We report the synthesis of vanadium(V) oxo complex 1 with a pincer-type dianionic mesoionic carbene (MIC) ligand L 1 and the general formula [VOCl(L 1 )]. A comparison of the structural (SC-XRD), electronic (UV–vis), and electrochemical (cyclic voltammetry) properties of 1 with the benzimidazolinylidene congener 2 (general formula [VOCl(L 2 )]) shows that the MIC is a stronger donor also for early transition metals with low d-electron population. Since electrochemical studies revealed both complexes to be reversibly reduced, the stronger donor character of MICs was not only demonstrated for the vanadium(V) but also for the vanadium(IV) oxidation state by isolating the reduced vanadium(IV) complexes [Co(Cp*) 2 ][1] and [Co(Cp*) 2 ][2] ([Co(Cp*) 2 ] = decamethylcobaltocenium). The electronic structures of the compounds were investigated by computational methods. Complex 1 was found to be a moderate precursor for salt metathesis reactions, showing selective reactivity toward phenolates or secondary amides, but not toward primary amides and phosphides, thiophenols, or aryls/alkyls donors. Deoxygenation with electron-rich phosphines failed to give the desired vanadium(III) complex. However, treatment of the deprotonated ligand precursor with vanadium(III) trichloride resulted in the clean formation of the corresponding MIC vanadium(III) complex 6 , which undergoes a clean two-electron oxidation with organic azides yielding the corresponding imido complexes. The reaction with TMS-N 3 did not afford a nitrido complex, but instead the imido complex 10 . This study reveals that, contrary to popular belief, MICs are capable of supporting early transition-metal complexes in a variety of oxidation states, thus making them promising candidates for the activation of small molecules and redox catalysis.

We report the facile synthesis of a rare niobium(V) imido NHC complex with a dianionic OCO-pincer benzimidazolylidene ligand (L 1 ) with the general formula [NbL 1 (N t Bu)PyCl] 1-Py. We achieved this by in situ deprotonation of the corresponding azolium salt [H 3 L 1 ][Cl] and subsequent reaction with [Nb(N t Bu)Py 2 Cl 3 ]. The pyridine ligand in 1-Py can be removed by the addition of B(C 6 F 5 ) 3 as a strong Lewis acid leading to the formation of the pyridine-free complex 1. In contrast to similar vanadium(V) complexes, complex 1-Py was found to be a good precursor for various salt metathesis reactions, yielding a series of chalcogenido and pnictogenido complexes with the general formula [NbL 1 (N t Bu)Py(EMes)] (E = O (2), S (3), NH (4), and PH (5)). Furthermore, complex 1-Py can be converted to alkyl complex (6) with 1 equiv of neosilyl lithium as a transmetallation agent. Addition of a second equivalent yields a new trianionic supporting ligand on the niobium center (7) in which the benzimidazolylidene ligand is alkylated at the former carbene carbon atom. The latter is an interesting chemically "noninnocent" feature of the benzimidazolylidene ligand potentially useful in catalysis and atom transfer reactions. Addition of mesityl lithium to 1-Py gives the pyridine-free aryl complex 8, which is stable toward "overarylation" by an additional equivalent of mesityl lithium. Electrochemical investigation revealed that complexes 1-Py and 1 are inert toward reduction in dichloromethane but show two irreversible reduction processes in tetrahydrofuran as a solvent. However, using standard reduction agents, e.g., KC 8 , K-mirror, and Na/Napht, no reduced products could be isolated. All complexes have been thoroughly studied by various techniques, including 1 H-, 13 C{ 1 H}-, and 1 H-15 N HMBC NMR spectroscopy, IR spectroscopy, and X-ray diffraction analysis.

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 1 H/ 11 B/ 13 C/ 19 F/ 55 Mn 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.

We report the synthesis of 17 molybdenum and tungsten complexes supported by the ubiquitous BDI ligand framework (BDI = β-diketiminate). The focal entry point is the synthesis of four molybdenum and tungsten(V) BDI complexes of the general formula [MO(BDIR)Cl2] [M = Mo, R = Dipp (1); M = W, R = Dipp (2); M = Mo, R = Mes (3); M = W, R = Mes (4)] synthesized by the reaction between MoOCl3(THF)2 or WOCl3(THF)2 and LiBDIR. Reactivity studies show that the BDIDipp complexes are excellent precursors toward adduct formation, reacting smoothly with dimethylaminopyridine (DMAP) and triethylphosphine oxide (OPEt3). No reaction with small phosphines has been observed, strongly contrasting the chemistry of previously reported rhenium(V) complexes. Additionally, the complexes 1 and 2 are good precursors for salt metathesis reactions. While 1 can be chemically reduced to the first stable example of a Mo(IV) BDI complex 15, reduction of 2 resulted in degradation of the BDI ligand via a nitrene transfer reaction, leading to MAD (4-((2,6-diisopropylphenyl)imino)pent-2-enide) supported tungsten(V) and tungsten(VI) complexes 16 and 17. All reported complexes have been thoroughly studied by VT-NMR and (heteronuclear) NMR spectroscopy, as well as UV–vis and EPR spectroscopy, IR spectroscopy, and X-ray diffraction analysis.

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.

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.

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Twenty‐one vanadium bis‐phenolate benzimidazolylidene complexes, spanning three oxidation states, have been investigated. Special emphasis is placed on their salt metathesis reactivity and the accessibility of the +IV oxidation state by reductive or oxidative routes, starting from vanadium(V) or vanadium(III) respectively. While the reductive route is highly dependent on the reducing agent and starting material used, the oxidative route gives clean access to vanadium(IV) dihalide complexes. The low‐valent vanadium(III) complexes are excellent precursors for salt metathesis reactions which lead to the isolation of a rare vanadium(III) NHC alkyl complex. All new complexes have been characterized by (paramagnetic) 1H NMR and 51V NMR, UV–VIS, IR and EPR spectroscopy as well as elemental analysis. Cyclic voltammetry has been performed in selected cases to study the influence of imido or phenolate supporting ligands towards the redox‐potential of the vanadium(V/IV) redox couple compared to the parent oxo‐chlorido complex A.