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In the world of science, in particular the section concerning the field of chemistry, when the results encountered during the experiment do not meet our expectations, our shrewdness may play an important role to open up new unexplored fields that could be much more interesting than what we were seeking. In those cases, our research undergoes an unforeseen shift, delivering novel and challenging results that may altogether alter our point of view and our future work. We have then struck serendipity. Specifically, in our investigation linked to palladacycles we have found that the new trends in their reactivity, as well as in their structure, have been, in many cases, related to this experience, broadening our research scope within this field. Herein, we describe our most relevant findings, which have shed new light upon the reactivity of palladacycles, thus opening new routes that lead to novel unexpected structures. Box of surprises: Serendipitous discoveries have long‐since been at the heart of the new advancements in science, and more often than not they provide striking findings that exceed the most promising expectations; thus, serendipity emerges to extend the frontiers of chemistry one step further. Palladacycles have not been strangers to this issue and, herein, some distinguished disclosures are depicted where serendipity yielded remarkable, yet not sought, results. [ABSTRACT FROM AUTHOR]

The Cover Feature shows four structures depicting (clockwise from the top‐left corner) a beautiful tetranuclear layered compound, a bis‐pseudopentacoordinated palladium moiety, the only known trinuclear thiosemicarbazone palladacycle, and the sandwiched coordination of the potassium cation by small crown ether rings attached to the metallated phenyl enclosures of a dinuclear diphosphine‐bridged palladium complex. All of these unexpected findings put forward the presence of serendipity in the reactivity of palladacycles and highlight the relevance of such an experience in their chemistry. More information can be found in the Review by A. Fernández‐Figueiras et al. on page 754 in Issue 10, 2018 (DOI: 10.1002/open.201800036). [ABSTRACT FROM AUTHOR]