Reactions of Laser-Ablated Molybdenum and Tungsten Atoms with Dioxygen. Resolved Infrared Spectra of Natural Molybdenum and Tungsten Isotopic Oxides in Argon Matrices

Abstract

Laser-ablated molybdenum and tungsten atoms were reacted with dioxygen and 18O-substituted dioxygen. The products of these reactions were isolated in solid argon matrices at 10 K and studied by matrix infrared spectroscopy. Analysis of spectra enabled identification of reaction products, which included MoO2, (O2)MoO2, MoO3, WO, WO2, (O2)WO2, and WO3. Resolution of isotopic splitting due to natural isotopic abundance of the metal verified the presence of a single metal atom in these molecules and allowed for calculation of bond angles for the molybdenum and tungsten dioxide molecules and their dioxygen complexes.

A Critical Appraisal of the Experimental Data on the Molecular Structure and Spectra of Halides, Oxides, and Hydrides of the s-, d-, and f-Block Elements

“…Further, the assignment of n 1 has been questioned. [97] If MoO 3 were planar this would agree with data on WO 3 [11] and RuO 3 , [98] both reported as D 3h . UO 3 is exceptional in that it is apparently T-shaped in argon matrices and, as a result, has been extensively studied.…”

“…Figure 6 shows the dramatic change in the Passing now to the second-and third-row transition elements, the earlier members are, like those of the first row, strongly nonlinear: Zr and Hf (1138); [87] Nb (1088), Ta (1068); [96] Mo (1228), and W (1248). [97] It is noteworthy that in the case of molybdenum, with seven isotopes of natural abundance greater than 9 %, it was possible to use 16 (symmetrical) 16 O 2 or 18 O 2 species to calculate an upper limit to the angle (1258), and more than 40 isotopomers to calculate a lower limit (1198). RuO 2 was reported [98] to have a bond angle of 1498, and if RhO 2 and IrO 2 are linear, as indicated by ESR measurements, [99] then the general pattern for the second-and third-row transition element dioxides appears to be similar to that established for the first row.…”

Metal Cluster Models for Heterogeneous Catalysis: A Matrix‐Isolation Perspective

“…Furthermore, trioxides MO 3 have been obtained for M=Cr, Fe, Mo, Ru, W, Re, Os, and potentially for Pt, and tetroxides MO 4 have been obtained for Ru, Os, and Ir . For example, Iron oxide, FeO, by annealing forms the side‐on FeO(O 2 ) complex that by irradiation with visible light forms FeO 3 .…”

Eine kritische Bewertung der experimentellen Daten über Molekülstruktur und Spektren der Halogenide, Oxide und Hydride der s-, d- und f-Block-Elemente

“…(2) und (4)] dieselbe Intensität und Frequenz, da gilt sin 2 q cos 2 q. Man beachte die in Abbildung 6 dargestellte, drastische ¾nderung von CrO 2 zu MnO 2 in Hinblick auf Wenn wir uns nun den Übergangsmetallen der zweiten und dritten Reihe zuwenden, stellen wir fest, daû die Oxide der frühen Elemente wie die der Elemente der ersten Reihe streng nichtlinear sind: Zr und Hf (1138), [87] Nb (1088), Ta (1068), [96] Mo (1228) und W (1248) [97] (wiederum ohne Fehlerbereich). Bemerkenswert ist, daû es im Fall von Molybdän, bei dem sieben natürliche Isotope mit einem gröûeren Anteil als 9 % vorkommen, möglich war, 16 (symmetrische) 16 O 2oder 18 O 2 -Verbindungen zur Berechnung eines oberen Grenzwerts für den Bindungswinkel (1258) und mehr als 40 Isotopomere zur Berechnung eines unteren Grenzwerts (1198) heranzuziehen.…”

“…Darüber hinaus wurde die Zuordnung von n 1 angezweifelt. [97] Wenn MoO 3 planar sein sollte, würde dies mit Daten über WO 3 [11] und RuO 3 [98] übereinstimmen, die bekanntlich beide D 3h -konfiguriert sind. UO 3 ist in dem Sinn eine Ausnahme, daû es in Argon-Matrices offensichtlich T-förmig ist und daher ausführlich untersucht wurde.…”