Trinuclear complexes with Pt2M(μ3-S) groups and the ease of inversion at sulfur

Three- and Four-Coordinate Gold(I) Complexes

“…External Au-Br contacts are responsible for the aggregation of these units into dimers. A new type of complex with a three-coordinate gold-(I) center is the trinuclear [Pt 2 Au(µ 3 -S)(µ-PPh 2 CH 2 -PPh 2 ) 2 ]Cl, 75 obtained from [Pt 2 (µ-S)(µ-PPh 2 CH 2 -PPh 2 )(η 1 -PPh 2 CH 2 PPh 2 )] (which acts as a tridentate ligand) and [AuCl(SMe 2 )], according to eq 5. Although the Au-S distance of 2.621(8) Å is long, the P-Au-P angle of 143.9(3)°clearly shows a deviation from linearity.…”

Platinum(II) and Palladium(II) Dibenzo[a,e]cyclooctatetraene (DBCOT) Oxo and Halide Complexes: Comparison to 1,5-COD Analogues

“…Au1 and Au3 occupy adjacent “axial” positions, allowing them to participate in aurophilic interactions. There are also short Pt−Au distances (Pt1−Au1, Pt3−Au3, Pt2−Au2), indicating related closed shell Pt−Au interactions. − Despite the presence of two different types of Pt and O centers, the Pt−O distances (1.975(13)−2.028(14) Å) are identical within experimental error, as are the Au−O distances (2.075(15)−2.084(14) Å). However, the O−Pt−O angles do differ, with the unique O1−Pt2−O2 angle significantly greater (95.6(6)°) than the corresponding angles of Pt1 (90.4(6)°) and Pt3 (89.6(5)°).…”

“…There are also short Pt-Au distances (Pt1-Au1, Pt3-Au3, Pt2-Au2), indicating related closed shell Pt-Au interactions. [25][26][27][28][29] The trimeric structure of 6 with Pt-Au and Au-Au interactions is in contrast to the analogous COD product, which is the dimer [Pt(µ 3 -O)(COD)(AuPPh 3 )] 2 (BF 4 ) 2 . 4 There are no Au-Au or Pt-Au interactions in the dimer, and the Pt 2 O 2 Au 2 core is nearly planar.…”

Copper(I)−Purine−Phosphine Complexes. Syntheses and Molecular Structures of [Cu2(μ-HL1)2(μ-dppm)(η1-dppm)2] and {[Cu3(μ3-Cl)2(μ-dppm)3][Cu(HL2)2]} (H2L1= 8-Mercaptotheophylline and H2L2= 8-Ethyl-3-methylxanthine)

“…Thus, one of the dppm ligands adopts a η 2 -bridging mode while the other two act in a η 1 -terminal fashion. The ability of the dppm ligands to adopt different coordination modes, such as η 1 -terminal, η 2 -chelate, and η 2 -bridging, arises from their stereochemical flexibility. − It should be stressed that a few examples of metal complexes having two of these dppm coordination modes are found in the literature, − our complex being, to the best of our knowledge, the first example reported so far for a copper(I) complex.…”