Untersuchungen zur Metallierung der Cyclophosphane P4(Cme3)3(Sime3), P4(Cme3)2(Sime3)2, P4(Sime3)4 |
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| Authors: | G Fritz J Hrer K Stoll |
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| Institution: | G. Fritz,J. Härer,K. Stoll |
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| Abstract: | Investigations Concerning the Metallation of the Cyclotetraphosphanes P4(Cme3)3(Sime3), P4(Cme3)2(Sime3)2, and P4(Sime3)4 The reaction of white phosphorus with LiCme3 and me3SiCl yields P4(Sime3)(Cme3)3 1 . With n-buLi this crystalline cyclotetraphosphane forms the crystalline LiP4(Cme3)3. In the same manner, n-buLi, with trans-P4(Sime3)2(Cme3)2 2 to yields LiP4(Sime3)(Cme3)2, which in contrast to LiP4(Cme3)3 decomposes within a few hours yielding P(Sime3)2n-bu 6 , P(Sime3)3 8 , LiP(Sime3)2 9 and also the cyclic compounds P4(Sime3)(Cme3)3 10 , LiP4(Cme3)3 11 and LiP3(Cme3)2 12 . The composition of the product mixture depends on the molar ratio of 2 to LiC4H9. At a molar ratio of 1:1 11 and 12 are not jet observed. At molar ratios of 1:1.5 and 1:2 P(Sime3)3 is not found. The amount of 11 and 12 grows with increasing concentration of n-buLi. On addition of n-buLi the solution of P4(Sime3)4 immediately turns red. Li3P7 and Li2P7(Sime3) (among others) are formed so fast that the first intermediates in the lithiation sequence so far could not be elucidated. These results demonstrate clearly that replacement of two me3Si groups in P4(Sime3)4 by two me3C groups excludes the rearrangement of LiP4(Sime3)(Cme3)2 to a P7-molecule. |
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