Reactions of ferrocene-derived bis(hydroxymethyl) phosphine sulfides FcCH(R)P(S)(CH2OH)2 (R=H, CH3) with cyclic thionylphosphazenes: crystal structures of FcCH2P(S)(CH2O)2PN(NPCl2)[NS(O)Ph] and FcCH2P(S)(CH2O)2PN2P[N(Me)CH2]2[NS(O)Ph] (Fc=ferrocenyl)

The cyclic six-membered thionylphosphazenes, (NPCl2)2[NS(O)X] X=Cl (1), Ph (2) and 4-ClC6H4 (3) as well as the monospirocyclic derivatives (NPCl2)NP[N(Me)CH2]2[NS(O)Ph] (4) and (NPCl2)NP[N(Me)CH2]2[NS(O)4-ClC6H4] (5) were synthesized. Reactions of these compounds were carried out with dilithiated ferrocene-derived hydroxymethyl phosphine sulfides, FcCH2P(S)(CH2OH)2 (6) and FcCH(CH3)P(S)(CH2OH)2 (7) under different conditions. Reactions of 1 with 6 and 7 did not yield any desired products. In contrast, 1:1 reactions of 2 with 6 and 7 readily yielded air stable monospirocyclic compounds FcCH2P(S)(CH2O)2PN(NPCl2)[NS(O)Ph] (8) and FcCH(CH3)P(S)(CH2O)2PN(NPCl2)[NS(O)Ph] (9), respectively. Controlled reactions of 4 and 5 with 6 were performed in which dispirocyclic compounds FcCH2P(S)(CH2O)2PN2P[N(Me)CH2]2[NS(O)Ph] (10) and FcCH2P(S)(CH2O)2PN2P[N(Me)CH2]2[NS(O)4-ClC6H4] (11) were isolated. The product obtained in the 1:1 reaction of HOCH2(CF2)2CH2OH with (NPCl2)2[NS(O)4-ClC6H4] (3) when reacted with 6 resulted in the dispirocyclic compound FcCH2P(S)[(CH2O)2PN2P (OCH2CF2)2][NS(O)4-ClC6H4] (12). Compound 12 was found to exist as isomers. To confirm the formation of isomers, {[CH2N(Me)]2PN2P(OCH2CF2)2}[NS(O)Ph] (13) was synthesized by the reaction of 4 with HOCH2(CF2)2CH2OH which was also found to exist as isomers. Attempts to synthesize intermolecular bridged compounds of 2 with 6 and 7 resulted in compounds 8 and 9 exclusively. The crystal structures of compounds 8 and 10 were determined.