Intramolecular C-N bond activation by a geometrically constrained PIII-centre.

In this work the first examples of C-N bond activation by insertion into a geometrically constrained PIII-centre are shown. The mechanisms of these activation processes leading to new PV species were studied both experimentally and computationally. Interestingly, in the case of insertion of the PIII-centre into an N-C(O)H bond, an unstable phosphoranyl-formaldehyde intermediate is probably formed, which undergoes decarbonylation in the presence of a catalytic amount of HCl producing a hydrophosphorane.

Dual Reactivity of a Geometrically Constrained Phosphenium Cation.

A geometrically constrained phosphenium cation in bis(pyrrolyl)pyridine based NNN pincer type ligand (1+ ) was synthesized, isolated and its preliminary reactivity was studied with small molecules. 1+ reacts with MeOH and Et2 NH, activating the O-H and N-H bonds via a P-center/ligand assisted path. The reaction of 1+ with one equiv. of H3 NBH3 leads to its dehydrogenation producing 5. Interestingly, reaction of 1+ with an excess H3 NBH3 leads to phosphinidene (PI ) species coordinating to two BH3 molecules (6). In contrast, [1+ ][OTf] reacts with Et3 SiH by hydride abstraction yielding 1-H and Et3 SiOTf, while [1+ ][B(C6 F5 )4 ] reacts with Et3 SiH via an oxidative addition type reaction of Si-H bond to P-center, affording a new PV compound (8). However, 8 is not stable over time and degrades to a complex mixture of compounds in matter of minutes. Despite this, the ability of [1+ ][B(C6 F5 )4 ] to activate Si-H bond could still be tested in catalytic hydrosilylation of benzaldehyde, where 1+ closely mimics transition metal behaviour.

Geometrically constrained square pyramidal phosphoranide.

Geometrical constriction of main group elements leading to a change in the reactivity of these main group centers has recently become an important tool in main group chemistry. A lot of focus on using this modern method is dedicated to group 15 elements and especially to phosphorus. In this work, we present the synthesis, isolation and preliminary reactivity study of the geometrically constrained, square pyramidal (SP) phosphoranide anion (1-). Unlike, trigonal bipyramidal (TBP) phosphoranides that were shown to react as nucleophiles while their redox chemistry was not reported, 1- reacts both as a nucleophile and reductant. The chemical oxidation of 1- leads to a P-P dimer (1-1) that is formed via the dimerization of unstable SP phosphoranyl radical (1˙), an unprecedented decay pathway for phosphoranyl radicals. Reaction of 1- with benzophenone leads via a single electron transfer (SET) to 1-OK and corresponding tetraphenyl epoxide (4).

Phosphorus mediated imidazolinium to oxazolium ring rearrangement.

An unexpected rearrangement occurred when an imidazolinium based OCO pincer-type ligand (1) reacted with PCl3 producing a chlorophosphine with a pendant oxazolium "arm" (3). The mechanism of this rearrangement was studied both experimentally and by density functional theory (DFT) computations. The deprotonation of 3 led to further unexpected results.

A self-catalyzed reaction of 1,2-dibenzoyl-o-carborane with hydrosilanes - formation of new hydrofuranes.

The activation of Si-H bonds is a very important transformation both in organic and inorganic chemistry. Herein we report that 1,2-dibenzoyl-o-carborane (1) reacts with Si-H bonds, yielding new hydrofurane-type products. The mechanism of this Si-H bond activation was studied both experimentally and by DFT calculations, and supposedly proceeds in an FLP-type manner.

Ambiphilic geometrically constrained phosphenium cation.

In this work the synthesis of a geometrically constrained phosphenium cation is shown. In contrast to previously reported phosphenium cations, the geometrical constriction of the P-center in this cation makes it ambiphilic and reactive towards small molecules such as H2O, ROH and NH3.