Cyclophosphazenmetalloxide, eine neue Verbindungsklasse, und Modellverbindungen für Polymerisationen von Phosphazenen

Abstract

plausibel: Im ersten Schritt reagiert 1 mit zwei Aquivalenten Titantetrachlorid zu 5. Dies zerfallt dann sehr schnell in einer S,,-Reaktion zu 3 und einem Aquivalent PhBCl,. Das entstandene PhBCl, setzt sich rnit einem weiteren Aquivalent 5 zu 4 um, wobei zwei Aquivalente Titantetrachlorid frei werden, die wiederum mit 1 reagieren. Die Struktur von Verbindung 3 1aRt sich als ein geometrischer Korper beschreiben, dessen Oberflache aus vier gebogenen, nicht regelmaBigen Vierecken besteht, oder als ein [**I Diese Arheit wurde vonUnilever Research, Port Sunlight, und der Unwer-Angen. Cheni. 104 (1992) N r . 5 VCH krlagsgesellschafi m h H , W4940 Weinhein?. 1992 ~1044-8249/92/0505-0~15 3 3.50 + .ZS/O

Synthesis and Structural Characterization of P-Functionalized Metallacyclophosphazenes

“…Both compounds exhibit an essentially planar six-membered ring with obtuse angles at the nitrogen atoms and acute angles at both the phosphorus and metal atoms, a feature that has been found also in the structures of the previously investigated phenyl- 2c and CF 3 -substituted vanadacyclophosphazenes 3 and the phenyl-substituted molybdenum heterocycle 2a. Both compounds have almost planar NMe 2 groups, a common feature of dimethylamino heteroelement compounds .…”

“…The synthesis of metallacyclophosphazenes bearing carbon on phosphorus proceeds straightforwardly from metal halides in their highest oxidation states with evolution of hydrogen chloride . However, a different strategy has to be employed for P-functional heterocycles.…”

“…Variation of the substituents on phosphorus was limited to carbon species such as CF 3 , Me, 4-ClC 6 H 4 , and a cyclic amine, N(CH 2 ) 2 O, respectively. The chemistry of these systems was limited to ligand exchange at the metal center 2b, and polymerization reactions of the phenyl-substituted systems . We were interested in elucidating the reactivity of the phosphorus-bound substituents under retention of the ring skeleton.…”

Neue Cyclophosphazene mit Metallen der III. Hauptgruppe als Ringbausteine / New Cyclophosphazenes with Metals of Main Group III as Building Blocks

“…Seit 1986 ist es uns gelungen, verschiedene Ü bergangsm etalle m it form al h o h er O xidations stufe in Phosphazenringsystem e zu in k o rp o rieren [1,2]. Spirocyclische C helatverbindungen von [H N PPh2N PPh2N H ]_ sind schon länger b ek an n t [3,4].…”

First Unsolvated and Unsilylated Barium Phosphazene Complex: Synthesis and Characterization

“…Cyclometallaphosphazene complexes having transition metal as building block were first discovered by Roesky et. Many cyclophosphazene have been used in oxidation catalyst, polymerization and for generating new materials [8][9][10][11][12]. in 1986 [7-8].…”