Carbene analog

Group 14 carbene analogs

The heavier group 14 carbenes are silylenes, R₂Si:, germylenes R₂Ge: (example diphosphagermylene), stannylenes R₂Sn: and plumbylenes R₂Pb:, collectively known as metallylenes and regarded as monomers for polymetallanes. The oxidation state for these compounds is +2 and stability increases with principal quantum number (moving down a row in the periodic table). This makes dichloroplumbylene PbCl₂ and dichlorostannylene SnCl₂ stable ionic compounds although they exist as polymers or ion pairs.

Group 14 carbene analogs do not form hybrid orbitals but instead retain (ns)²(np)² electron configuration due to the increasing s p gap for larger elements. Two electrons remain in an s-orbital and therefore their compounds have exclusively singlet ground states and not the triplet ground state which can be observed in carbenes depending on the substituents. The s-orbital (lone pair) is inert and the vacant p-orbital is very reactive. Stable group 14 carbenes require stabilization of this p-orbital which is usually accomplished by coordination of a Cp* ligand or coordination to nitrogen, oxygen or phosphorus containing ligands, although stabilization can be achieved through steric protection alone.

General methods for the synthesis of carbon-substituted (aryl or alkyl) metallylenes are reduction of M⁴⁺ species or substitution reactions at M²⁺ halides. Stable metallylenes require bulky substituents in order to prevent nucleophilic attack of the metal center at the p-orbital. Examples of these bulky substituents in R₂M: are mesityl, Dis (di(trimethylsilyl)methyl) and adamantyl groups. With insufficient steric shielding the metallylene will form a dimer or a polymer. The first isolable dialkylgermylene was synthesised in 1991:

Me₅C₅GeCl + LiCH(Si(Me₃))₂ → Me₅C₅GeCH(Si(Me₃))₂

Me₅C₅GeCH(Si(Me₃))₂ + LiC(Si(Me₃))₃ → (SiMe₃)₃CGeCH(Si(Me₃))₂

Stable diarylgermylenes also require bulky ligands:

Ge[N(SiMe₃)₂]₂ + 2 LiC₅H₃(C₁₀H₇)₂ → Ge[LiC₅H₃(C₁₀H₇)₂]₂

The C-M-C bond angle in metallylenes is less than 120° confirming hybridization other than sp². The higher p-character for the C-M^II bond compared to the C-M^IV bond is reflected in its slightly higher bond length.

N-heterocyclic silylenes are known to be stable for months and have been studied extensively.

Group 15 carbene analogs

In the group 15 elements the neutral nitrogen carbene analog (RN) is called a nitrene. The phosphorus analog is a phosphinidene. There are charged group 15 carbene analogs as well, most notably phosphenium ions (R₂P⁺) which are isolobal with (hetero-)carbenes possessing a singlet ground state.

Group 16 carbene analogs

Carbene analogs of group 16 elements have been first reported in 2009. Sulfur, selenium, and tellurium dications have been found to be stabilized by the diiminopyridine ligand DIMPY. For example, the reaction product of triflate S(OTf)₂ and (2,6-diisopropylphenyl)₂DIMPY at -78 °C results in an air-stable dicationic sulfur compound with a naked S²⁺ atom coordinated by three nitrogen atoms by dative bonds.