Transition metal organometallics and the 18th rule

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The discussion centers on the application of the 18-electron rule in organometallic compounds. The user questions their electron counting for the compounds [(BuO)3 Mo Mo (OBu)3] and W(CO)3(P Pr3)2(H2), seeking validation of their calculations of 12 and 16 electrons, respectively. They also inquire about exceptions to the 18-electron rule, specifically regarding the dimerization of V(CO)6 and the compounds Mo2(OSiMe3)6 and W(Me6). Additionally, the user asks why metallocenes are primarily known for transition metals from vanadium to nickel. The thread highlights the complexities and nuances of electron counting in transition metal organometallics.
Bibinou
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Hello everybody,

I have some problems in order to count the electrons in compound using the 18th electrons rule.

In the compound [(BuO)3 Mo Mo (OBu)3] I count 12 electrons (6 e- for Mo, 3 * 1e- for Metal-Metal bound, and 3 * 1e- for OBu). Is it correct?

In the compound W(CO)3(P Pr3)2(H2) I count 16 electrons (6 e- for W, 3 * 2e- for CO and 2*2e- for P Pr3). Is it correct?

Moreover, it exist exceptions to the 18-electron rule.
Why cannot V(CO)6 dimerize?
What about the compound Mo2(OSiMe3)6 and W(Me6)?

Why are Metallocenes [M (C5H5)2] are only known for M = V to Ni ?

I thank you very much for your help
 
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