(η5-Carb-oxy-cyclo-penta-dien-yl)(η7-cyclo-hepta-trien-yl)manganese(I) hexa-fluorido-phosphate.

The title compound, [Mn(C7H7)(C6H5O2)]PF6 or [(Cht)Mn(Cp'CO2H)]PF6, with Cht = cyclo-hepta-trienyl and Cp' = C5H4, is an air-stable, purple, heteroleptic, cationic sandwich complex with manganese in oxidation state +I and π-coordinating cyclo-hepta-trienyl and cyclo-penta-dienyl ligands. The latter ligand carries the carb-oxy-lic acid functionality. This 'tromancenium-8-carb-oxy-lic acid' with hexa-fluorido-phosphate as counter-ion represents a rare case of a cationic carb-oxy-lic acid. Structurally, this organometallic carb-oxy-lic acid displays the common motif of planar Osp 2⋯H-Osp 3/Osp 3-H⋯Osp 2 hydrogen-bonded carb-oxy-lic acid dimers with anti-oriented metallocenyl moieties, the cationic charge of which is balanced by octa-hedrally shaped hexa-fluorido-phosphate anions. Positional disorder is observed in the cyclo-hepta-trienyl ring and the PF6 - anion.

Curious Case of Cobaltocenium Carbaldehyde.

Cobaltocenium carbaldehyde (formylcobaltocenium) hexafluoridophosphate, a long sought-after functionalized cobaltocenium salt, is accessible from cobaltocenium carboxylic acid by a three-step synthetic sequence involving (i) chlorination to the acid chloride, (ii) copper-borohydride reduction to the hydroxymethyl derivative, and (iii) Dess-Martin oxidation to the title compound. Due to the strongly electron-withdrawing cationic cobaltocenium moiety, no standard aldehyde reactivity is observed. Instead, nucleophilic addition followed by haloform-type cleavage prevails, thereby ruling out common useful aldehyde derivatization. One-electron reduction of cobaltocenium carbaldehyde hexafluoridophosphate affords the deep-blue, isolable cobaltocene carbaldehyde 19-valence-electron radical whose spin density is located fully at cobalt and not at the formyl carbon atom. 1H/13C NMR, IR, EPR spectroscopy, high-resolution mass spectrometry, cyclic voltammetry, single crystal structure analysis (XRD), and density functional theory are applied to characterize these unusual formyl-cobaltocenium/cobaltocene compounds.

Clathrochelate Complexes Containing Axial Cymantrene and Tromancenium Moieties.

New clathrochelate complexes of manganese, iron and cobalt containing peripheral organometallic manganese moieties cymantrene or tromancenium were synthesized via self-assembly from di/tri-topic dioximes, metal templates and cymantrene/tromancenium boronic acid pinacol esters. These air-stable, highly colored, oligometallic complexes are composed of various combinations of MnIFeIIMnI, MnICoIIMnI, MnIMnIIMnIIMnI and MnICoIICoIIMnI metal assemblies with corresponding complicated magnetic and electrochemical properties. Full spectroscopic and structural characterization by 1H/11B/13C NMR, HRMS, IR, UV-vis, single crystal XRD and CV (cyclic voltammetry) is provided. Tetrametallic complexes containing tromanceniumyl substituents with two CoII or MnII central metals exhibit promising anticancer properties against different tumor cell lines.

Borylated Cymantrenes and Tromancenium Salts with Unusual Reactivity.

In continuation of our study of the chemistry of cationic (cycloheptatrienyl)(cyclopentadienyl)manganese(I) sandwich complexes, so-called "tromancenium" salts, we report here on their boron-substituted derivatives focusing on useful boron-mediated synthetic applications. Transmetalation of lithiated tricarbonyl(cyclopentadienyl)manganese ("cymantrene") with boric or diboronic esters affords monoborylated cymantrenes that are converted by advanced high-power LED photosynthesis followed by oxidation with tritylium to their 8-boron-substituted tromancenium complexes. These new functionalized tromancenium salts are fully characterized by 1H/11B/13C/19F/55Mn NMR, IR, UV-vis, HRMS spectroscopy, single-crystal structure analysis (XRD) and cyclic voltammetry (CV). IR spectra were thoroughly analyzed by density functional theory (DFT) on the harmonic approximation in qualitative agreement of calculated vibrations with experimental values. Uncommon chemical reactivity of these borylated tromancenium salts is observed, due to the strongly electron-withdrawing cationic tromancenium moiety. No Suzuki-type cross-coupling reactions proved so far achievable, but unusual copper-promoted amination with sodium azide under microwave irradiation is possible. Diazoniation of aminotromancenium affords an extremely reactive dicationic tromanceniumdiazonium salt, which is too labile for standard Sandmeyer reactions, in contrast to analogous chemistry of cobaltocenium salts. Overall, borylated tromancenium salts display unexpected and intriguing chemical properties with the potential for novel synthetic applications in future work.

