Base-Stabilized Cationic Silyne with a π-Accepting Phosphonio Substituent.

A base-stabilized C-phosphonio-Si-amino-silyne 3 was synthesized, using an original method, through a coupling reaction between two Lewis-base-stabilized low-valent species: a silyliumylidene ion 1 and a P,S-bis-ylide 2 [C(0)-complex]. This new isolable cationic silyne 3 displays remarkably high stability at room temperature [t1/2 = 7 days in tetrahydrofuran (THF)] and a unique silyne reactivity thanks to the effect of phosphonio substituent.

Reversible Isomerization Between Silacyclopropyl Cation and Cyclic (Alkyl)(Amino)Silylene.

A phosphine-stabilized silacyclopropyl cation 2 has been synthesized and fully characterized. Of particular interest, 2 reversibly isomerizes into the corresponding seven-membered cyclic (alkyl)(amino)silylene 3 at room temperature via a formal migratory ethylene insertion into the Si-P bond. Although silylene 3 has not been spectroscopically detected, its transient formation has been evidenced by the isolation of the corresponding disilene dimer 5 as well as by trapping reactions.

Labile Base-Stabilized Silyliumylidene Ions. Non-Metallic Species Capable of Activating Multiple Small Molecules.

Several base-stabilized silyliumylidene ions (2 and 3) with different ligands were synthesized. Their behaviour appeared strongly dependent on the nature of ligand. Indeed, in contrast to the poorly reactive silyliumylidene ions 3 c,d stabilized by strongly donating ligands (DMAP, NHC), the silylene- and sulfide-supported one (2-H and 3 a) exhibits higher reactivity toward various small molecules. Furthermore, their capability to successively activate multiple small molecules was clearly demonstrated by processes involving successive reactions with silane/formamide, CO2 and H2 . Moreover, HBPin adduct of 3 a (8-C) catalyzes the hydroboration of pyridine. Of particular interest, silylene-supported silyliumylidene complex 2-H is one of the rare species able to activate two H2 molecules.

Lewis Base Adducts of Phosphine-Stabilized Pb(II) Cations: Synthesis and Catalytic Hydroamination of Alkynes.

Phosphine-stabilized Pb(II) cations, generated by chloride abstraction from chloroplumbylene 1, readily react with Lewis bases (L) such as phosphines and amines to give the corresponding donor-acceptor complexes 3. These complexes 3 react with phenylacetlylene via alkyne insertion into the Pb-L bond to afford the corresponding vinylplumbylenes 4. Of particular interest, the stable complex 4-HNiPr2 (with a secondary amine) can be used as a hydroamination catalyst of phenylacetylene.

Reductive Elimination at Pb(II) Center of an (Amino)plumbylene-Substituted Phosphaketene: New Pathway for Phosphinidene Synthesis.

A stable (amino)plumbylene-substituted phosphaketene 3 was synthesized by the successive reactions of PbCl2 with two anionic reagents (lithium amidophosphine and NaPCO). Of particular interest, the thermal evolution of 3, at 80 °C, leads to the transient formation of corresponding amino- and phosphanylidene-phosphaketenes (6 and 7), via a reductive elimination at the PbII center forming new N-P and P-P bonds. Further evolution of 6 gives a new cyclic (amino)phosphanylidene phosphorane 4, which shows a unique reactivity as a phosphinidene. This result provides a new synthetic route to phosphinidenes, extending and facilitating further their access.

Reversible Silylene Insertion Reactions into Si-H and P-H σ-Bonds at Room Temperature.

Phosphine-stabilized silylenes react with silanes and a phosphine by silylene insertion into E-H σ-bonds (E=Si,P) at room temperature to give the corresponding silanes. Of special interest, the process occurs reversibly at room temperature. These results demonstrate that both the oxidative addition (typical reaction for transient silylenes) and the reductive elimination processes can proceed at the silicon center under mild reaction conditions. DFT calculations provide insight into the importance of the coordination of the silicon center to achieve the reductive elimination step.

Donor-Stabilized 1,3-Disila-2,4-diazacyclobutadiene with a Nonbonded Si⋠⋠⋠Si Distance Compressed to a Si=Si Double Bond Length.

A donor-stabilized 1,3-disila-2,4-diazacyclobutadiene presents an exceptionally short nonbonded Si⋅⋅⋅Si distance (2.23 Å), which is as short as that of Si=Si bonds (2.15-2.23 Å). Theoretical investigations indicate that there is no bond between the two silicon atoms, and that the unusual geometry can be related to a significant coulomb repulsion between the two ring nitrogen atoms. This chemical pressure phenomenon could provide an alternative and superior way of squeezing out van der Waals space in highly strained structures, as compared to the classical physical methods.