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Advanced Inorganic Chemistry, Third Edition by F. Albert, And Geoffrey Wilkinson, Cotton

By F. Albert, And Geoffrey Wilkinson, Cotton

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39 The s t r u c t u r a l f e a t u r e s of t h e s e h a l i d e s a r e now w e l l understood and have been extens i v e l y documented (118, 181, 428, 5 5 2 ) . I n summary, based upon s t r u c t u r a l a n a l y z e s on NbgF15 (5531, NbgC114 ( 5 9 5 ) , TagC115 (40) I T a g B r l 5 (401, and Tag114 ( 4 1 ) , a l l t h e h a l i d e s of t h e t y p e s MgX14 and MgX15 a r e found t o c o n t a i n t h e [MgX12In+ c l u s t e r ( s e e s t r u c t u r e 13). * Of p a r t i c - u l a r s i g n i f i c a n c e i s t h e o b s e r v a t i o n t h a t no gross s t r u c t u r a l changes occur w i t h i n t h e [ M ~ x n+ I ~ cI l u s t e r s a s n i s v a r i e d from 2 t o 3 t o 4.

I I/x\ I 0 I On t h e b a s i s of lX/’ 0 10 I t h e i r i n f r a r e d s p e c t r a , T i O C 1 2 (216) , T i O B r 2 (219) , and T i 0 1 2 ( 2 2 1 ) must a l s o be polymeric oxygen-bridged species. On t h e o t h e r hand, Dehnicke and Weidlein ( 2 2 4 ) have s u g g e s t e d t h a t Z r O C 1 2 has an i o n i c l a t t i c e ( Z r O 2 + I m ( Z r O C l ~ 2 - ) m , s i n c e it has a f a i r l y h i g h zirconium-oxygen s t r e t c h i n g frequency (877 cm-’) ; t h e a u t h o r b e l i e v e s t h a t t h i s i s u n l i k e l y and t h a t , by analogy w i t h s p e c t r a l d i f f e r e n c e s observed between NboCl3 and MoOBr3, d i s c u s s e d p r e v i o u s l y , w e can e x p e c t 32 R .

The complexes formed by the trihalides and their probable structures, as deduced from spectral and magnetic data and conductance measurements, are summarized in the following reaction schemes (306, 312, 315, 317, 337).

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