sp Carbon chains surrounded by sp3 carbon double helices: wire-like Pt(CC)nPt moieties that are spanned by two α,ω-diphosphines that bear heteroatoms or alkyl substituents

Coordination‐Driven Self‐Assembly, Structures, and Dynamic Properties of Diplatinum Hexatriynediyl and Butadiynediyl Complexes in which the sp Carbon Chains are Shielded by sp3 Carbon Chains: Towards Endgroup–Endgroup Interactions

“…19. [13] As noted with other complexes of the type PtC x Pt-m/ Ar, [13][14][15] the mass spectra of PtC 6 Pt-m/Ar exhibited intense molecular ions. The PtC CC 13 C NMR spectroscopy signals of these diarylalkylphosphine adducts (PtC C, 95.7- Figure 1.…”

“…[13][14][15] One involves phosphine ligand substitution, or "coordinationdriven self-assembly", and the other an alkene metathesis/ hydrogenation sequence. The products contain endgroupspanning a,w-diphosphines that sterically shield the sp carbon chains.…”

“…In one approach, described elsewhere, the sp 3 chains were functionalized. [15] In a parallel approach, and the subject of this investigation, we sought to extend the above chemistry from PtC 8 Pt and PtC 12 Pt systems to lower homologues with shorter C x bridges. It was thought that endgroup-endgroup steric interactions would eventually destabilize the achiral conformation B and slow the A/A' equilibrium.…”

“…Both PtC 6 Pt and PtC 4 Pt exhibited the C 6 H 4 R/C 6 F 5 /C 6 H 4 R p-stacking interaction commonly seen in this series of compounds. [5,11,[13][14][15]26] The average centroid-centroid distances are also given in Table 2. Consistent with the inversion center, the endgroups in Pt'C 6 Pt' were also coplanar.…”

“…As summarized in Table 5, cyclic voltammograms of representative adducts were recorded under conditions employed for related complexes earlier. [5,6,[11][12][13][14][15] Partially reversible oxidations were observed, as reflected by the i c/a and DE values. Mixed-valent platinum(II)/platinumA C H T U N G T R E N N U N G (III) radical cations were presumed to form.…”