Rhodocenium Functionalization Enabled by Half-Sandwich Capping, Zincke Reaction, Diazoniation and Sandmeyer Chemistry.

In continuation of our exploration of metallocenium chemistry we report here on innovative ways toward monofunctionalized rhodocenium salts applying half-sandwich capping reactions of cyclopentadienyl rhodium(III) halide synthons with cyclopentadienyl ylides containing pyridine, phosphine or dinitrogen leaving groups, followed by Zincke and Sandmeyer reactions. Thereby amino, diazonio, bromo, azido and iodo rhodocenium salts containing valuable functional groups are accessible for the first time. Target compounds were characterized by spectroscopic (1H/13C/103Rh-NMR, IR, HR-MS), structural (single crystal XRD) and electrochemical (CV) methods and their properties were compared to those of isoelectronic cobaltocenium compounds. These new functionalized rhodocenium complexes significantly expand the so far extremely limited chemical space of rhodocenium salts with promising options for the future development in the area of rhodocenium chemistry.

Cobaltoceniumselenolate Gold(I) Complexes: Synthesis, Spectroscopic, Structural and Anticancer Properties.

Cobaltoceniumselenolate is an unusual, highly air-sensitive, mesoionic compound containing a very soft anionic selenium donor atom. Here we explore its coordination chemistry with Au(I) metal centers and show that its hetero- and homoleptic gold complexes are highly colored, air-stable compounds, which were characterized by 1H/13C/31P/77Se NMR, IR, UV-Vis, HR-MS and single crystal XRD. Cytotoxicity of these polar, water-soluble complexes was studied against various standard cancer cell lines (A549MDA-MB-231, HT-29) revealing good anticancer activity of all three complexes.

Cationic Cycloheptatrienyl Cyclopentadienyl Manganese Sandwich Complexes: Tromancenium Explored with High-Power LED Photosynthesis.

In this contribution, we revisit the neglected and forgotten cationic, air-stable, 18-valence electron, heteroleptic sandwich complex (cycloheptatrienyl)(cyclopentadienyl)manganese, which was reported independently by Fischer and by Pauson about 50 years ago. Using advanced high-power LED photochemical synthesis, an expedient rapid access to the parent complex and to functionalized derivatives with alkyl, carboxymethyl, bromo, and amino substituents was developed. A thorough study of these "tromancenium" salts by a range of spectroscopic techniques (1H/13C/55Mn-NMR, IR, UV-vis, HRMS, XRD, XPS, EPR), cyclic voltammetry (CV), and quantum chemical calculations (DFT) shows that these manganese sandwich complexes are unique metallocenes with quite different chemical and physical properties in comparison to those of isoelectronic cobaltocenium salts or (cycloheptatrienyl)(cyclopentadienyl) sandwich complexes of the early transition metals. Electrochemically, all tromancenium ions undergo a chemically partially reversible oxidation and a chemically irreversible reduction at half-wave or peak potentials that respond to the substituents at the Cp deck. As exemplarily shown for the parent tromancenium ion, the product generated during the irreversible reduction process reverts at least partially to the starting material upon reoxidation. Quantum-chemical calculations of the parent tromancenium salt indicate that metal-ligand bonding is distinctly weaker for the cycloheptatrienyl ligand in comparison to that of the cyclopentadienyl ligand. Both the HOMO and the LUMO are metal and cycloheptatrienyl-ligand centered, indicating that chemical reactions will occur either metal-based or at the seven-membered ring, but not on the cyclopentadienyl ligand.

(Cobaltoceniumyl-amido)-pyridinium hexa-fluorido-phosphate.

