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The reaction of Ag+ with Ru3(CO)12 in a CO atmosphere under concommittant irradiation with UV-light yields a salt of the metal-only Lewis-pair [Ag{Ru(CO)5}2]+. Switching the silver cation for a more process-selective deelectronator yields a salt of the homoleptic transition metal carbonyl cation [Ru2(CO)10]2+, which fills the gap between the known cations [Ru(CO)6]2+ and [Ru3(CO)14]2+. The amount of π-backdonation in this series was studied by a combination of vibrational spectroscopy and computed relaxed force constants. [ABSTRACT FROM AUTHOR]

The reaction of Ag+ with Ru3(CO)12 in a CO atmosphere under concommittant irradiation with UV-light yields a salt of the metal-only Lewis-pair [Ag{Ru(CO)5}2]+. Switching the silver cation for a more process-selective deelectronator yields a salt of the homoleptic transition metal carbonyl cation [Ru2(CO)10]2+, which fills the gap between the known cations [Ru(CO)6]2+ and [Ru3(CO)14]2+. The amount of π-backdonation in this series was studied by a combination of vibrational spectroscopy and computed relaxed force constants. [ABSTRACT FROM AUTHOR]

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Ein selektives Deelektronierungsreagenz mit einem sehr hohen Potential von +2.00 V (Lösung)/+2.41 V (Festkörper) vs. Fc+/0 wurde entwickelt und angewendet, welches auf einem raumtemperaturstabilen Perfluornaphthalin(NaphthalinF)‐Radikalkationsalz basiert. Durch die Deelektronierung von kommerziellem NaphthalinF durch [NO]+[F{Al(ORF)3}2]− im Festkörper kann [NaphthalinF]+⋅[F{Al(ORF)3}2]− (ORF=OC(CF3)3) in Gramm‐Maßstäben erhalten werden. Durch eine Thermodynamikanalyse wurde das Festkörperpotential des [NO]+‐Edukts zu +2.34 V vs. Fc+/0 mit [F{Al(ORF)3}2]− als Gegenion ermittelt, welches sich von +1.14 V vs. Fc+/0 für das kleinere [SbF6]−‐Anion stark unterscheidet. In selektiven Reaktionen wurde die Selektivität von [NaphthalinF]+⋅ in der Deelektronierung einer Vielzahl von organ(ometall)ischen Molekülen und Elementen in Lösung demonstriert: So wurden die Molekülstrukturen der Acen‐Dikationen [Tetracen]2+ und [Pentacen]2+ erhalten und der Carbonylkomplex des Ferrocen‐Dikations [Fc(CO)]2+ spektroskopisch nachgewiesen, sowie das [P9]+‐Kation aus weißem Phosphor, lösungsmittelfreies Kupfer(I)‐Salz aus Kupfermetall und der dikationische Fe(IV)‐Scorpionatkomplex [Fe(sc)2]2+ hergestellt. [ABSTRACT FROM AUTHOR]

The title silver(I) complex salts [Ag{Re2(CO)10}{Re(CO)5}2]+[Al(ORF)4]− (AgRe4; ORF=‐OC(CF3)3) and [Ag{Ir4(CO)12}2]+[Al(ORF)4]− (AgIr8) form upon reaction of Ag+[Al(ORF)4]− and the transition metal carbonyls (TMCs) Re2(CO)10 and Ir4(CO)12 respectively. The solid‐state structure of the AgRe4 cluster shows an unexpected asymmetric coordination motif, wherein the silver(I) cation has inserted into the Re−Re bond of one Re2(CO)10 moiety, while the other dirhenium carbonyl coordinates only over one metal atom towards the silver(I) cation. The AgIr8 cluster is formed by the edge‐on coordination of two Ir4 tetrahedra and the silver cation in a D2 symmetric fashion with a torsion angle of 46.5°. QTAIM analysis shows bond paths between the silver atom and the nearby metal atoms in all cases, whereas only the non‐inserted Re2(CO)10 moiety shows additional bond paths between the carbonyl ligands and the silver cation. In addition, the insertion of the Ag+ cation into the Re−Re bond in Re2(CO)10 removes the bond path between the two rhenium atoms. The EDA‐NOCV analysis suggests an increase of the interaction energy between the silver(I) cation and the respective metal carbonyls from the metal centered transition metal carbonyl (TMC) donors W(CO)6

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

Die Octacyanometallate K4[Mo(CN)8] und K4[W(CN)8] werden in der supersauren Mischung von wasserfreiem Fluorwasserstoff und Antimonpentafluorid vollständig protoniert. Die dabei entstandenen Komplexe [Mo(CNH)8]4+[SbF6]−4 und [W(CNH)8]4+[SbF6]−4 sind die ersten Beispiele für achtfach koordinierte homoleptische Komplexe mit Isoblausäure‐Liganden (CNH). Diese Verbindungen wurden kristallographisch untersucht und zeigen Netzwerke aus Wasserstoffbrückenbindungen mit kurzen N⋅⋅⋅H⋅⋅⋅F‐Kontakten. Tieftemperatur‐NMR‐Messungen in HF bestätigen einen schnellen Protonenaustausch sogar bei −40 °C. Durch die Protonierung steigt die Wellenzahl der ν(C≡N)‐Schwingung um etwa 50 cm−1, was im Einklang mit DFT‐Rechnungen steht. [ABSTRACT FROM AUTHOR]

