Reaction of group iv hydrides with fluoroacetylenes

• Published in: Journal of organometallic chemistry Vol. 6; no. 2; pp. 117 - 125
• Main Authors: Cullen, W.R., Styan, G.E.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 1966
• ISSN: 0022-328X; 1872-8561
• DOI: 10.1016/S0022-328X(00)93646-5

Hexafluoro-2-butyne reacts easily with the tin hydrides R 3SnH (R = alkyl) to give mainly trans-R 3SnC(CF 3)C(CF 3)H. The dihydride, (n-C 4H 9) 2SnH 2, reacts similarly. (CH 3) 3SiH and (C 2H 5) 3GeH add to the butyne on UV irradiation. In the case of the silane a 1:2 adduct, (CH 3) 3SiCHCF 3CHCF 3Si(CH 3) 3, is also produced. Heating (CH 3) 3SiH and CF 3CCCF 3 yields both 1:1 and 1:2 adducts. (CH 3) 3SnH and CF 3CCH give the non-terminal adducts (CH 3) 3SnC(CF 3)CH 2 and the cis- and trans-isomers of the terminal adducts. The mechanism of these reactions is discussed and evidence is presented suggesting that tin hydride additions to alkynes involve some degree of nucleophilic attack by the hydride.