Phosphanchalkogenide und ihre Metallkomplexe. V. Derivate von [2.2]Paracyclophanylphosphanena

Abstract

Abstract The known compound diphenyl([2.2]paracyclophanyl)phosphane 1 reacted smoothly with elemental sulfur or selenium to give the phosphane chalcogenides 3 and 4. The corresponding chlorido- or bromido-gold(I) complexes were however not obtained by the usual reaction with (tht)AuCl or (tht)AuBr. For the latter, direct oxidation of the reaction mixture with elemental bromine led to small quantities of {(PCP)PPh2Br}+ [AuBr4]− 5 (PCP = [2.2]paracyclophanyl). Attempts to obtain the alkyl phosphane di-isopropyl([2.2]paracyclophanyl)phosphane 2 were at first unsuccessful because of contamination by the phosphonium derivatives [ i Pr2(PCP)PH]+X− (X = Cl 6, X = Br 7), but the mixture was found to react with elemental sulfur or selenium to give the phosphane chalcogenides 8 and 9. The gold(I) complexes (PCP) i Pr2PEAuX [E = S, X = Cl (10), Br (11); E = Se, X = Cl (12), Br (13)] were obtained by the reactions of 8 and 9 with (tht)AuX. The chlorido complexes 10 and 12 were oxidized by PhICl2 to the gold(III) complexes (PCP) i Pr2PEAuCl3 14 (E = S) and 15 (E = Se). An excess of PhICl2 led to the fully oxidized compound {(PCP) i Pr2PSeCl}+[AuCl4]− 16. The bromido complexes 11 and 13 were oxidized by elemental bromine to (PCP) i Pr2PEAuBr3 17 (E = S) und 18 (E = Se), the latter however with a poor yield. Further oxidation was not achieved. The reactions of the chalcogenides 3, 4, 8 and 9 with elemental iodine led to the products 19, 20, 21 (1:1 adducts) and 22 (1:1 adduct with additional disordered diiodine), respectively.