The title compound, [Co(C5H5)(C10H9N2)]PF6, was synthesized from deproton-ated 1-amino-pyridinium iodide, followed by microwave-assisted nucleophilic aromatic substitution of iodo-cobaltocenium iodide. After anion exchange with potassium hexa-fluorido-phosphate, the title compound crystallizes as orange prisms in the space group Pc. This very stable pyridine nitrene adduct is the first example of a cobaltocenium derivative, formally containing a nitrene nitro-gen species.

Bis(µ-cobaltoceniumseleno-late-1:2κ2 Se:Se)bis[bis-(cobaltoceniumseleno-late-κSe)mercury(II)] tetra-kis-(hexa-fluorido-phosphate) aceto-nitrile disolvate.

The title compound, [Co6Hg2(C5H5)6(C5H4Se)6](PF6)4·2CH3CN or [Hg2(CcSe)6][PF6]4·2CH3CN (Cc = C10H9Co), was obtained as bright-orange needle-shaped crystals. It is a salt containing a tetra-cationic dimercury species with six cobaltoceniumseleno-late ligands, four hexa-fluorido-phosphate counter-ions and two aceto-nitrile solvent mol-ecules. The cation (point group ) has a bi-tetra-hedral {Hg2Se6} core with two bridging Se atoms and four terminal Se atoms.

Oxidative access via aqua regia to an electrophilic, mesoionic dicobaltoceniumyltriazolylidene gold(III) catalyst.

A gold(III) complex with the hitherto most electron poor mesoionic carbene ligand is presented. Aqua regia was the oxidizing agent of choice for the synthesis of this unusual organometallic compound. The AuIII complex is redox-rich, and also acts as a catalyst for oxazole formation, delivering selectively a completely different isomer compared to its AuI congener.

Direct Amination of Cobaltocenium Hexafluoridophosphate via Vicarious Nucleophilic Substitution.

In this communication we report a convenient, as short as possible synthesis of aminocobaltocenium hexafluoridophosphate, a very useful compound for further functionalization in cobaltocenium chemistry. Via vicarious nucleophilic substitution of hydrogen of cobaltocenium hexafluoridophosphate with 1,1,1-trimethylhydrazinium iodide as nucleophile bearing its own leaving group, a one-step amination of cobaltocenium in 50% isolated yield is possible, a major improvement over the standard multistep procedure involving common Curtius rearrangement chemistry.

Redox-Rich Metallocene Tetrazene Complexes: Synthesis, Structure, Electrochemistry, and Catalysis.

Thermal or photochemical metal-centered cycloaddition reactions of azidocobaltocenium hexafluoridophosphate or azidoferrocene with (cyclooctadiene)(cyclopentadienyl)cobalt(I) afforded the first metallocenyl-substituted tetrazene cyclopentadienyl cobalt complexes together with azocobaltocenium or azoferrocene as side products. The trimetallic CpCo compounds are highly conjugated, colored, and redox-active metallo-aromatic compounds, as shown by their spectroscopic, structural, and electrochemical properties. The CpCo-tetrazenido complex with two terminally appended cobaltocene units catalyzes electrochemical proton reduction from acetic acid at a mild overpotential (0.35 V). Replacing cobaltocene with ferrocene moieties rendered the complex inactive toward catalysis.

Crystal structures of 1'-amino-cobaltocenium-1-carb-oxy-lic acid chloride monohydrate and of its azo dye 1'-[2-(1-amino-2,6-dimethylphenyl)diazen-1-yl]cobaltocenium-1-carb-oxy-lic acid hexa-fluorido-phosphate monohydrate.

1'-Amino-cobaltocenium-1-carb-oxy-lic acid chloride, [Co(C5H6N)(C6H5O2)]Cl·H2O, (3), and its azo derivative 1'-[2-(1-amino-2,6-dimethylphenyl)diazen-1-yl]cobaltocenium-1-carb-oxy-lic acid hexa-fluorido-phosphate, [Co(C13H14N3)(C6H5O2)]PF6·H2O (5) were obtained from cobaltocenium-1,1'-di-carb-oxy-lic acid hexa-fluorido-phosphate by converting one carboxyl group to its chloro-carboxyl derivative followed by chloride/azide exchange, Curtius rearrangement, diazo-tiation and azo coupling with 2,6-di-methyl-aniline. Both title compounds crystallize as their monohydrates. In the crystal structure of 3, both functional groups lie in the same direction, with the Cp rings being nearly eclipsed, and participate in an extended hydrogen-bonded supra-molecular network including the counter-ion and the water mol-ecule of crystallization. Although the functional groups in 5 are somewhat further apart, bearing a greater torsion angle with the Cp rings now staggered, a similar supra-molecular network is observed with not only the carb-oxy-lic acid and azo groups, but also with the more remote amino group participating in a hydrogen-bonded network, again including the counter-ion and the water mol-ecule. The hexa-fluorido-phosphate ion shows positional disorder. Compound 3 was refined as an inversion twin. In 5, each of the six F atoms is disordered over two sets of sites in a 1:1 ratio.

