Download Halogen Chemistry by Viktor Gutmann (Eds.) PDF

By Viktor Gutmann (Eds.)

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Molecular orbital e n e r g y l e v e l s for (M^Xia)^"'' (this w o r k ) . V a l u a b l e confirmation of t h i s m o l e c u l a r o r b i t a l d i a g r a m could b e o b t a i n e d b y a s t u d y of t h e m a g n e t i c p r o p e r t i e s of t h e oxidized species (TagBrig)^"^. I f t w o u n p a i r e d electrons a r e o b s e r v e d , t h e m o l e c u l a r o r b i t a l d i a g r a m w o u l d a p p e a r t o b e correct, a l t h o u g h d i a m a g n e t i s m w o u l d n o t necessarily confirm or d e n y i t .

C C o t t o n a n d M a g u e (1964b). ^ C o t t o n a n d M a g u e (1964a). « F e r g u s s o n et al. ( 1 9 6 4 ) . / E l d e r a n d P e n f o l d (1965). 9 C o t t o n a n d L i p p a r d (1965). / 2-49 ReCla* 2-29 ( n o n - b r i d g i n g ) 2-40 (bridging) Rel—CI = 2-30 R e l l — C I = 2-29 Rel—Br = 2-48 R e l l — B r = 2-38 2-36 2-31 2-48 2-49 Cs3[(Re3Cl3)Cl,]i' [(Re3Cl3)Cle(Ph3P)3]'' R e — X (out of plane) (Â) R e — R e (Â) 2-72 2-57 2-66 ( b r i d g i n g ) 2-52 R e — X (centrifugal) (Â) 155° Cl_ReI—CI CI—Rell—CI Br—Rel—Br Br—Rel—IBr 163° 159° 158° 159° 153° 159° 134° X (out of plane)—Re^ X (out o f plane)* 178° 178° 181° 181° 183° 183° bridging X — R e bridging X^ TABLE V .

Mo6Cl8)Cl4 is insoluble in n i t r o b e n z e n e a n d a c e t o n i t r i l e , b u t is soluble in o t h e r u n i d e n t a t e d o n o r s o l v e n t s t o form [(Mo6Cl8)Cl4(EtOH)2] ( L i n d n e r , 1922; L i n d n e r et al, 1923), [(Mo6Cl8)Cl4(py)2], [(Mo6Cl8)Cl4(Et3N)2] (Sheldon, 1960a), [(Mo6Cl8)Cl4(MeSO)2] a n d [(Mo6Cl8)Cl4(DMF)2] ( C o t t o n a n d Cur­ tis, 1965). T h e s e r e a c t i o n s a r e reversible o n h e a t i n g . Similarly, [(Mo6Cl8)Cl4 (Ph3AsO)2], [(MoeCl8)Cl4(Ph3PO)2] (Sheldon, 1961a), [(MoeCl8)Cl4 (Ph3P)2] a n d [(Mo6Cl8)Cl4(pyO)2] ( J .

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