Gold–Heterometal Interactions and Bonds

Highly Luminescent Octanuclear AuI–CuI Clusters Adopting Two Structural Motifs: The Effect of Aliphatic Alkynyl Ligands

“…These fragments are held together by the Au-Au interactions and p À C C À Au bonding. The structural motif of the central heterometallic alkynyl part {Au 2 Cu 2 A C H T U N G T R E N N U N G (C 2 R) 4 } has been recently reported in dimeric form as an independent complex {Au 2 Cu 2 (ethisterone) 4 } 2 . [3] However, this tetranuclear unit was isolated only for the sterically demanding steroid alkyne ligand, while for those with smaller substituents (R = 1-cyclohexanolyl and 1-cyclopentanolyl) no similar compounds were reported.…”

“…The gold-gold distances in 5 and 6 range from 2.9062(3) to 2.9945(3) and fall in the range found for the aurophilic contacts. [3,6,14] The copper atoms occupy asymmetrical positions between the [AuA C H T U N G T R E N N U N G (C 2 R) 2 ] À anions in the {Au 2 Cu 2 A C H T U N G T R E N N U N G (C 2 R) 4 } fragments. The bonding CuAu contacts in 5 and 6 are 2.8112(7) and 2.8270(6) , respectively, which are not exceptional and correlate well with previously reported data.…”

“…[2,3] In order to facilitate metalmetal bond formation and stabilize the polymetallic complexes various types of bridging ligands have been successfully employed in preparative chemistry of gold. [4] Among them the alkynyl moiety has proven to be an excellent building block in construction of homo- [5][6][7] and heterometallic [3,8,9] coinage-metal assemblies of fascinating structural topologies through the combination of s-and p-bonding mode of the CC unit. As homoleptic alkynyl complexes often demonstrate a tendency for polymerization to give the products of low solubility, which are difficult to characterize, [7,10,11] the ancillary phosphine ligands are used to prevent the infinite aggregation and confine the metal cluster to the certain size and shape.…”

The gold(i)⋯lead(ii) interaction: a relativistic connection

“… 8 , 9 These facts prompted many groups to investigate more closely other closed-shell heavy metal complexes, or even heterometallic gold-containing ones with identical d 10 or different (s 2 , d 8 ) configurations. 10 Theoretical studies that often accompany these syntheses have confirmed that a more general term was needed: metallophilicity. These studies conclude that the interactions between the metals arise, among others, from dispersion forces reinforced in different percentages by relativistic effects.…”

Amalgamating at the molecular level. A study of the strong closed-shell Au(i)⋯Hg(ii) interaction

“…Following this method our group succeeded in obtaining a number of heterometallic complexes displaying non-supported interactions between Au(I) and other closed shell metal ions such as Tl(I), Ag(I) or Bi(III). [2][3][4] In the case of Cu(I), the acid-base strategy did not lead to the desired products. An alternative strategy, such as a transmetallation reaction, had to be employed to obtain complexes bearing unsupported Au(I)Á Á ÁCu(I) contacts.…”