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)
التفاصيل البيبلوغرافية
العنوان:
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, (NPCl 2 ) 2 [NS(O)X] X=Cl ( 1 ), Ph ( 2 ) and 4-ClC 6 H 4 ( 3 ) as well as the monospirocyclic derivatives (NPCl 2 )NP[N(Me)CH 2 ] 2 [NS(O)Ph] ( 4 ) and (NPCl 2 )NP[N(Me)CH 2 ] 2 [NS(O)4-ClC 6 H 4 ] ( 5 ) were synthesized. Reactions of these compounds were carried out with dilithiated ferrocene-derived hydroxymethyl phosphine sulfides, FcCH 2 P(S)(CH 2 OH) 2 ( 6 ) and FcCH(CH 3 )P(S)(CH 2 OH) 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 FcCH 2 P(S)(CH 2 O) 2 PN(NPCl 2 )[NS(O)Ph] ( 8) and FcCH(CH 3 )P(S)(CH 2 O) 2 PN(NPCl 2 )[NS(O)Ph] ( 9 ), respectively . Controlled reactions of 4 and 5 with 6 were performed in which dispirocyclic compounds FcCH 2 P(S)(CH 2 O) 2 PN 2 P[N(Me)CH 2 ] 2 [NS(O)Ph] ( 10 ) and FcCH 2 P(S)(CH 2 O) 2 PN 2 P[N(Me)CH 2 ] 2 [NS(O)4-ClC 6 H 4 ] ( 11 ) were isolated. The product obtained in the 1:1 reaction of HOCH 2 (CF 2 ) 2 CH 2 OH with (NPCl 2 ) 2 [NS(O)4-ClC 6 H 4 ] ( 3 ) when reacted with 6 resulted in the dispirocyclic compound FcCH 2 P(S)[(CH 2 O) 2 PN 2 P (OCH 2 CF 2 ) 2 ][NS(O)4-ClC 6 H 4 ] ( 12 ). Compound 12 was found to exist as isomers. To confirm the formation of isomers, {[CH 2 N(Me)] 2 PN 2 P(OCH 2 CF 2 ) 2 }[NS(O)Ph] ( 13 ) was synthesized by the reaction of 4 with HOCH 2 (CF 2 ) 2 CH 2 OH 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.
