Insertion into phosphorus-silicon bonds

Difluorocarbene generated by the thermolysis of trimethyltnfluoromethylsilane reacts with disilanes by insertion into the silicon-silicon bond [S] (equation 9) Thermolysis of pentafluoroethyltnfluorosilane at 200 °C gives tetrafluoro ethylidene carbene, which reacts with phosphorus trifluonde to give trifluoro vinyltetrafluorophosphorane [9] (equation 10) and with perfluorotnmethylphos-phine to give perfluorodimethyhsopropylphosphine and perfluoro-2-butene [9] (equation 10)... 

Insertion into the phosphorus silicon bond primarily generates a phosphaalkene, which splits off trimethylsilylthiolate and frees the phosphathioketene 1. A renewed addition of the phosphide followed by a splitting off of thiolate finally yields the diphosphaallene 2 [Eq. (54)]. 

Polozov, A.M., Mustaphin, A.H., and Khotinen, A.V., Insertion of carbenes into P-H bonds. Part 5. Synthesis of new phosphonates and phosphinates in reactions catalysed by Cu, Pd, Rh, Ni complexes. Phosphorus, Sulfur Silicon Relat. Elem., 73, 153, 1992. 

Carbon dioxide can also form carbamates by reaction with amides of non-metallic elements [78-84, 136-144]. Most examples reported in the literature deal with amides of silicon, germanium, and phosphorus. Among these, the insertion of the heterocumulene into the P-N bond of hexaalkylphosphorus triamides P(NR2)3, which affords phosphocarbamates species of formula P(NR2)3 (02CNR2) t, has received particular attention for its potential in chemical synthesis, because this reaction opens a route to the phosgeneless synthesis of carbamate esters [138,139] and ureas [140]. 

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