Reactions of organotin compounds. VIII. The reactions of tin hydrides with perfluorovinyl silicon compounds

Abstract

The reactions of trimethyltin hydride and dimethyltin dihydride with (CH3)3SiCF=CFZ and (CH3),-Si(CF=CF2)2 respectively have been investigated. Under thermal conditions, reaction led to organotin fluorides and fluorovinyl-silanes. However, under ultraviolet irradiation at 2 5 O , addition products were isolated of which (CH3)3SiCFHCF2Sn(CH3)3 and (CH3)3SiCF[Sn(CH3)3]CFzH were fully characterized. Evidence is presented which shows that these addition products are formed by a free radical process and that their decomposition to organotin fluorides and fluorovinyl-silanes proceeds 11io a b-fluorine elimination. Spectroscopic data are presented for a number of new organo-silanes.

Reactions of organotin compounds. IX. The reactions of tin hydrides with perfluorovinyl germanium and tin compounds

“…The cl~aracter-ization of the addition products of trimethyltin hydride with (CH3),GeCF=CF2 and (CH,),-SnCF=CF, is based on their n.m.r. spectra, which are completely analogous to those of the addition products of trimethyltin hydride with (CH,),SiCF=CF, (5). The general pattern of the proton spectrum of these addition products is given in Fig.…”

“…Trimethyltin hydride reacted with (CH,),Si-CF-CF, in the presence of free radical sources (5) to form two addition products, (CH,),Si-CFHCF,Sn(CH,), and (CH,),SiCF [Sn(CH,),]-CF,H. These deposit trimethyltin fluoride at room temperature by P-fluorine elimination to give (CH,),SiCH=CF, and cis-(CH,),SiCF= CFH respectively.…”

“…All general techniques have been described previously (5). Trimethyltin hydride and dimethyltin dihydride were prepared by the procedure of Finholt et 01.…”

“…azobisisobutyronitrile), and ultraviolet irradiation (1-3, 5, 6), and the retardation caused by efficient scavengers (e.g. galvinoxyl (4,5)). We have also described the reactions of trimethyltin hydride and dimethyltin dihydride (5) with (CH,),SiCF=CF, and (CH,),Si(CF=CF,),, where conclusive evidence for a free radical mechanism was obtained again by the use of such a scavenger and initiators.…”

Reactions of organotin compounds. X. Reactions of tin hydrides with CF2=CFRe(CO)5, CF3CF=CFRe(CO)5, and some fluorinated alkenes

“…At 45" for48 h in butyronitrile, only a limited reaction occurred with the formation of cis-CFH=CFRe(CO), and CF2=CHRe-(CO), in approximately equal amounts. The reaction therefore occurs much less readily under thermal conditions than the comparable additions of trimethyltin hydride to perfluorovinyl-silicon, germanium, and tin derivatives (1,2).…”