Octacyanometalates K4[Mo(CN)8] and K4[W(CN)8] are completely protonated in superacidic mixtures of anhydrous hydrogen fluoride and antimony pentafluoride. The resulting hydrogen isocyanide complexes [Mo(CNH)8]4+ [SbF6]−4 and [W(CNH)8]4+ [SbF6]−4 are the first examples of eight‐coordinate homoleptic metal complexes containing hydrogen isocyanide (CNH) ligands. The complexes were crystallographically characterized, revealing hydrogen‐bonded networks with short N⋅⋅⋅H⋅⋅⋅F contacts. Low‐temperature NMR measurements in HF confirmed rapid proton exchange even at −40 °C. Upon protonation, ν(C≡N) increases of about 50 cm−1 which is in agreement with DFT calculations. [ABSTRACT FROM AUTHOR]

In the title compound, di-μ-cyanato-1:2κ²N:C;2:3κ²C:N-di­cyanato-2κ²C-bis­(1,4,7,10,13,16-hexa­oxa­cyclo­octa­deca­ne)-1κ6O;3κ6O-1,3-dipotassium(I)-2-platinum(II), [K2Pt(CN)4(C12H24O6)2] or [K(18-crown-6)]2·[Pt(CN)4], two trans-orientated cyano groups of the square-planar [Pt(CN)4]2− dianion (Pt· · ·Pt site symmetry 1) bind to one potassium ion each, which are additionally coordinated by the six O atoms of 18-crown-6. No PtPt inter­actions occur in the crystal, but very weak Pt· · ·H contacts (2.79 Å) are observed. [ABSTRACT FROM AUTHOR]

In the title compound, di-μ-cyanato-1:2κ²N:C;2:3κ²C:N-di­cyanato-2κ²C-bis­(1,4,7,10,13,16-hexa­oxa­cyclo­octa­deca­ne)-1κ6O;3κ6O-1,3-dipotassium(I)-2-platinum(II), [K2Pt(CN)4(C12H24O6)2] or [K(18-crown-6)]2·[Pt(CN)4], two trans-orientated cyano groups of the square-planar [Pt(CN)4]2− dianion (Pt· · ·Pt site symmetry 1) bind to one potassium ion each, which are additionally coordinated by the six O atoms of 18-crown-6. No PtPt inter­actions occur in the crystal, but very weak Pt· · ·H contacts (2.79 Å) are observed. [ABSTRACT FROM AUTHOR]

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

To access the hitherto almost unknown class of clustered transition metal carbonyl cations, the trimetal dodecacarbonyls M 3 (CO) 12 (M = Ru, Os) were reacted with the oxidant Ag + [WCA] - , but yielded the silver complexes [Ag{M 3 (CO) 12 } 2 ] + [WCA] - (WCA = [Al(OR F ) 4 ] - , [F{Al(OR F ) 3 } 2 ] - ; R F = -OC(CF 3 ) 3 ). Addition of further diiodine I 2 to increase the redox potential led for M = Ru non-specifically to divalent mixed iodo-Ru II -carbonyl cations. With [NO] + , even the N-O bond was cleaved and led to the butterfly carbonyl complex cation [Ru 4 N(CO) 13 ] + in low yield. Obviously, ionization of M 3 (CO) 12 with retention of its pseudo-binary composition including only M and CO is difficult and the inorganic reagents did react non-innocently. Yet, the radical cation of the commercially available perhalogenated anthracene derivative 9,10-dichlorooctafluoroanthracene (anthracene Hal ) is a straightforward accessible innocent deelectronator with a half-wave potential E 1/2 of 1.42 V vs. Fc 0/+ . It deelectronates M 3 (CO) 12 under a CO atmosphere and leads to the structurally characterized cluster salts [M 3 (CO) 14 ] 2+ ([WCA] - ) 2 including a linear M 3 chain. The structural characterization as well as vibrational and NMR spectroscopies indicate the presence of three electronically independent sets of carbonyl ligands, which almost mimic M(CO) 5 , free CO and even [M(CO) 6 ] 2+ in one and the same cation., Competing Interests: The authors declare no conflict of interest., (This journal is © The Royal Society of Chemistry.)

Homoleptic eightfold coordinated methyl isocyanide complexes of W(IV) and W(V) have been prepared for the first time. The reaction of [NBu 4 ] 4 [W(CN) 8 ] with methyl triflate (MeOTf) gives [W(CNMe) 8 ][OTf] 4 . The even stronger methylating mixture of methyl fluoride (MeF) and arsenic pentafluoride (AsF 5 ) in liquid sulfur dioxide (SO 2 ) is able to fully alkylate both [NBu 4 ] 4 [W(CN) 8 ] and [NBu 4 ] 3 [W(CN) 8 ]. The paramagnetic octakis(methyl isocyanide)tungsten(V) complex [W(CNMe) 8 ][AsF 6 ] 5 is thermally highly unstable above -30 °C. All compounds have been characterized via single-crystal X-ray diffraction and IR, Raman, and NMR or EPR spectroscopy.