 )A derived from the soluble silver compound Ag(A) (characterized by single-crystal/powder XRD, Raman spectra, and quantum-mechanical calculations).

AgPO2F2 and Ag9(PO2F2)14: the first Ag(i) and Ag(i)/Ag(ii) difluorophosphates with complex crystal structures.

The reaction of AgF2 with P2O3F4 yields a mixed valence Ag(I)/Ag(II) difluorophosphate salt with AgAg(PO2F2)14 stoichiometry - the first Ag(ii)-PO2F2 system known. This highly moisture sensitive brown solid is thermally stable up to 120 °C, which points at further feasible extension of the chemistry of Ag(ii)-PO2F2 systems. The crystal structure shows a very complex bonding pattern, comprising of polymeric Ag(PO2F2)14(4-) anions and two types of Ag(I) cations.

Ag[Fe(CO)5]2(+) : a bare silver complex with Fe(CO)5 as a ligand.

Attempts to prepare Fe(CO)5 (+) from Ag[Al(OR(F) )4 ] (R(F) =C(CF3 )3 ) and Fe(CO)5 in CH2 Cl2 yielded the first complex of a neutral metal carbonyl bound to a simple metal cation. The Ag[Fe(CO)5 ]2 (+) cation consists of two Fe(CO)5 molecules coordinating Ag(+) in an almost linear fashion. The ν(CO) modes are blue-shifted compared to Fe(CO)5 , with one band above 2143 cm(-1) indicating that back-bonding is heavily decreased in the Ag[Fe(CO)5 ]2 (+) cation.

AgS2O6CF3: the first trifluoromethylsulfonylsulfate(VI).

We describe the synthetic route towards a novel class of salts, trifluoromethylsulfonylsulfates, as exemplified by the silver(I) derivative (AgS2O6CF3). Formation proceeds via direct reaction between a triflate precursor, AgSO3CF3, and SO3. The title compound crystallizes in the P2(1)/c unit cell with a = 5.

Crystal and electronic structure, lattice dynamics and thermal properties of Ag(I)(SO3)R (R = F, CF3) Lewis acids in the solid state.

Trifluoromethansulfonate of silver(I), AgSO(3)CF(3) (abbreviated AgOTf), extensively used in organic chemistry, and its fluorosulfate homologue, AgSO(3)F, have been structurally characterized for the first time. The crystal structures of both homologues differ substantially from each other. AgOTf crystallizes in a hexagonal system (R3 space group, No.