Interaction of SbCl₅²⁻ and Thioether Groups at the Open Coordination Sites of Platinum(II) Diimine Complexes

Abstract

In the solid-state, the approximately square planar cation in orange crystals of [Pt(NO(2)phen)(ttcn)](PF(6))(2) (NO(2)phen = 5-nitro-1,10-phenanthroline; ttcn = 1,4,7-trithiacyclononane) has a short apical Pt...S(ttcn) distance (2.9415(15) A). In acetonitrile solution, the electronic spectrum shows a long-wavelength absorption band (412 nm; 2200 M(-1) cm(-1)), consistent with the notion that the axial Pt...S(ttcn) interactions stabilize states having metal-to-ligand charge-transfer (MLCT) character. Reaction with the hexachloroantimonate(V) salt of tris(4-bromophenyl)aminium (TBPA(+)) results in complex redox chemistry, involving the platinum complex, SbCl(5)(2-) and TBPA(+). In the case of Pt(bpy)(ttcn)(2+), orange-yellow crystals of [Pt(bpy)(ttcn)](2)(Sb(4)Cl(16)) were isolated from the reaction, whereas the reaction with Pt(NO(2)phen)(ttcn)(2+) consistently yielded red crystals of [Pt(NO(2)phen)(ttcn)](SbCl(5)) x 2 CH(3)CN. In the latter case, the geometry of the cation, including the apical Pt...S(ttcn) distance (2.9390(12) A), is very similar to that of the PF(6)(-) salt. However, the basal plane of each square pyramidal SbCl(5)(2-) opposes the nearly parallel coordination plane of an adjacent Pt(NO(2)phen)(ttcn)(2+) complex, resulting in an unusually short intermolecular Pt...Sb distance of 3.4259(3) A. The longest wavelength maximum in the diffuse reflectance spectrum and the solid-state emission maximum are shifted by approximately 1200 cm(-1) and approximately 700 cm(-1), respectively, to the red of those of the PF(6)(-) salt, consistent with perturbation of the complex's electronic structure because of the Pt...Sb interaction.

Triple the fun: tris(ferrocenyl)arene-based gold(i) complexes for redox-switchable catalysis

“…To the best of our knowledge, a rhenium(0) carbonyl complex by Nataro and co-workers is the only other example to contain both ferrocenium and a phosphane-bound metal complex fragment, 141 while the +III oxidation state of iron in reported bis[1,1 0 -bis(diphenylphosphanyl)ferrocenium] hexadecachlorotetraantimonate(III) by the group of Kasim 142 has been questioned by both Nataro and Connick. 143 Not backed up by a solid-state molecular structure, Grandberg and co-workers also reported a phosphanyl ferrocenium-based gold(III) bromide complex in 1977. 144 Last but not least, a very recent report by the Lapinte group details a related tetranuclear iron(II/III) halfsandwich array with potential use in molecular electronics.…”

Synthesis of mononuclear and dinuclear palladium (II) complexes containing oxadithioether ligands and their catalytic activities in norbornene polymerization

“…The reaction of 4b and 6b with BF 3 ÁOEt 2 (5 equiv) in CDCl 3 in an NMR tube at room temperature led to the transformation of κ 2 -O,O-acetylacetonate ligand within 6 min (the conversion was 39% for 4b and 68% for 6b based on 1 H NMR data for CH-acac at 5.0-5.7 ppm) and appearance of a new signal at 6.0 ppm attributed to BF 2 (acac). New signals from BF 4 anion coordination were also detected by 19 F NMR (À150.83, À149.57 ppm), BF 2 (acac) (À138.71 ppm), and an unidentified signal that was observed at À153.87 ppm. No Pd-black was observed.…”

“…[63,70,72] The average Pd-Cl bond length (2.301 Å) lies in the usual range found for four-coordinate Pd (II) complexes. [1] The two trans-arranged Cl atoms form a Cl1-Pd1-Cl2 angle of 179.347 (19), and the angle between the sulfur atoms of S1-Pd1-S2 of 173.760 (16) indicates slight deformation of the square planar geometry for palladium. The 16-member ring has a "parallelogram shape" when viewed along the Cl-Pd bond with sides formed by the extended S-(CH 2 ) 2 O(CH 2 ) 2 -S chains and the trans S-Pd-S linkages.…”

Hemilabile bonding of 1-oxa-4,7-dithiacyclononane in cyclometallated palladium(ii) complexes

“…[Pd( ppyCHO)( [30][31][32][33][34][35][36] show the same solution behavior in 1 H and 13 C NMR. We have noted that the lack of axial mirror symmetry in this cyclometallated complex (and previously reported complexes) is not manifested in lower symmetry of the fluxional [9]aneS 3 as the 13 C NMR spectrum indicates only a single averaged 13 Fig.…”