Oxidation alkoxo derivatives

PtMe2(OR)(N-N)(OH2)] OH (47) (Eq. 6.16) [30, 31]. These complexes, likely resulting from an oxidative ROH addition, were characterized by elemental analysis, IR and NMR spectroscopy, conductivity measurements and conversion to derivatives containing weakly coordinating bulky anions. These reachons are of interest because they represent the first examples of oxidation of plahnum(ll) complexes with alcohols and provide the first stable alkoxoplahnum(lV) complexes. The alkoxo-platinum(lV) bond is inert against solvolysis by alcohols, water and even dilute perchloric acid. 

Oxo complexes are important aspects of the high valent chemistry of Nb and Ta. Much of the interest derives from their use as soluble reactivity models of metal oxo fragments relevant to heterogeneous oxidation catalysis. Volatile or hydrolysable alkoxo species have been explored as precursors for oxide films. 

Mono-Cp and bis-Cp titanium hydrido derivatives have been reviewed.1027 The hydrido alkoxo complex Cp 2Ti(H)(OMe) is obtained by oxidative addition of CH3OH to Cp 2Ti, generated from Cp 2Ti(Me3SiC=CSiMe3).1363... 

Other examples which strongly support the existence of a metal-metal double bond are furnished by the dinuclear alkoxo-bridged dimers (10). Several synthetic procedures have been reported for the preparation of these compounds. They include the oxidation of quadruply bonded tungsten compounds in alcoholic HCl solutions, the oxidation of [W2Cl9] in alcohols, the electrolytic reduction of alcoholic solutions of WCle and the alcoholysis of WCU. Other alkoxy derivatives can be prepared by a simple alcohol exchange reaction."... 

The remarkable utility of the amide route has been established by the synthesis of alkoxides of molybdenum and tungsten (M) in their lower oxidation states (+3 or +4), e.g. [M(0R)3] and [M(OR)4] . Derivatives of the empirical formula M(OR)3 are of special interest as, in these, association occurs primarily through the formation of metal-metal triple (M=M) bonds rather than through the normal alkoxo bridges (Eq. 2.113)... 

As discussed in Section 8.02.3.4.3, nitrous oxide (N=N=0) and aryl azides (N=N=NAr) react with nickel alkyls giving alkoxo and amido complexes as the result of the insertion of 0x0 or nitrene units in the Ni-G bond. Nickelacyclopentanes react in the same fashion, affording cyclic alkoxo and amido derivatives,... 

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