15 research outputs found
Reversible Dissociation of a Dialumene
Dialumenes are neutral Al(I) compounds with Al=Al multiple bonds. We report the isolation of an amidophosphineâsupported dialumene. Our Xâray crystallographic, spectroscopic, and computational DFT analyses reveal a long and extreme transâbent Al=Al bond with a low dissociation energy and bond order. In solution, the dialumene can dissociate into monomeric Al(I) species. Reactivity studies reveal two modes of reaction: as dialumene or as aluminyl monomers
Hydrofunctionalisation of an Aromatic Triphosphabenzene
The aromatic heterocycle 2,4,6-tri-tert-butyl-1,3,5-triphosphabenzene reacts with a series of silanes, germanes and stannanes, with weaker E-H bonds reacting in an increasingly facile manner. All react by 1,4-addition to give bicyclic products with diastereomeric ratios varying with the substrate. Density functional theory (DFT) calculations show that activation of the E-H bond occurs across the 1,4-C/P axis of the triphosphabenzene, with the small energetic differences with respect to the stereochemistry of the addition offering insight into the experimentally observed diastereomeric ratios
A Transient Vinylphosphinidene via a PhosphireneâPhosphinidene Rearrangement
A room-temperature-stable
crystalline 2<i>H</i>-phosphirene
(<b>1</b>) was prepared by treatment of an electrophilic diamidocarbene
with <i>tert</i>-butylphosphaalkyne. Compound <b>1</b> is shown to react as a vinylphosphinidene generated via phosphireneâphosphinidene
rearrangement. Thermolysis is shown to affect CâN bond scission
while reactions with C<sub>6</sub>Cl<sub>4</sub>O<sub>2</sub> or (tht)ÂAuCl
afford formal oxidation of the phosphindene center and the phosphinidene-insertion
into an aromatic CâC bond of a mesityl group, respectively.
The latter reaction is the first example of a phosphorus analog of
the BuÌchner ring expansion reaction