Synthesis and structural characterization of 1,8-biscobaltocen-1′-ylium-naphthalene dication: Towards paramagnetic, cofacially stacked metallocenes

The double nucleophilic addition of 1,8-dilithionaphthalene to cobaltocenium cations reveals the neutral dinuclear complex 1,8-bis[(η⁵-cyclopentadienyl)(η⁴-1′,3′-cyclopentadien-5′-yl)cobalt(I)]-naphthalene (2). Abstraction of two hydrides yields the dinuclear dicationic complex 1,8-biscobaltocen-1′-ylium-naphthalene bis(tetrafluoroborate) (3(BF₄)₂). Both complexes are characterized by X-ray structure analysis. In addition, the redox chemistry of 3(BF₄)₂ was investigated, demonstrating the electrochemical stability of three oxidation states +2, +1 and 0.     

Cobaltocenium Carboxylate Transition Metal Complexes: Synthesis,Structure, Reactivity,and Cytotoxicity

Cobaltocenium carboxylate is an unusual betaine that functions as a formally neutral carboxylate ligand with late transition metal centers comprising Co²⁺, Ni²⁺, Cu²⁺, Ag⁺, Zn²⁺, Cd²⁺, Hg²⁺, and Rh⁺. Structurally, a rich coordination chemistry is observed – from simple monomeric homoleptic complexes to heteroleptic dimeric, trimeric, and polymeric compounds, as shown by X‐ray diffraction of 11 compounds. Chemically, thermal decarboxylation was investigated aiming at the formation of cobaltocenium‐carbene transition metal complexes, in analogy to such chemistry of imidazolium carboxylate betaines. Cytotoxicity studies of cobaltocenium carboxylate transition metal complexes were performed to evaluate the medicinal bioorganometallic potential of these compounds. While cobaltocenium carboxylate was inactive, its complexes with Ag⁺, Cd²⁺, and Hg²⁺ triggered significant cytotoxic effects.     

Synthesis and electrochemistry of 1,1′-bis(phosphino)cobaltocenium compounds

The electrochemistry of 1,1′-bis(diphenylphosphino)cobaltocenium hexafluorophosphate ([dppc][PF₆]), 1,1′-bis(dicyclohexylphosphino)cobaltocenium hexafluorophosphate ([dcpc][PF₆]), 1,1′-bis(di-iso-propylphosphino)cobaltocenium hexafluorophosphate ([dippc][PF₆]), and 1-(di-tert-butylphosphino)cobaltocenium hexafluorophosphate ([1-dtbpc][PF₆]) was examined in methylene chloride with tetrabutylammonium hexafluorophosphate as the supporting electrolyte. A reversible reductive wave followed by an irreversible wave at more negative potentials was observed. Ten new phosphinothioyl ([dppcS₂][PF₆], [dcpcS₂][PF₆], [dippcS₂][PF₆], [1-dtbpcS][PF₆], and 1,1′-bis(dicyclohexylphosphinothioyl)ferrocene) and phosphinoselenoyl derivatives ([dppcSe₂][PF₆], [dcpcSe₂][PF₆], [dippcSe₂][PF₆], [1-dtbpcSe][PF₆], and 1,1′-bis(dicyclohexylphosphinoselenoyl)ferrocene) were prepared and characterized, and the structures of eight of these compounds were determined. The electrochemistry of these phosphinochalcogenyl cobaltocenium compounds, as well as the previously prepared [dppcO₂][PF₆], displayed two reversible reductive waves at potentials less negative than that of the free phosphines. A correlation was found to exist between the Hammett substituent constant σ_p and the reduction potentials of these compounds. In addition, the phosphinoselenoyl [dppcSe₂][PF₆], [dcpcSe₂][PF₆], and [dippcSe₂][PF₆] displayed an electrochemically irreversible oxidative wave, potentially indicating an intramolecular Se-Se bonded trication. The electrochemistry of three new and five previously reported transition metal complexes of the general formula [M_nCl₂(P^∩P)][PF₆] (M = Pd or Pt, n = 1, P^∩P = dppc, dcpc or dippc; M = Au, n = 2, P^∩P = dppc or dcpc)) was also examined displaying at least two reductive waves at potentials less negative than that of the free phosphines. Comparison of the electrochemical data with that previously obtained for analogous ferrocenes indicates that a correlation exists between the reduction potentials of the cobaltocenium phosphines and the potentials at which oxidation of the ferrocene phosphines occurs. In addition, the structure of [Au₂Cl₂(dppc)][PF₆] was determined.     

