The related anthracene as well as potassium derivatives are well known.
Structure of (C6H5)3CNa(thf)3 ("trityl sodium"), omitting all but the oxygen of the thf ligands. Selected distances: rNa-C(central)=256 pm, rNa-C(ipso) = 298 pm (avg of three).
Simple organosodium compounds such as the alkyl and aryl derivatives are generally insoluble polymers. Because of the its large radius, Na prefers a higher coordination number than does lithium in organolithium compounds. Methyl sodium adopts a polymeric structure consisting of interconnected [NaCH3]4 clusters. When the organic substituents are bulky and especially in the presence of chelating ligands like TMEDA, the derivatives are more soluble. For example, [NaCH2SiMe3]TMEDA is soluble in hexane. Crystals have been shown to consist of chains of alternating Na(TMEDA)+ and CH2SiMe− 3 groups with Na–C distances ranging from 2.523(9) to 2.643(9) Å.
Although organosodium chemistry has been described to be of "little industrial importance", it once was central to the production of tetraethyllead. A similar Wurtz coupling-like reaction is the basis of the industrial route to triphenylphosphine:
3 PhCl + PCl3 + 6 Na → PPh3 + 6 NaCl
The polymerization of butadiene and styrene is catalyzed by sodium metal.
Organic derivatives of the heavier alkali metals
Organopotassium, organorubidium, and organocaesium are less commonly encountered than organosodium compounds and of limited utility. These compounds can be prepared by treatment of alkyl lithium compounds with the potassium, rubidium, and caesium alkoxides. Alternatively they arise from the organomercury compound, although this method is dated. The solid methyl derivatives adopt polymeric structures. Reminiscent of the nickel arsenide structure, MCH3 (M = K, Rb, Cs) has six alkali metal centers bound to each methyl group. The methyl groups are pyramidal, as expected.
Evidence for the formation of heavy alkali metal-organic intermediates is provided by the equilibration of cis-2-butene and trans-2-butene catalysed by alkali metals. The isomerization is fast with lithium and sodium, but slow with the higher alkali metals. The higher alkali metals also favor the sterically congested conformation. Several crystal structures of organopotassium compounds have been reported, establishing that they, like the sodium compounds, are polymeric.
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