New homoleptic metal carbonyl cations: the syntheses, vibrational and¹³C MAS NMR spectra of hexacarbonyl-ruthenium(II) and-osmium(II) undecafluorodiantimonate(V), [Ru(CO)₆][Sb₂F₁₁]₂and [Os(CO)₆][Sb₂F₁₁]₂

Abstract

The new homoleptic carbonyl cations [ R ~( C 0 ) ~1 2 + and [os(co)6]2+ are obtained as [Sb2FI11-salts by the reductive carbonylation of M(S03F)3 (M = Ru, Os), under very mild conditions (60-90 "C, 1 atm CO), in liquid SbF5 in a simple, one-step procedure, and are characterized by FT Raman, FTlR and 13C MAS NMR spectroscopy.

Metal-Specific Reactivity in Single-Atom Catalysts: CO Oxidation on 4d and 5d Transition Metals Atomically Dispersed on MgO

“…These bands appear in the spectral region for the CO stretching in (poly)carbonyls of transition metals in high oxidation states. 57 In this case (Figure 6b), band frequencies are in fair agreement with the υCO vibrations registered at 2190-2216 cm -1 for Ru(CO)6 2+ cationic carbonyl complexes 58 and can thus be tentatively assigned to CO linearly bound to Ru δ+ centers. The bands likely reflect the development of new surface sites via the protrusion of metal centers on the catalyst surface.…”

Chapter 17. The noble metals

“…43 The vibrational and NMR spectra of [os(c0)6]'+ have been reported. 44 The complexes [Os(H),X,(PPr',),] (X = C1, Br or I), which show a trigonal prismatic C, structure in the solid state, exist in equilibrium with a non-symmetric isomer in solution; the isomers interconvert via three discrete processes;45 [Os(H),(PPr',),(L-S,O)] (L = N-acetyl-L-cysteine) also exhibits this distorted geometry.46 Protonation or ferrocenium ion oxidation of [OS(H),(PPr'3),] yields [Os(H),(H,)(PPr',),] +, which undergoes successive substitutions by acetonitrile to afford [0sH(H,)(NCMe),(PPri3),] Treatment of H,OsBr, with C,HMe, in HBr-MeOH affords [(OSH(Cp*),},(OS,Br,)], whose crystal structure contains the eclipsed rotamer of [Os,Br,12-; the observed 0 s -0 s distance of 2.219(2)A is slightly longer than those in the staggered forms of this anion. 52 The square-planar complexes [OsCl(NO)(PPr',R),] (R = Pr', Ph), which are the first 16-electron osmium(0) species to be structurally characterized, undergo facile oxidative addition reactions with H, and alkynes.…”

Das Tetrakis(carbonyl)dioxoosmium(VI)-Kation:trans-[OsO2(CO)4]2+

“…B. der oktaedrischen [M(CO) 6 ] 2 -Ionen (M Fe, [4] Ru, Os [5] ). Thermisch stabile Salze werden in der Regel mit dem supersauren Anion [Sb 2 F 11 ] À [6] erhalten.…”

“…In HF/SbF 5 (1) Es gibt aber drei Probleme mit dieser Gleichung: 1) Eine befriedigende Elementaranalyse dieses sehr reaktiven Materials konnte nicht erhalten werden, und die Massen-sowie Redox-Bilanzen (CO 2 -Bestimmung) sind mit Fehlern zwischen 10 und 20 % sehr ungenau.…”

“…Im 13 [21] diamagnetisch. [14,15] [5] und [Ir(CO) 6 ] 3 (d 121), [18] wobei die Verschiebung der Iridiumverbindung die bei Metallcarbonyl-Kationen und deren Derivaten bisher kleinste ist. [3] Für die isoelektronischen Spezies trans-[OsO 2 (CN) 4 ] 2À [23] und [Os(CN) 6 ] 4À [24] sind d c -Werte von 120 bzw.…”