Phosphides, from lithium reaction

Heterometallic alkali metal phosphide complexes with transition metals have also been reported. The complex [(Cy2P)3Hf(ju.-PCy2)2Li (DME)] results from the reaction of LiPCy2 with HfCl4(THF) (98). This complex persists in solution. Jones et al. have reported the synthesis and reactivity toward a range of electrophiles of a series of lithium di-t-butylphosphido(alkyl)cuprates [RCu(PBu2)Li] (R = Me,... 

Organosilylphosphines are conveniently prepared by cleavage of alkyldiaryl-phosphines with lithium in THF, followed by treatment with chlorotrimethyl-silane,15 and tris(trimethylsilyl)phosphine has been prepared from the reaction of chlorotrimethylsilane with a mixture of sodium and potassium phosphides.16... 

Several reports have appeared of the application of unusual organometallic reagents in phosphine synthesis. Treatment of 2-lithiopyridine with anhydrous zinc chloride results in the formation of a 2-pyridylzinc reagent which can be used to introduce the 2-pyridyl group at phosphorus in a controlled manner. Thus, e.g., in its reaction with phenyldichlorophosphine, the 2-pyridyl-(phenyl)chlorophosphine (15) is formed. This has then been converted via the phosphide route into a new class of binucleating ligands (16). The sterically crowded dichlorophosphine (17) (accessible from the reaction of phosphorus trichloride with lithium diphenyl(2-pyridyl)methanide) is converted into the thermally stable phosphirane (18) on treatment with calcium, strontium or barium cyclooctatetraenide.The reaction of phenyldichlorophosphine with the readily accessible titanacycle (19) affords a convenient route to the phosphetene (20). ... 

The ladder structures found in 5-block amides are common structural motifs in phosphides as well. Solvent free [LiP(SiMe3)2]6 displays such an arrangement in the solid state, with four five-coordinate and two four-coordinate P atoms and four three-coordinate and two two-coordinate Li atoms the Li—P distances range from 2.38 A to 2.63 A (see Figure 52)." Li4(/X2-PR2)20 3 PR2)2(TFIF)2, formed from the reaction of P(SiMe3)3 with Bu Li in TFIF, has a fused tricyclic (LiP)4 ladder skeleton. The Li atoms are three-coordinate, with each of the two terminal lithiums bound to two P atoms and one THF, while the two internal lithiums have three phosphorus atoms as neighbors (see Figure 53)." " In solution, there is no NMR evidence for Xi- P... 

It is known from the preceding research that phosphorus-rich silylphosphanes or their related lithium phosphides undergo, with LiBu in ether, reactions in which a structural transformation occurs, as shown in Scheme 16 20). The reactions of the partially silylated tri- and cyclotetraphosphanes were explored in order to come closer to understanding the above reactions. It can be taken for granted that the P—C bond is not affected in such reactions. 

Some interest in group 12 phosphide and arsenide complexes has come from their possible applications as precursors for IFV semiconductors (see Semiconductors). They can be prepared by two different ways, namely, by metaUa-tion reaction of phosphines and arsines with diorganozinc compounds (equation 32), and by transmetallation reaction between organozinc halides and lithium salt of the corresponding phosphines and arsines (equation 33). 

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