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The reaction of PCl 3  at r. t. with an equimolar amount of NaR* in heptane gives the colorless phosphane R*PCl 2  (1), the colorless diphosphane R*ClP-PClR* (2), the light green diphosphene R*P=PR* (4), the cyclotetraphosphane R* 2 P 4 Cl 2  (6) (not isolated), the light yellow bis(cyclotriphosphanyl) P 6 R* 4  (7), the cyclotriphosphane R* 2 P 3 Cl (8) (not isolated), and the colorless bicyclophosphane P 4 R* 2  (9).With a threefold molar amount of NaR* in tetrahydrofuran the blue violet triphosphanide NaP 3 R* 2  (10), the dark red tetraphosphanide NaP 4 R* 3  (11), and the orange pentaphosphanediide Na 2 P 5 R* 3  (12) are formed from PCl 3  besides the phosphanides NaPR* 2 , Na 2 PR* (isolated), NaP 2 R* 3  and Na 2 P 2 R* 2 . With a four-fold molar amount of KR* in benzene PCl 3  gives the green diphosphanediide K 2 P 2 R* 2  and the red phosphanediide K 2 PR*, and with an equimolar amount of ZnR* 2  in heptane the compounds 1, 2, 4, 7 and 8 are obtained. The compound R*P=PR* (4), the first diphosphene with two silyl substituents, is formed in high yields from the action of Na on R*PCl 2  in heptane at 90 "C. It gives a [2+4] cycloadduct with 2,3-dimethylbutadiene and phosphanides (Na 2 P 2 R* 2  or Na 2 PR*) with Na or NaR*. Bicyclotetraphosphane P 4 R* 2  (9) (structure: two R*P 3  rings with a common edge) is exclusively obtained from Na 2 P 4 R* 2  (formed quantitatively from P 4  and 2 NaR*) and TCNE. 9 may be reduced (Na, THF) with reformation of Na 2 P 4 R* 2  and reacts in the presence of NaR* with formation of dark red NaP 4 R* 3  (11) (structure: P 3  ring with two R* substituents in trans position and one PNaR* substituent). Straightforward syntheses of halogenophosphanes include (i) reactions of ZnR* 2  with PCl 3  or PBr 3  (mole ratio 1 : 2) in heptane to form R*PCl 2  (1) or R*PBr 2 , and (ii) reaction of R* 2  with R*PCl 2  (mole ratio 1 : 2) without a solvent, or of KR* and PCl 3  (mole ratio 2 : 1) in benzene to formR*ClP-PClR* (2). The halogenophosphanes R* 2 P 3 Cl (8) (structure: P 3  ring with two R* substituents in trans position and one Cl substituent) as well as R*2P 4 Cl 2  (6) (structure: P 4  ring with alternating R* and Cl substituents) have not been isolated. The  31 P-NMR spectra and the pathways of formation of the phosphorus compounds are discussed

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Zur Reaktion von PCl3 mit NaR*, KR* und ZnR*2 (R* = SitBu 3 ) [1]: Bildung des Diphosphens R*P=PR*, Tetraphosphans P 4 R *  2  , Tetraphosphanids NaP 4 R *  3  sowie von Halogenphosphanen R *  m P m Cl p  / On the Reaction of PCl 3  with NaR*, KR* and ZnR* 2  (R*= Si t Bu 3 ) [1]: Formation of the Diphosphene R*P=PR*, Tetraphosphane P 4 R* 2 , Tetraphosphanide NaP 4 R* 3  as well as Halogenophosphanes R* m P n Cl p