Synthesis and application of novel ionic phosphine ligands with a cobaltocenium backbone

Six novel ionic phosphine ligands with a cobaltocenium backbone, 1,1′-bis(dicyclohexylphosphino) cobaltocenium hexafluorophosphate () (1a), 1,1′-bis(di-iso-propylphosphino) cobaltocenium hexafluorophosphate () (2a), 1,1′-bis(di-tert-butylphosphino) cobaltocenium hexafluorophosphate () (3a), and the monophosphine ligand (Cc⁺ = cobaltocenium; R = Cy, 1b; R = i-Pr, 2b; R = t-Bu, 3b) were synthesized and characterized by elemental analysis, spectroscopy, and X-ray diffraction techniques. These ligands are air-stable and useful for Suzuki coupling reactions in the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (), enabling high catalytic activity.     

Synthesis of cobaltocenium salts for use as redox labels and their incorporation into Nafion films

A cobaltocenium label was covalently attached to two antidepressants, nortriptyline and desipramine, via an amide linkage, and also to the hydrazine derivative of the biologically important compound biotin (vitamin H), again via an amide linkage. Analytically pure samples of these new cobaltocenium salts could be obtained by chromatography on silica gel followed by elution with aqueous acetone solutions containing sodium chloride (NaCl). These positively charged cobaltocenium ions preconcentrate in a polyanionic Nafion film coated on a glassy carbon surface, albeit at different concentration levels. One factor which seems to influence the amount of cobaltocenium ion that enters the film is polarity since the cobaltocenium ion containing the rather polar biotin preconcentrates at the lowest level in the relatively hydrophobic Nafion. Square-wave voltammograms of Nafion films containing these cobaltocenium cations exhibit a one-electron, reversible, reduction wave at approximately ?1.1 V (vs Ag/AgCl) with peak currents that are sufficiently large to permit detection of 10^?8 M quantities of these substances in the bulk solution.     

Cu(I), Ag(I) complexes containing (η 5-cyclopentadienyl) [η 5-1-(diphenylphosphino) cyclopentadienyl] cobaltocenium

{Cu₄Br₅[(η ⁵-C₅H₄PPh₂)(η ⁵-C₅H₅)Co]₄}[PF₆]₃, [(η ⁵-C₅H₄PPh₂)(η ⁵-C₅H₅)Co]⁺ = ((η ⁵-cyclopentadienyl)[η ⁵-1-(diphenylphosphino) cyclopentadienyl] cobaltocenium) and {Ag(NO₃)(CH₃COCH₃)[(η ⁵-C₅H₄PPh₂)(η ⁵-C₅H₅)Co]} _n [PF₆] _n have been synthesized and characterized by elemental analyses, infrared spectroscopy, X-ray diffraction techniques, and by cyclic voltammetry. {Cu₄Br₅[(η ⁵-C₅H₄PPh₂)(η ⁵-C₅H₅)Co]₄}[PF₆]₃ contains four coplanar copper atoms bridged by four μ-Br and one central μ ₄-Br occupying the apex of a square pyramid, and {Ag(NO₃)(CH₃COCH₃)[(η ⁵-C₅H₄PPh₂)(η ⁵-C₅H₅)Co]} _n [PF₆] _n affording a 1-D coordination zigzag polymer.     

Crystal Structures and Magnetic Properties of Charge-Transfer Salts: Cobaltocenium Bis(cis 1,2-diphenylethene-1,2-dithiolato)metalates (Metal = Ni,Pd, Pt)

Charge-transfer salts [Co(C₅H₅)₂][M(dpt)₂] (M = Ni and Pt; dpt = cis-1,2-diphenylethene-1,2-dithiolate) were synthesized and crystallographically characterized. [Co(C₅H₅)₂][Ni(dpt)2] crystallizes in the monoclinic space group C2/c with a = 25, 607(3) Å, b = 9.4151(11) Å, c = 14.407(4) Å, β = 101.373(22)°, V = 3405.3(10) Å₃ and Z = 4. [Co(C₅H₅)₂][Pt(dpt)₂] belongs to the triclinic space group $ {\rm P}\bar 1 $ with a = 9.4666(11) Å, b = 13.9869(12) Å, c = 14.2652(9) Å, α = 99.983(6)°, β = 90.034(7)°, γ = 109.751(7)°, V = 1747.2(3) ų and Z = 2. Both structures consist of ··· D⁺A^?D⁺A^?D⁺A^? ··· linear chains with the local C₅ axis of the eclipsed [Co(C₅H₅)₂]⁺ cation parallel to the best MS₄ plane of the [M(dpt)₂]^? anion. Magnetic susceptibility measurements show that χ_M T values of the complexes [Co(C₅H₅)₂][M(dpt)₂] (M = Ni, Pd, and Pt) remain nearly constant in the temperature range 15–300 K, but decrease rapidly with further decreasing of temperature, indicating weak antiferromagnetic interactions at low temperatures.