Synergy between Experimental and Computational Chemistry Reveals the Mechanism of Decomposition of Nickel-Ketene Complexes.

A series of (dppf)Ni(ketene) complexes were synthesized and fully characterized. In the solid state, the complexes possess η-(C,O) coordination of the ketene in an overall planar configuration. They display similar structure in solution, except in some cases, the η-(C,C) coordination mode is also detected.

Synthesis, mechanism of formation, and catalytic activity of Xantphos nickel π-complexes.

A general synthetic route to the first Xantphos nickel alkyne and alkene complexes has been discovered. Various Ni π-complexes were prepared and characterized. NMR experiments indicate benzonitrile undergoes ligand exchange with a Xantphos ligand of (Xant)2Ni, a compound that was previously believed to be unreactive.