Ansa versus spiro substitution of cyclophosphazenes: Is fluorination essential for ansa to spiro transformation of cyclophosphazenes?

被引：45

作者：

Muralidharan, K

Venugopalan, P

Elias, AJ ^{[1
]}

机构：

[1] Indian Inst Technol, Dept Chem, Hauz Khas, New Delhi 110016, India

[2] Indian Inst Technol, Dept Chem, Kanpur 208016, Uttar Pradesh, India

[3] Panjab Univ, Dept Chem, Chandigarh 160014, India

来源：

INORGANIC CHEMISTRY | 2003年 / 42卷 / 10期

关键词：

D O I：

10.1021/ic034119v

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Fluorinated ansa substituted cyclophosphazenes endo-FcCH(2)P(S)(CH2O)(2)[P(F)N](2)(F2PN) [Fc = ferrocenyl] (1) and exo-FcCH(2)P(S)(CH2O)(2)[P(F)N](2)(F2PN) (2) readily transform to the spirocyclic compound [FcCH(2)P(S)(CH2O)(2)PN]-(F2PN)(2) (3) not only in the presence of CsF but also with non-fluorinated bases such as CS2CO3, K2CO3, KOBut, Et3N, DABCO, DBN, and DBU. The analogous tetrachloro ansa compound exo-FcCH(2)P(S)(CH2O)(2)[P(Cl)N](2)(Cl2PN) (5), however, did not transform to the chlorinated spiro compound (6) in the presence of these bases. With excess of CsF, P-Cl bonds of 5 were found to undergo fluorination leading to the formation of 2, which transformed to spirocyclic compound 3. Time dependent P-31 NMR spectroscopy was used to monitor this transformation. Crystal structure studies on the ansa substituted compounds 4 and 5 have shown weak bonding interactions involving C-(HCl)-Cl-..., C-(HO)-O-..., and C-(HS)-S-... interactions.

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页码：3176 / 3182

页数：7

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