Carbene analog

Carbene analogs in chemistry are carbenes with the carbon atom replaced by another chemical element. Just as regular carbenes they appear in chemical reactions as reactive intermediates and with special precautions they can be stabilized and isolated as chemical compounds. Carbenes have some practical utility in organic synthesis but carbene analogs are mostly laboratory curiosities only investigated in academia. Carbene analogs are known for elements of group 13, group 14, group 15 and group 16.

Group 13 carbene analogs

In group 13 elements the boron carbene analog is called a borylene or boranylidene.

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.[1] 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:[2]

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:[3]

Ge[N(SiMe3)2]2 + 2 LiC5H3(C10H7)2 → Ge[LiC5H3(C10H7)2]2
compoundC-M distance (pm)C-M-C angle (°)Absorbance (nm)
(Ardip)2Ge203.3 204.8113.8608
(Ardip)2Pb239.0 238.0121.5586
Stable Ge, Sn, Pb metallylenes with Ardip = C6H3-2,6-[C6H3-2,6-(C3H7)2]2 [4]

The C-M-C bond angle in metallylenes is less than 120° confirming hybridization other than sp2. The higher p-character for the C-MII bond compared to the C-MIV 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.[5][6] 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.


  1. Stable Heavier Carbene Analogues Yoshiyuki Mizuhata, Takahiro Sasamori, and Norihiro Tokitoh Chem. Rev. 2009, 109, 3479–3511 doi:10.1021/cr900093s
  2. Synthesis and solid-state structure of (Me3Si)3CGeCH(SiMe3)2, a monomeric dialkylgermylene P. Jutzi, A. Becker, H. G. Stammler, B. Neumann Organometallics, 1991, 10 (6), pp 1647–1648 doi:10.1021/om00052a002
  3. Ligand-Protected Strain-Free Diarylgermylenes Gerald L. Wegner, Raphael J. F. Berger, Annette Schier, and Hubert Schmidbaur Organometallics, 2001, 20 (3), pp 418–423 doi:10.1021/om000743t
  4. Synthesis and Characterization of the Monomeric Sterically Encumbered Diaryls E{C6H3-2,6-(C6H3-2,6-Pri2)2}2 (E = Ge, Sn, or Pb) Geoffrey H. Spikes, Yang Peng, James C. Fettinger, Philip P. Power, Davis Zeitschrift für anorganische und allgemeine Chemie Volume 632 Issue 6, Pages 1005 - 1010 2006 doi:10.1002/zaac.200500532
  5. Remarkably Stable Chalcogen(II) Dications Caleb D. Martin, Christine M. Le, and Paul J. Ragogna J. Am. Chem. Soc., Article ASAP 2009 doi:10.1021/ja9073968
  6. Reactive Dications Tamed Main-Group Chemistry: Stabilizing positive charge with three nitrogen atoms yields stable group 16 complexes Steve Ritter Chemical & Engineering News October 12, 2009 Volume 87, Number 41 pp. 12 - 12 Link
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