(Ferrocenylmethyl)phosphane (1) oxidation with hydrogen peroxide, elemental sulfur and grey selenium produced (ferrocenylmethyl)phosphane oxide 1O, sulfide 1S and selenide 1Se, respectively, as the first isolable primary phosphane chalcogenides lacking steric protection. At elevated temperatures, compound 1O disproportionated into 1 and (ferrocenylmethyl)phosphinic acid. In reactions with [(η6 -mes)RuCl2 ]2 , 1O underwent tautomerization into a phosphane complex [(η6 -mes)RuCl2 {FcCH2 PH(OH)-κP}], whereas 1S and 1Se lost their P-bound chalcogen atoms, giving rise to the phosphane complex [(η6 -mes)RuCl2 (FcCH2 PH2 -κP)] (Fc=ferrocenyl, mes=mesitylene). No tautomerization was observed in the reaction of 1O with B(C6 F5 )3 , which instead produced a Lewis pair FcCH2 P(O)H2 -B(C6 F5 )3 . Phosphane oxide 1O added to C=O bonds of aldehydes and ketones and even to cumulenes PhNCE (E=O and S). However, both PH hydrogens were only employed in the reactions with aldehydes and cyanates.
Keywords: metallocenes; phosphanes; primary phosphane chalcogenides; structure elucidation; synthesis.
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