Metal-metal cooperative bond activation by heterobimetallic alkyl, aryl, and acetylide Pt/Cu complexes.

We report the selective formation of heterobimetallic Pt/Cu complexes that demonstrate how facile bond activation processes can be achieved by altering the reactivity of common organoplatinum compounds through their interaction with another metal center. The interaction of the Cu center with the Pt center and with a Pt-bound alkyl group increases the stability of PtMe towards undesired rollover cyclometalation. The presence of the Cu center also enables facile transmetalation from an electron-deficient tetraarylborate [B(Ar)] anion and mild C-H bond cleavage of a terminal alkyne, which was not observed in the absence of an electrophilic Cu center.

Controlled and Reversible Stepwise Growth of Linear Copper(I) Chains Enabled by Dynamic Ligand Scaffolds.

Reversible stepwise chain growth in linear Cu assemblies can be achieved by using the dynamic, unsymmetric naphthyridinone-based ligand scaffolds L1 and L2. With the same ligand scaffolds, the length of the linear copper chain can be varied from two to three and four copper atoms, and the nuclearity of the complex is easily controlled by the stepwise addition of a Cu precursor to gradually increase the chain length, or by the reductive removal of Cu atoms to decrease the chain length. This represents a rare example of a stepwise controlled chain growth in extended metal atom chains (EMACs).