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Arrow pushing mechanism is just a formal way of thinking how the reaction might be occurring. Unfortunately, organic chemistry textbooks present it as if all of these reactions were occurring in real time, step by step, and we are able to watch it like a movie. The reality must be far more complex. If you were truly investigating a reaction mechanism, we have to design very clever experiments (there are books on this topic). It is experimental data that determines the true outcome of an organic reaction not the arrow pushing formalism. Usually, when chemists find out the experimental products, then they postulate arrow pushing mechanisms.

Coming to the rust question. Rust has puzzled chemists and engineers for decades because it causes millions of dollars of losses every year. Your equation is a very simplistic way of thinking that rust forms in a single step. $$4Fe^0(s) + 3O_2(g) + 2nH_2O(l) \ce{->} 2Fe_2O_3┬ĚnH_2O(s)$$

It does not proceed in a single step. Our atmospheric chemistry is very complex, you have carbon dioxide, you have sulfur dioxide, nitrogen oxides, ozone, water vapors, sunlight, plenty of free radicals and plenty of minor trace components. Then there are different phases of rust too. You can have a quick look at Google Scholar and one such representative abstract (On the mechanism of atmospheric rusting of iron and protective rust layer on low alloy steels)[Abstract][1]

In short, people still do PhD in this field and one can only imagine how complex corrosion science is. [1]: https://www.jstage.jst.go.jp/article/jcorr1974/23/1/23_1_17/_article/-char/ja/