Tolman's rule

Last updated February 07, 2025

Tolman's rule states that, in certain chemical reactions, the steps involve exclusively intermediates of 18- and 16 electron configuration. The rule is an extension of the 18-electron rule. This rule was proposed by American chemist Chadwick A. Tolman.^[1] However, there are exceptions to Tolman's rule, even for reactions that proceed via 2e⁻ steps, because many reactions involve intermediates with fewer than 16 electrons.

Many examples of homogeneous catalysis involving organometallic complexes involve shuttling of complexes between 16- and 18-electron configurations. 16-electron complexes often form adducts with Lewis bases and, if low-valent, undergo oxidative addition.

CH 3 I + cis -[Rh(CO) 2 I 2] - \to [(CH 3)Rh(CO) 2 I 3] -

Conversely, complexes of 18 electron configuration tend to dissociate ligands or undergo reductive elimination:

Rh(PPh 3) 3 ClH 2 \to Rh(PPh 3) 3 Cl + H 2

References

↑ Tolman, C.A. (1972). "The 16 and 18 electron rule in Organometallic Chemistry and Homogeneous Catalysis". Chem. Soc. Rev. 1 (3): 337–353. doi:10.1039/CS9720100337.

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[1] Tolman, C.A. (1972). "The 16 and 18 electron rule in Organometallic Chemistry and Homogeneous Catalysis". Chem. Soc. Rev. 1 (3): 337–353. doi:10.1039/CS9720100337.

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Tolman's rule

See also

References