Organometallic compounds, addition conductivity

An extensive study on the use of benzothiazoles as carbonyl equivalents has been conducted (78TL5, 9). The 2-lithiobenzothiazole (576) readily adds to carbonyl compounds to furnish on dehydration of the carbinol a vinylbenzothiazole (578). The benzothiazole nucleus can then be unmasked by a sequence of reactions involving (a) Af-methylation with methyl fluorosulfonate, (b) addition of either hydride (NaBKU) or an organometallic (MeLi) to afford the iV-methylbenzothiazoline and (c) hydrolysis of the crude Af-methylbenzothiazo-line (e.g. AgN03). A representative example is shown in Scheme 126. 

A nonstandard synthesis of the first uranium cluster containing an isopolyoxo-metalate core was reported recently [310b], Reduction of [Cp UCl2] (Cp7 — 1,2,4-/-Bu3C5H2) with two equivalents of KC8 in THF, followed by an addition of two equivalents of pyridine N-oxide, was conducted in an attempt to produce the organometallic dioxo species [Cp7U02]. However, the cluster compound [Cp (bipy)2][U6013] was isolated instead as the main product (54% yield) from this reaction. 

An additional family of organometallic materials is the cyanometallates, which are Prussian blue analogues. These are microporous materials, similar to zeolites, with relatively large adsorption space and small access windows [237-241], These Prussian blue analogues develop zeolite-like structures based upon a simple cubic (T[M(CN)6]) framework, in which octahedral [M(CN)6]" complexes are linked via octahedrally coordinated, nitrogen-bound Tm+ ions [237], In the prototypic compound, that is, Prussian blue, specifically (Fe4[Fe(CN)6]3 14H20), charge balance with the Fe3+ ions conducts to vacancies at one-quarter of the [Fe(CN)6]4 complexes [242],... 

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