Understanding palladium complexes structures and reactivities: beyond classical point of view

Palladium catalyzed cross‐coupling reactions are one of the most widely used class of transformation as shown by the Nobel prize awarded in 2010 to Heck, Negishi, and Suzuki. Computational chemistry has a long‐standing partnership with organometallics catalysis, especially with palladium. But even in a largely explored field, novelties can emerge from interplay between experiments and theory. Recent advances grounded on computational chemistry have shown that cooperative effect can explain reactivities; that despite the large number of well‐known Pd(0)/Pd(II) catalytic cycle, Pd(IV) is also a realistic intermediate in some cases; that noncovalent interactions can regulate selectivities. So, despite its wide use and recognition, palladium complexes are still full of surprises! WIREs Comput Mol Sci 2013, 3:529–541. doi: 10.1002/wcms.1137