Oxidation states mixed

Bonds to Oxygen.—Compounds of Lower Oxidation State. Mixed sulphur-phosphorus anhydrides result when sulphonic acids and dialkyl hydrogen phosphites react according to equation (17).448 Further work on the preparation of trimethylsilyl esters of phosphorous acids has been carried out by... 

Some interesting examples of early high oxidation state-late low oxidation state mixed metal-metal organome-tallics with RU4 unit have been prepared.An example is shown in Equation... 

The reduction of molybdate salts in acidic solutions leads to the formation of the molybdenum blues (9). Reductants include dithionite, staimous ion, hydrazine, and ascorbate. The molybdenum blues are mixed-valence compounds where the blue color presumably arises from the intervalence Mo(V) — Mo(VI) electronic transition. These can be viewed as intermediate members of the class of mixed oxy hydroxides the end members of which are Mo(VI)02 and Mo(V)0(OH)2 [27845-91-6]. MoO and Mo(VI) solutions have been used as effective detectors of reductants because formation of the blue color can be monitored spectrophotometrically. The nonprotonic oxides of average oxidation state between V and VI are the molybdenum bronzes, known for their metallic luster and used in the formulation of bronze paints (see Paint). 

Oxidation Catalysis. The multiple oxidation states available in molybdenum oxide species make these exceUent catalysts in oxidation reactions. The oxidation of methanol (qv) to formaldehyde (qv) is generally carried out commercially on mixed ferric molybdate—molybdenum trioxide catalysts. The oxidation of propylene (qv) to acrolein (77) and the ammoxidation of propylene to acrylonitrile (qv) (78) are each carried out over bismuth—molybdenum oxide catalyst systems. The latter (Sohio) process produces in excess of 3.6 x 10 t/yr of acrylonitrile, which finds use in the production of fibers (qv), elastomers (qv), and water-soluble polymers. 

Soda. Ash Roasting. Some of the first processes to recover selenium on a commercial basis were based on roasting of copper slimes with soda ash to convert both selenium and tellurium to the +6 oxidation state. Eigure 1 shows flow sheets for two such processes. Slimes are intensively mixed with sodium carbonate, a binder such as bentonite, and water to form a stiff paste. The paste is extmded or peUetized and allowed to dry. Care in the preparation of the extmdates or pellets is required to ensure that they have sufficient porosity to allow adequate access to the air required for oxidation. 

Sohd uranium—phosphate complexes have been reported for the IV and VI oxidation states, as well as for compounds containing mixed oxidation states of U(IV) and U(VI). Only a few sohd state stmctures of U(IV) phosphates have been reported, including the metaphosphate U(P03)4, the pyrophosphate U(P202), and the orthophosphate, CaU(PO4)2. The crystal stmcture of orthorhombic CaU(POis similar to anhydrite (194). Compounds of the general formula MU2(PO4)3 have been reported for M = Li, Na, and K, but could not be obtained with the larger Rb and Cs ions (195). In the sohd state, uranium(IV) forms the triclinic metaphosphate, U(P03)4. Each uranium atom is eight-coordinate with square antiprismatic UOg units bridged by... 

By heating the metal with appropriate oxides or carbonates of alkali or alkaline earth metals, a number of mixed oxides of Ru and Os have been made. They include NasOs Og, LifiOs Og and the ruthenites , M Ru 03, in all of which the metal is situated in octahedral sites of an oxide lattice. Ru (octahedral) has now also been established by Ru Mdssbauer spectroscopy as a common stable oxidation state in mixed oxides such as Na3Ru 04, Na4Ru2 07, and the ordered perovskite-type phases M Ln Ru Og. 

This indicates a change in the formal oxidation state of the iron from -F2.25 to -F2.5, and mixed Fe /Fe species have been postulated. Flowever, it appears likely that these clusters are best regarded as electronically delocalized systems in which all the Fe atoms are equivalent. 

Cobalt provides only a few examples of this oxidation state, namely some fluoro compounds and mixed metal oxides, whose purity is questionable and, most notably, the thermally stable, brown, tetraalkyl, [Co(l-norbomyl)4]. Prepared by the reaction of C0CI2 and Li(l-norbomyl), it is the only one of a series of such compounds obtained for the first row transition... 

Ni has a coordination sphere of 5 or 6 mixed S-, N-, 0-donors and is believed to undergo redox cycling between III, II and I oxidation states. 

As it turns out, a direct experimental measure of kEE for Mn(sar)3+/Mn(sar)2+ was later reported,35 making use of an ingenious method36 for evaluating electron exchange by the mixing of the enantiomeric forms in different oxidation states ... 

The magnetic properties of Pu compounds in different oxidation states are reviewed. New measurements on Pu(C8H8)2, PuFi, [(C2Hs)itN]2PuCl6, and [ (C2H5)itN]itPu(NCS)s are presented. The interpretation of the data is based on intermediate, j-j mixed crystal field states and orbital reduction due to covalency. Especially in the case of the organometallic compounds a large orbital reduction is found. 

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