C–H Activation of Cycloalkenes by Dimetallynes (M = Ge, Sn) under Ambient Conditions

Abstract

Treatment of the dimetallynes Ar'EEAr' [E = Ge, Sn; Ar' = C(6)H(3)-2,6-(C(6)H(3)-2,6-iPr(2))(2)] with a cyclic olefin-cyclopentadiene (CpH), cyclopentene, 1,4-cyclohexadiene (CHD), or cyclohexene-showed that, with the exception of cyclohexene, they react readily, affording C-H activation at room temperature. Reaction of the digermyne and distannyne with CpH gave the cyclopentadienyl anion, which is bound in a π-fashion to a mononuclear group 14 element center, along with evolution of hydrogen gas. Unusually, the digermyne also reacted with cyclopentene to give the same dehydroaromatization product, formed from triple C-H activation/dehydrogenation. It also was found to react with CHD to give a mixture of (Ar'GeH)(2), benzene, and a new 7-germanorbornadiene species bound to a cyclohex-2-enyl fragment.

Activation of Small Molecules by Compounds that Contain Triple Bonds Between Heavier Group‐14 Elements

“…Instead, the reaction selectively activates the C(sp 3 )À Hb ond in CpH to give 23 [32] or 24 [33] (Scheme 14). The expected Diels-Alder [4+ +2] cycloaddition was not observed.…”

Oxidation and Reduction

“…It was also found to react with CHD to give a mixture of (Ar GeH) 2 , benzene, and a new 7-germanorbornadiene species bound to a cyclohex-2-enyl fragment. 343 A 1,2-diphenyl-2,5-cyclohexadienyl rubidium complex isolated from the Birchtype reduction of 1,2-diphenylbenzene with rubidium metal in THF has been characterized. 344 The Ru(II) complex (192)-catalysed reductive amination of allylic alcohols RCH=CHCH 2 OH, by various amines R 1 R 2 NH to give R(CH 2 ) 3 NR 1 R 2 , in toluene was described; formic acid and the allylic alcohol act as the hydrogen source.…”

Anorganische Chemie 2011

“…Untersuchungen zur Reaktivität der schweren Homologen von Alkenen und Alkinen waren im Jahr 2011 ein Schwerpunkt in der Chemie der Elemente der Gruppe 14. So wurde für die Germanium(I)‐ und Zinn(I)‐Terphenyl‐Verbindungen ArGeGeAr und ArSnSnAr gezeigt, dass sie mit Cycloalkenen C‐H‐Aktivierungsreaktionen eingehen und Alkylderivate bilden 1_70…”