Molecular Perchlorato Complexes of Iridium(I), Rhodium(I), and Cobalt(I)

✍ Scribed by Dr. J. Peone Jr; Prof. Dr. L. Vaska

• Publisher: John Wiley and Sons
• Year: 1971
• Tongue: English
• Weight: 233 KB
• Volume: 10
• Category: Article
• ISSN: 0044-8249
• DOI: 10.1002/anie.197105111

✦ Synopsis

Si-Fluorinated, C-chlorinated carbosilanes such as ( 3 d ) , ( 4 c ] , and ( 5 d ) are readily accessible in good yields, however, by photochlorination of the CH, groups in compounds of type (3 b ) -( 5 b) (see Table ). 'H-NMR studies of the reaction course in CC1, solution show that partially chlorinated derivatives, e.g. ( ) and (3f), can also be prepared in the same way. Compound ( 3 e ) may be obtained by fluorination of (3g)[2*41 with ZnF, at 80°C in acetonitrile or benzene, and (3h) likewise from (3 i) f71.

Si-Fluorinated, C-chlorinated carbosilanes are rapidly hydrolyzed by atmospheric moisture and differ considerably in their chemistry from the corresponding perchlorinated compounds. Thus (F,Si),CCl, ( I d ) reacts with LiCH, to give [(CH3)3Si],CC12, whereas in the case of (CI,Si),CCl, ( I c) methylation starts at the C-Cl bond and initially yields (C1,Si),C(CH,)C1131.