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The review provides a survey of the key classes of PtIIcomplexes containing cis‐{Pt(η1‐hydrocarbyl)(η2‐unsaturated ligand)} moieties, which have been isolated or at least unequivocally characterized in solution. These compounds, which mimic reactive intermediates of fundamental catalytic processes, have been classified in four general types, which display a cisarrangement of an alkyl group and a monoalkene (I), an aryl group and a monoalkene (II), an alkyl group and a monoalkyne (III), and an aryl group and a monoalkyne (IV). A discussion of their main structural and chemicalfeatures, disclosing the factors affecting their reactivity, dynamic behavior, and relative stability, is presented. In some remarkable cases (IIIand IV), it is the cisarrangement of the hydrocarbyl fragments that promotes unusual reactivity.

This review provides a survey of the key‐class of Pt0complexes of general formula [Pt(N,N′‐chelate)(η2‐olefin)]. The main spectroscopic, structural and chemical features are discussed, in terms of electronic and steric properties of the ancillary ligands. The versatile reactivity towards electrophiles is described as a very useful entry to PtIIcompounds with a wide assortment of ligands, such as halido, hydrido, hydrocarbyl, organometal, organoelement and carbene fragments, in some cases stabilised for the first time by the careful choice of the N,N′‐ligand. Remarkably, the reactions can be an equilibrium, and their relevant thermodynamic parameters have also been collected, thus allowing a thorough discussion of the electronic and steric factors which affect its position.