Cobaltocenylidene: A Mesoionic Metalloceno Carbene, Stabilized in a Gold(III) Complex.

Oxidative addition of cobaltoceniumdiazonium bis(hexafluoridophosphate) with (pseudo)halide aurates gave gold(III) complexes containing zwitterionic cobaltoceniumide as a ligand. Its selenium derivative, cobaltoceniumselenolate, was obtained by an electrophilic aromatic substitution reaction of iodocobaltocenium iodide with Na2 Se. Spectroscopic and structural data in combination with DFT calculations showed that this cobaltocenylidene species is a mesoionic carbene quite different from common N-heterocyclic carbenes. Its ligand properties (TEP, singlet-triplet gap, nucleophilicity, π-acidity, Brønsted basicity) are in part comparable to those of cyclic (amino)(alkyl/aryl)carbenes. Electrochemistry data showed that the mesoionic cobaltoceniumides are more electron-rich than their parent ferrocenes. The reversible reduction of the tricyanido gold complex appears 50 mV negative of the cobaltocenium/cobaltocene couple, whereas that of the selenide derivative is shifted cathodically by 550 mV.

Highly Electrophilic, Catalytically Active and Redox-Responsive Cobaltoceniumyl and Ferrocenyl Triazolylidene Coinage Metal Complexes.

A convenient access to a triad of triazoles with ferrocenyl and cobaltoceniumyl substituents is reported. N-Alkylation, deprotonation and metalation with CuI /AgI /AuI synthons affords the heteroleptic triazolylidene complexes. Due to the combination of neutral, electron-donating ferrocenyl substituents and cationic, strongly electron-withdrawing cobaltocenium substituents, the mesoionic carbene (MIC) ligands of these complexes are electronically interesting "push-pull", "pull-push" and "pull-pull" metalloligands with further switchable redox states based on their fully reversible FeII /FeIII , (ferrocene/ferrocenium) and CoIII /CoII , (cobaltocenium/cobaltocene) redox couples. These are the first examples of metal complexes of (di)cationic NHC ligands based on cobaltoceniumyl substituents. DFT calculated Tolman electronic parameter (TEP) of the new MIC ligands, show these metalloligands to be extremely electron-poor NHCs with properties unmatched in other carbene chemistry. Utilization of these multimetallic electronically tunable compounds in catalytic oxazoline synthesis and in antitumor studies are presented. Remarkably, 1 mol % of the AuI complex with the dicationic MIC ligand displays full catalytic conversion, without the need for any other additives, in less than 2 hours at ambient temperatures. These results thus firmly establish these new classes of cobaltoceniumyl based (di)cationic MIC ligands as prominent players in several branches of chemistry.

Bonding, Hyperfine Interactions, and Lattice Dynamics of Cationic and Neutral Ferrocenyl-Substituted Allylic and Cumulenic Compounds.

The synthesis and spectroscopic characterization (by mass, UV-visible, IR, NMR and (57)Fe Mössbauer spectroscopy) of three new compounds related to seven recently published ferrocenyl-substituted allylic and cumulenic compounds are reported and have made it possible to effect a systematic evaluation of the parameters extractable from temperature-dependent gamma ray resonance studies. For the neutral species, the hyperfine parameters (IS and QS) of the sigma-bonded ferrocenyl groups are insensitive to the structural details of the allylic or cumulenic carbon framework. The temperature dependence of the recoil-free fraction is dominated by the Cp ring-iron atom interaction, and is not diagnostic of the detailed molecular architecture. In the case of the carbocationic complexes, two distinct iron sites are resolvable from the Mössbauer data. The detailed temperature-dependent behavior of the hyperfine parameters and recoil-free fraction for 10 complexes with either equivalent termini, linked by similar, but different types of bridges (neutral 1-5), or with inequivalent moieties linked by related or identical connectors (cationic 6-10), has been elucidated over the temperature range 90