Abstract Complexes of iron in high oxidation states are captivating research subjects due to their pivotal role as active intermediates numerous catalytic processes. Structural and spectroscopic studies well-defined model complexes often provide evidence these intermediates. In addition the fundamental molecular electronic structure insights gained by complexes, reactivity also affects our understanding reaction mechanisms for small molecule bond-activation chemistry. Here, we report...

Charging up the iron in ferrocene salts Ferrocene is archetype of sandwich compounds, so called because a metal atom inserted between two carbon rings. The elucidation ferrocene's structure was pivotal to development organometallic chemistry during mid-20th century. ease with which center molecule can toggle +2 and +3 oxidation states has made compound common electrochemical standard. Malischewski et al. report synthesis isolation +4 state, they characterize crystallographically...

Abstract In contrast to the well‐known 2‐norbornyl cation, structure of which was a matter long debate until its pentacoordinated nature recently proven by an X‐ray structure, pentagonal‐pyramidal dication hexamethylbenzene has received considerably less attention. This species first prepared Hogeveen in 1973 at low temperatures magic acid (HSO 3 F/SbF 5 ), for he proposed non‐classical (containing hexacoordinated carbon) based on NMR spectroscopy and reactivity studies, but no crystal been...

Abstract Ferrocene, Cp 2 Fe, is quantitatively protonated in a mixture of liquid HF/PF 5 to yield [Cp FeH](PF 6 ), which was characterized by 1 H/ 13 C NMR and 57 Fe Mössbauer spectroscopy as well single‐crystal X‐ray diffraction analysis. analysis at 100 K revealed disordered, iron‐coordinated hydrido ligand, unambiguously located aspherical atom refinement K, analyzing the non‐disordered crystal structure 30 revealing non‐agostic structure.

Fine-tuning of the electrostatic potentials sulfonium cations influences lengths S⋯N chalcogen bonds in supramolecular assemblies.

Herein, we report the solvent-dependent reactivity of Fe(CO)5 toward AsF5 in either anhydrous HF or liquid SO2. The reaction with superacid HF/AsF5 leads to protonation iron center and allows for first-time structural characterization [FeH(CO)5]+ solid state, representing one most acidic transition metal hydride complexes ever be isolated structurally characterized. In aprotic but oxidation-stable solvent SO2, is oxidized dimerized [Fe2(CO)10]2+, which isoelectronic well-known Mn2(CO)10....

We report the synthesis and structural characterization of rhodocene anion [Rh(C5(CH3)5)(C5(CF3)5)]− [1]− as [Co(C5(CH3)5)2]+ salt, representing an unprecedented coexistence metallocene cations anions in different oxidation states. was synthesized by reduction rhodocenium cation [Rh(C5(CH3)5)(C5(CF3)5)][BF4] [1]+[BF4]− with two equivalents decamethylcobaltocene [Co(C5(CH3)5)2], since strongly electron-withdrawing effect [C5(CF3)5)]− ligand shifts first second potentials [1]+ to moderate...

Hetero-tetra-metallic complexes, FeNOCuLnCo (Ln = Gd, Tb, Dy), combining magnetic properties and photo-isomerism, were obtained through the rational assembly of photo-switching nitroprusside anion FeNO with new Schiff base CuLnCo precursors. Herein, we describe synthesis characterisation these compounds followed by a demonstration their multifunctional character. Particularly noteworthy is FeNOCuTbCo complex, one few examples photo-isomerizable single-molecule magnet (SMM) significant first...

The photolytically induced arene displacement of [Fe(C5H5)(oDCB)][PF6] (oDCB = ortho-dichlorobenzene) in the presence [NEt4][C5(CF3)5] afforded highly fluorinated and benchstable ferrocene [Fe(C5H5)(C5(CF3)5)]. perfluorinated Cp* ligand exerts an extreme electron withdrawing effect on with Epa up to 1.70 V (vs. Fc/Fc+). This proved be highest value obtained for any reported so far. corresponding stable storable ferrocenium complex [Fe(C5H5)(C5(CF3)5)][AsF6] was generated quantitative yield...

The air‐ and water stable perfluorinated Cp* [C5(CF3)5]− is presented as a candidate for the vastly underexplored group of weakly coordinating carbanions (WCCAs). Its extreme electron deficiency combined with stabilization negative charge within an aromatic system results in low basicity, yielding very weak coordination ability. As Cp anions usually possess strongly pronounced carbanionic character, resembles extraordinary exception both WCA chemistry. However, ability remains ambivalent due...

The electron-deficient ferrocene [Fe(C5H5)(C5(CF3)5)] is complemented by the synthesis and full characterisation of analogous bench-stable ruthenocene [Ru(C5H5)(C5(CF3)5)]. These complexes have been studied with respect to substitution lability perfluorinated Cp* ligand under mild conditions. Photolysis metallocenes in MeCN converted [C5(CF3)5]- into a weakly coordinating anion. This gave access highly reactive piano-stool [M(C5H5)(MeCN)3][C5(CF3)5] (M = Fe, Ru). unstable iron half-sandwich...

