Ternary oxides, reduced

Our work was initiated on the reduced ternary molybdenum oxides with the thought that the metal cluster electron count (MCE) should be variable for the Mo308 cluster units. Based on Cotton s previous molecular orbital treatment of such clusters (16) it appeared that MCE s from 6 to 8 could be accommodated, but it was not clear whether the seventh and eighth electrons would occupy bonding or antibonding orbitals with respect to the M-M interactions. We thus set about to determine this from structural data on suitable compounds. The attempted replacement of Zn2+ with Sc3+ to secure the compound ZntSc°Mo308 was conducted via the reaction shown in equation 1. 

R. E. McCarley No, we have done very little work along this line, although I think important results will be obtained from studies of mixed 0, S phases. So far we have found no direct structural analogies between the reduced ternary molybdenum oxide phases and the various ternary sulfide or selenide phases of the Chevrel type. 

When the terbium content in the ternary oxides is increased, the oxygenreleasing peaks of these oxides move to lower temperatures and higher values. This shows that doping Tb into CeC>2 will make CeC>2 systems more easily reduced. 

The astute reader will recognize that this compound is a metal-metal bonded adaptation of the well-known hollandite structure (19). Further, the metal cluster configuration is like that in CsNb Cl.. (20), though the latter compound possesses a double layer structure rather than the tunnel structure observed here. Finally these new structures provide only a glimpse of what is possible, and an excitement about new compounds of unusual structure and properties yet to come from studies of highly reduced ternary and quaternary refractory metal oxide systems. 

Nakamura T., Isothermal decomposition of ternary oxide AxByO on an isobar-stability of perovskite ABO3 (A = La, Sm, Dy B = Mn, Fe) in a reducing atmosphere. J. Solid State Chew. 38 (1981) pp.229 -238. 

However, this approach could not be used to establish the absolute stereochemistry of hydrogen transfer because the reduced and oxidized forms of S-deazaflavin, once released from the enzyme, undergo a rapid scrambling reaction that results in racemization at C-5 of the reduced species (83). Nevertheless, subsequent X-ray crystallographic measurements on the stable ternary enzyme-FAD-NADP complex demonstrated that the re and si faces of the isoalloxazine and nicotinamide rings (respectively) are next to one another (74) ... 

Several ternary oxides of formula A M02 (A = Na, K M = Co, Cr) have been synthesized by solid-state reactions. Depending on the stability and the reducing character of the materials obtained, various synthesis methods may be used. They are described here from the simplest to the most sophisticated. 

Additional areas of lanthanide halide chemistry that have been reviewed include the synthesis, phase studies, and structures of complex lanthanide halides - compounds formed between one or more group 1 cation and lanthanide element halides (Meyer 1982). Halides in combination with lanthanide elements in the II, III, and IV oxidation states were considered with the chemistry of the heavier halides being emphasized. More recently the reduced ternary lanthanide halides (Meyer 1983) and the reduced halides of the lanthanide elements were reviewed (Meyer 1988). The latter review considered lanthanides in which the formal oxidation state of the cation was 2 and included hydride halides, oxide halides, mixed-valence ternary halides, and reduced halide clusters. Corbett et al. (1987) discussed the structures and some bonding aspects of highly reduced lanthanide halides and compounds stabilized by a second-period element bound within each cluster, e.g., SC7CIJ2B, SC5CI5B, YjCljC. 

Li H, Zhang Y, Chang G, Liu S, Tian J, Luo Y, Asiri AM, Al-Youbi AO, Sun X. Environmentally friendly photocatalytic synthesis of potphyrin/Ag nanoparticles/reduced graphene oxide ternary nanohybrids having superior catalytic activity. ChemPlusChem 2012 77 545-50. 

Hayashi H, Lightcap IV, Tsujimoto M et al (2011) Electron transfer cascade by organic/inorganic ternary composites of porphyrin, zinc oxide nanoparticles, and reduced graphene oxide on a tin oxide electrode that exhibits efficient photocurrent genraation. J Am Chem Soc 133(20) 7684-7687... 

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