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The 18-electron rule is a chemical rule of thumb used primarily for predicting and rationalizing formulas for stable transition metal complexes, especially organometallic compounds. [1] The rule is based on the fact that the valence orbitals in the electron configuration of transition metals consist of five ( n −1)d orbitals, one n s orbital ...
Many rules in chemistry rely on electron-counting: Octet rule is used with Lewis structures for main group elements, especially the lighter ones such as carbon, nitrogen, and oxygen, 18-electron rule [2] in inorganic chemistry and organometallic chemistry of transition metals, Hückel's rule for the π-electrons of aromatic compounds,
This tendency is called the 18-electron rule, because each bonded atom has 18 valence electrons including shared electrons. The heavy group 2 elements calcium, strontium, and barium can use the (n−1)d subshell as well, giving them some similarities to transition metals. [7] [8] [9]
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 ]
Main-group atoms generally obey the octet rule, while transition metals generally obey the 18-electron rule. The noble gases (He, Ne, Ar, Kr, Xe, Rn) are less reactive than other elements because they already have a noble gas configuration. Oganesson is predicted to be more reactive due to relativistic effects for heavy atoms.
In such cases, the rules of electron counting assume that the interstitial atom contributes all valence electrons to cluster bonding. In this way, [Fe 6 C(CO) 16 ] 2- is equivalent to [Fe 6 (CO) 16 ] 6- or [Fe 6 (CO) 18 ] 2- .
The rule is especially applicable to carbon, nitrogen, oxygen, and the halogens; although more generally the rule is applicable for the s-block and p-block of the periodic table. Other rules exist for other elements, such as the duplet rule for hydrogen and helium, and the 18-electron rule for transition metals.
As an approximate rule, electron configurations are given by the Aufbau principle and the Madelung rule. However there are numerous exceptions; for example the lightest exception is chromium, which would be predicted to have the configuration 1s 2 2s 2 2p 6 3s 2 3p 6 3d 4 4s 2 , written as [Ar] 3d 4 4s 2 , but whose actual configuration given ...