Reaction of KIn(CH₂CMe₃)₃H with Chlorodiphenylphosphine

Abstract

The reaction between KIn(CH 2 CMe 3 ) 3 H and ClPPh 2 in pentane or benzene produces significant yields of two indium-phosphorus compounds, (Me 3 CCH 2 ) 2 -InPPh 2 and (Me 3 CCH 2 ) 3 In‚P(CH 2 CMe 3 )Ph 2 . This unexpected adduct incorporates a neopentyl group that was originally a substituent on the indium reagent. The other products of the reaction are CMe 4 , H 2 , and KCl. The formation of all products is explained by a set of experimentally verified reactions.

Reactions of Neopentylindium(III) Derivatives with Isopropylphosphorus Compounds

“…The indium hydride In(CH 2 CMe 3 ) 2 H was unstable and rapidly decomposed , to H 2 , indium metal, and In(CH 2 CMe 3 ) 3 (eq 11). Thus, the source of hydrogen gas and indium metal in the isopropyl phosphine system is the decomposition of In(CH 2 CMe 3 ) 2 H. To ensure that hydrogen gas was not a product of a reaction between KIn(CH 2 CMe 3 ) 3 H with HP(i-Pr) 2 as in the phenylphosphine system, the reagents were combined as a benzene solution. No H 2 was formed in 14 days at room temperature.…”

“…4 However, when ClPPh 2 was used, the products included [(Me 3 CCH 2 ) 2 InPPh 2 ] n , (Me 3 CCH 2 ) 3 In‚P(CH 2 CMe 3 )Ph 2 , and H 2 . 5 In the following paper the results of our investigations of the reactions that occur in the ClP(i-Pr) 2 system are described. The detailed chemistry was different from the other two chlorophosphines as [(Me 3 -CCH 2 ) 2 InP(i-Pr) 2 ] 2 , (Me 3 CCH 2 ) 3 In‚P(H)(i-Pr) 2 , (Me 3 -CCH 2 ) 3 In‚P 2 (i-Pr) 4 , (Me 3 CCH 2 ) 3 In‚P(CH 2 CMe 3 )(i-Pr) 2 , and H 2 were formed.…”