Capturing a Ghost. Synthesis and Structural Characterization of Pd(dba)[P(o-Tol)3]2

In an effort to improve upon a literature synthesis of bis[tris(o-tolyl)phosphine]palladium(0) (1) from tris(o-tolyl)phosphine and Pd-2(dba)(3), we instead isolated a new compound which proved to have the composition Pd(dba)[P(o-Tol)(3)](2) (2), upon analysis by X-ray crystallography. While this is not the first known palladium compound containing both dba and phosphine ligands, it is, to our knowledge, the first containing dba and tris(o-tolyl)phosphine. This is significant, because mixtures of Pd-2(dba)(3) and tris(o-tolyl)phosphine are routinely used in cross-coupling protocols, and palladium complexes containing dba and tris(o-tolyl)phosphine have been cited as intermediates in organometallic and polymerization reactions. The most interesting crystallographic parameter for 2 is an abnormally long Pd-P bond length of 2.388(1) angstrom, which we believe is the cause of this complexs metastability. We also present an alternative synthesis of 1 that does not require a large excess of phosphine.