10.1021/om400335a.s001 Brennen A. Harding Brennen A. Harding Patrick R. Melvin Patrick R. Melvin William Dougherty William Dougherty Scott Kassel Scott Kassel Felix E. Goodson Felix E. Goodson Capturing a Ghost. Synthesis and Structural Characterization of Pd(dba)[P(<i>o</i>‑Tol)<sub>3</sub>]<sub>2</sub> American Chemical Society 2013 dba Pd tris literature synthesis alternative synthesis Structural Characterization phosphine ligands polymerization reactions palladium compound palladium complexes 2013-06-24 00:00:00 Journal contribution https://acs.figshare.com/articles/journal_contribution/Capturing_a_Ghost_Synthesis_and_Structural_Characterization_of_Pd_dba_P_i_o_i_Tol_sub_3_sub_sub_2_sub_/2402773 In an effort to improve upon a literature synthesis of bis­[tris­(<i>o</i>-tolyl)­phosphine]­palladium­(0) (<b>1</b>) from tris­(<i>o</i>-tolyl)­phosphine and Pd<sub>2</sub>(dba)<sub>3</sub>, we instead isolated a new compound which proved to have the composition Pd­(dba)­[P­(<i>o</i>-Tol)<sub>3</sub>]<sub>2</sub> (<b>2</b>), 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(<i>o</i>-tolyl)­phosphine. This is significant, because mixtures of Pd<sub>2</sub>(dba)<sub>3</sub> and tris­(<i>o</i>-tolyl)­phosphine are routinely used in cross-coupling protocols, and palladium complexes containing dba and tris­(<i>o</i>-tolyl)­phosphine have been cited as intermediates in organometallic and polymerization reactions. The most interesting crystallographic parameter for <b>2</b> is an abnormally long Pd–P bond length of 2.388(1) Å, which we believe is the cause of this complex’s metastability. We also present an alternative synthesis of <b>1</b> that does not require a large excess of phosphine.