Carbene analog

 ( Octet-deficient Functional Groups ) 

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.

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

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Group 14 carbene analogs The heavier group 14 carbenes are , R₂Si:, Germylene R₂Ge: (example diphosphagermylene), stannylenes R₂Sn: and Plumbylene R₂Pb:, collectively known as metallylenes and regarded as for . Stable Heavier Carbene Analogues Yoshiyuki Mizuhata, Takahiro Sasamori, and Norihiro Tokitoh Chem. Rev. 2009, 109, 3479–3511 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 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 Diradical 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: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

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

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

Stable also require bulky ligands: Ligand-Protected Strain-Free Diarylgermylenes Gerald L. Wegner, Raphael J. F. Berger, Annette Schier, and Hubert Schmidbaur Organometallics, 2001, 20 (3), pp 418–423

GeN(SiMe₃)₂₂ + 2 LiC₅H₃(C₁₀H₇)₂ → GeLiC₅H₃(C₁₀H₇)₂₂

Absorbance (nm)

608

600

586

Stable Ge, Sn, Pb metallylenes with Ardip = C6H3-2,6-C6H3-2,6-(C3H7)22 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

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.

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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.

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Group 16 carbene analogs Carbene analogs of group 16 elements have been first reported in 2009. Remarkably Stable Chalcogen(II) Dications Caleb D. Martin, Christine M. Le, and Paul J. Ragogna J. Am. Chem. Soc., Article ASAP 2009 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 Sulfur, selenium and tellurium 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 .

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