Extending the Coordination Chemistry of Molecular P₄S₃:  The Polymeric Ag(P₄S₃)⁺and Ag(P₄S₃)₂⁺Cations

Abstract

Upon reacting P(4)S(3) with AgAl(hfip)(4) and AgAl(pftb)(4) [hfip = OC(H)(CF(3))(2); pftb = OC(CF(3))(3)], the compounds Ag(P(4)S(3))Al(hfip)(4) 1 and Ag(P(4)S(3))(2)(+)[Al(pftb)(4)](-) 2 formed in CS(2) (1) or CS(2)/CH(2)Cl(2) (2) solution. Compounds 1 and 2 were characterized by single-crystal X-ray structure determinations, Raman and solution NMR spectroscopy, and elemental analyses. One-dimensional chains of [Ag(P(4)S(3))(x)](infinity) (x = 1, 1; x = 2, 2) formed in the solid state with P(4)S(3) ligands that bridge through a 1,3-P,S, a 2,4-P,S, or a 3,4-P,P eta(1) coordination to the silver ions. Compound 2 with the least basic anion contains the first homoleptic metal(P(4)S(3)) complex. Compounds 1 and 2 also include the long sought sulfur coordination of P(4)S(3). Raman spectra of 1 and 2 were assigned on the basis of DFT calculations of related species. The influence of the silver coordination on the geometry of the P(4)S(3) cage is discussed, additionally aided by DFT calculations. Consequences for the frequently observed degradation of the cage are suggested. An experimental silver ion affinity scale based on the solid-state structures of several weak Lewis acid base adducts of type (L)AgAl(hfip)(4) is given. The affinity of the ligand L to the silver ion increases according to P(4) < CH(2)Cl(2) < P(4)S(3) < S(8) < 1,2-C(2)H(4)Cl(2) < toluene.

Tetraalkylammonium Salts of Weakly Coordinating Aluminates: Ionic Liquids, Materials for Electrochemical Applications and Useful Compounds for Anion Investigation

“…Especially the P À X cations are incompatible with all other anion types. This also holds for a series of silver and copper(I) complexes with very weakly basic ligands, for example, P 4 , [29,30] P 4 S 3 , [31,32] S 8 , [33] P 3 N 3 Cl 6 , [34] or C 2 H 4 . [35,36] Since the starting materials to prepare compounds of the fluorinated aluminates are commercially available (best at P&M Invest Russia; http:// www.fluorine.ru) and the synthesis of the lithium aluminate salts [37][38][39] is a simple high yield procedure that we have performed in scales up to 250 g per batch, [40] it only appeared logical to extend the available substance classes to [NR 4 ] + salts.…”

“…A figure of 2 is deposited with the Supporting Information. For the [hfip] À and the [hftp] À anions, the tetraalkylammonium salts are the second examples of really ionic solid-state structures with isolated anions and cations, [41] while all the other species containing these anions, contain molecular structures with coordinated anions, for example, [(P 4 S 3 )AgA], [31,32] [(P 4 )AgA], [45] [(L) 2 AgA], [35,46] or [(L)AgA] [35,46] ( [47] and later in more detail by Glasser and Jenkins. [43,48] This concept allows thermodynamic predictions for condensed phases principally via formula unit volumes.…”

Dynamics and Counterion‐Dependence of the Structures of Weakly Bound Ag+–P4S3 Complexes

“…[18] Although both anions are rather similar, the structures of the adducts are very different. In fact, they are both polymeric, but whereas in [( (2) has an ionic structure with homoleptic polymeric cations and isolated anions.…”

Homoleptische Silber(I)‐Acetylen‐Komplexe

“…In dieser Weise ermöglichen auch [Al(OR F ) 4 ] À -WCAs (OR F = Fluoralkoxid) [14][15][16][17] die Stabilisierung und vollständige Charakterisierung von Salzen einiger Gasphasenkationen, die zuvor nur durch MS-Experimente bekannt waren. [7,[18][19][20][21] [22] unbekannten Stammverbindungen aller homolep-…”