Phosphorus(III) and phosphorus(V) compounds with ferrocenolato and 1,1′-ferrocendiolato substituents

Starting from ferrocenol, FcOH, and various chlorides of both three and five valent phosphorus, a series of mono-to trinuclear ferrocenolato derivatives Ph3-nP(OFc)(n) (n = 1 (1), 2 (2), 3 (3)), (FcO)(2)(P2N2Bu2)-Bu-t (4) as well as RP(E)(OFc)(2) (E = O, S; R = Cl (9a,b), OFc (10a,b), Me (11), Bu-n (12), Ph (13), Fc (14)), has been prepared. The corresponding reactions of the bifunctional 1,1'-ferrocenediol, fc(OH)(2), have been studied as a route to ferrocenophanes such as fcO(2)[(P2N2Bu2)-Bu-t] (5), fcO(2)PR (R = Cl (6), Ph (8)), fcO(2)P(O)R (R = Cl (15), Me (16), Bu-n (17), Ph (18), Bu-t (19), Fe (20), OFc (21)), fcO(2)[PO(2)fc](2) (7) and fcO(2)[P(O)O(2)fcl(2) (22). The new compounds have been characterized by a consistent set of H-1-, C-13-, and P-31-NMR spectroscopic data. In the case of 2-phenyl-1,3-dioxa-2-phospha-[3]ferrocenophane fcO(2)PPh (8), the molecular structure has been determined by a single crystal X-ray structure analysis.