We report the first complete series of structurally characterized cyclopentadienyl complexes coinage metals. Their unusually high stability is due to oxidative perfluorinated Cp* ligand [C 5 (CF 3 ) ] − .

One-electron oxidation of two series diaryldichalcogenides (C6F5E)2 (13a-c) and (2,6-Mes2C6H3E)2 (16a-c) was studied (E = S, Se, Te). The reaction 13a 13b with AsF5 SbF5 gave rise to the formation thermally unstable radical cations [(C6F5S)2]˙+ (14a) [(C6F5Se)2]˙+ (14b) that were isolated as [Sb2F11]- [As2F11]- salts, respectively. 13c afforded only product a Te-C bond cleavage, namely previously known dication [Te4]2+ [AsF6]- salt. [NO][SbF6] provided corresponding [(2,6-Mes2C6H3E)2]˙+...

Abstract The 16‐valence electron species [Cp* 2 Fe] 2+ (Cp*=η‐C 5 Me ), formally featuring a tetravalent iron ion, quantitatively binds CO in HF solution to form the stable, diamagnetic carbonyl Fe(CO)] . This dication forms salts presence of AsF 6 − and SbF that were crystallographically characterized. molecular structure crystals Fe(CO)](AsF ) displays cyclopentadienyl rings are clearly not parallel an equatorially bound η 1 ‐CO ligand. formal oxidation state +IV was investigated by 57 Fe...

Complexation of the green bismuthinidene (RBi) with two equivalents a highly fluorinated aryl iodide at low temperature allows crystallographic identification an unstable red species that can be regarded as intermediate in overall Bi(I) → Bi(III) oxidation process. Both C-I bonds are orientated toward filled 6p orbital bismuth (Bi-I distances 3.44-3.52 Å), leading to elongation by 0.05 and 0.07 Å. Density functional theory (DFT) calculations confirm center is indeed acting electron donor,...

The structures of three solvated monovalent cation salts the superweak anion B12F122- (Y2-), K2(SO2)6Y, Ag2(SO2)6Y, and Ag2(H2O)4Y, are reported discussed with respect to previously Ag+ K+ other weakly coordinating anions. K2(SO2)6Y Ag2(SO2)6Y isomorphous based on expanded cubic close-packed arrays Y2- anions M(OSO)6+ complexes centered in trigonal holes one layer B12 centroids (⊙). ions have virtually identical bicapped prism MO6F2 coordination spheres, M-O distances 2.735(1)-3.032(2) Å for...

The reaction of AgBF

Several cationic rhodium(I) complexes [Rh(COD)L2][C5(CF3)5] have been synthesized through substitution of the weakly bound [C5(CF3)5]- ligand from [Rh(COD)(C5(CF3)5)], further emphasizing its unique reactivity. Besides acetonitrile, pyridine derivatives with varying degrees fluorination employed as ligands in order to investigate influence upon binding affinity towards resulting [Rh(COD)]+ fragment and limit which can be displaced. Furthermore, newly compounds represent rare examples rhodium...

Herein, we present two different routes for the synthesis of perfluorinated trityl cation, which allowed handling free, uncoordinated species in organic solvents first time. The usage weakly coordinating anion [Al(OTeF

The oxidation power of the cyanocarbon TCNQ (tetracyano-quinodimethane) can be significantly increased to approximately E = +0.9 V vs. Cp2Fe by coordination up four equivalents strong fluorinated Lewis acid B(C6F5)3, resulting in a highly reactive but easy-to-use system. Thianthrene and tris(4-bromophenyl)amine were oxidized corresponding radical cations. Dianionic [TCNQ·4 B(C6F5)3]2- was formed upon reduction with two ferrocene or decamethylcobaltocene. B(C6F5)3]- are rare cases...

Abstract Triphenylpnictogens EPh 3 (E=N, P, As, Sb, Bi) are able to displace the perfluorinated Cp* ligand in [Rh(COD)(C 5 (CF ) )] (COD=1,5‐cyclooctadiene) up quantitative yield. The resulting ionic products contain [C ] − as uncoordinated counter anion. cations feature [Rh(COD)] + fragments, coordinated by one (N, Bi), two (P, As) or three (Sb) triphenylpnictogen moieties. Whereas coordination via pnictogen is observed for As and π‐coordination of aryl rings N Bi.

Joining the stable: The first examples of highly instable selenenyl fluorides RSeF are prepared from reaction on tin selenide RSeSnMe(3) with XeF(2). Through use extremely large protecting groups (m-terphenyl ligands) which stabilizes units against disproportionation, compounds could be isolated and characterized by NMR spectroscopy single-crystal structure analysis (see structure).

The B12F12– radical anion was generated by oxidation of [CoCp2+]2B12F122– with AsF5 in SO2. In the crystal structure [CoCp2+]B12F12–, displays a lowered symmetry (D2h) instead an Ih-symmetric dianion as result Jahn–Teller distortion. Moreover, shortening B–F bonds and subtle changes B–B are observed. DFT calculations show that, for unknown neutral B12F12, unprecedented structural isomers [e.g., octahedral B6(BF2)6] energetically favored icosahedral structure. structures energetics compared...