Gold(i) ethylene complexes supported by electron-rich scorpionates

Abstract

“Bottle-able” molecules with gold–ethylene bonds have been obtained using electron-rich scorpionates. Resulting molecules display enhanced gold → ethylene backbonding, and properties different from those involving electron-poor scorpionates.

Binding Interactions in Copper, Silver and Gold π‐Complexes

“…The experiments show that the BDE s of the given π‐ligands slightly decreased when the ancillary ligand was more electron deficient (see the y‐values of the connected points in Figure 7; for details see Figures S39–S41) pointing to the importance of the π‐back bonding. That trend is in agreement with the reported DFT data on three‐coordinate, gold tris(pyrazolyl)borate complexes [42] . Note that the formation of the complexes with the electron deficient ligands L 2 and L 3 was difficult and therefore we couldn't measure whole series of the complexes.…”

A dicoordinate gold(i)–ethylene complex

“…Au–C lengths in Bourissou's systems in Fig. 1 span from 2.141 to 2.175 Å), 7 but similar to cationic dicoordinate gold( i ) π-complexes with other alkenes. 5 The C C double bond is slightly shorter than that of free ethylene (1.263(10) Å vs. 1.313 Å, respectively) 20 and significantly shorter compared to the described tricoordinate gold( i ) ethylene complexes ( cf.…”

“…ionic) component and a minor role for π-backdonation in a linear coordination environment, which is markedly different to the situation found in related tricoordinate gold( i )–ethylene adducts. 7 These results provide valuable insights for the underdeveloped functionalisation of ethylene mediated by gold. 25 …”

“… 6 Only by using N- and P-based bidentate ligands the related tricoordinate gold( i ) π-ethylene adducts ( Fig. 1 ) 7 have been detected and characterized. Nonetheless, despite the growing interest for bidentate ligands in gold( i ) chemistry, 8 these species do not represent key intermediates in gold catalysis.…”

A Systematic Study of the Effects of Complex Structure on Aryl Iodide Oxidative Addition at Bipyridyl‐Ligated Gold(I) Centers

“…These data correlate with the qualitative observation that complexes with electronpoor bipyridyl ligands are less stable in CH 2 Cl 2 solution than their electron-rich counterparts.T his effect was particularly apparent with bipyridyl ligands bearing the 4-CN (2g•NTf 2 ) and 4-NO 2 (2h•NTf 2 )s ubstituents,w here,a fter only af ew minutes,the solution turned an intense purple color,which we attribute to the formation of Au nanoparticles.C ollectively, these observations show that more electron-rich bipyridyl ligands provide greater electron density at the Au I center and facilitate back-bonding.S imilar stabilization trends for Au I À (h 2 -C 2 H 4 )b inding have been observed by Dias and coworkers using electron-rich scorpionate ligands. [24] It is also pertinent to note that Gatineau, Gimbert and co-workers analyzed the dissociation of CO from LAuÀCO complexes Scheme 2. Synthesis of Au I 2,2'-bipyridyle thylene complexes 2a-i.…”