Coordination Behaviour of a Hexadentate 1,1′‐Ferrocenylene‐Bridged Bisphosphole towards Coinage Metal Centres

Abstract

Keywords: Gold / P ligands / Sandwich complexes / Coordination modes / Ab initio calculationsWe describe the synthesis of a ferrocenylene-bridged bis[2,5-bis(2-pyridyl)]phosphole ligand that shows additional rotational degrees of freedom relative to its previously described p-phenylene-bridged congener. The coordination behaviour of this ferrocenylene-based bis-N,P,N pincer towards coinage metal centres M I with M = Cu and Au was explored, revealing different coordination modes with and without involve-

Late Transition Metal Compounds with 1,1′‐Bis(phosphino)ferrocene Ligands

“…[22] The %V bur defines the percentage of the volume of a sphere surrounding a metal atom that is occupied by a ligand and is calculated with the recently updated SambVca 2 suite. [23] τ [e] 55.67 (7) 48.51 (14) [f ] [27] The structures of [Zn(2O 2 )Cl 2 ] and [Zn(3O 2 )Cl 2 ] were determined (Figure 3), and selected structural parameters are presented in Table 2. The structural parameters are similar, although the O-Zn-O bite angle in [Zn(3O 2 )Cl 2 ] is significantly wider than that of the related 2O 2 compound.…”

“…Intramolecular aurophilic interactions have been observed in other compounds containing 1,1′-bis(phosphino)ferrocene ligands, namely, [(AuSe-o-C 6 H 4 CH 2 -NMe 2 ) 2 (1)] (Au-Au 3.0243 Å) [33] and [(AuC≡Cbpy) 2 (1)] (Au-Au 3.2555 Å), [34] but in both of these systems only the dppf ligand bridges the two gold atoms. Although there are many examples of compounds with a chlorido ligand bridging an Au-Au interaction, [35] only the Au-Au distance in chlorido-bridged [Ag 12 Au 25 (μ-Cl) 14 [37] The shorter +2 (77.63°).…”

Cooperative Gold Nanoparticle Stabilization by Acetylenic Phosphaalkenes

“…Structural integrity of the surface-bound phosphinines is however debated in view of as olid-state MAS-NMR spectroscopic study. [9] With our interest to explore low-valent phosphoruscontaining systems for molecular electronics applications, [10] we were intrigued by the possibility to use phosphaalkenes as conducting anchoring groups on Au surfaces.T he inherent instability of phosphaalkenes has presumably kept many researchers from using l 3 s 2 -phosphanes for these kinds of …”

“…Structural integrity of the surface-bound phosphinines is however debated in view of as olid-state MAS-NMR spectroscopic study. [9] With our interest to explore low-valent phosphoruscontaining systems for molecular electronics applications, [10] we were intrigued by the possibility to use phosphaalkenes as conducting anchoring groups on Au surfaces.T he inherent instability of phosphaalkenes has presumably kept many researchers from using l 3 s 2 -phosphanes for these kinds of purposes.T his obstacle is easily met through kinetic stabilization provided by P-bound Mes* groups (Mes* = 2,4,6-(tBu) 3 C 6 H 2 ). However,steric protection of the P = Cunit could also impede strong binding of the phosphorus center to the Au surface.T he present paper is the first report that shows that l 3 s 2 -phosphanes in the form of phosphaalkenes can stabilize AuNPs,a lbeit only when in conjunction with acetylenes.E xperimental observations,s pectroscopic data, and theoretical evidence are presented to show that both structural features of acetylenic phosphaalkenes,t hat is,t he P = Cand the C Cunits are required in acooperative fashion for AuNP stabilization.…”

“…(Hetero-)Ene-yne motifs tested for AuNP preparation and stabilization.P hosphaalkenes (1-3), acetylenicp hosphaalkenes(4-7), and all-carbon reference compounds(8)(9)(10)(11).…”