Synthetic, Structural, Electrochemical, and Theoretical Studies of Heterometallic Aggregates with a [Pt₂(μ-S)₂M] Core (M = Hg, Au)

Abstract

Novel electroactive multimetallic compounds based on the [Pt(2)(mu(2)-S)(2)M] core, viz. [Pt(2)(PPh(3))(4)(mu(3)-S)(2)HgFc]PF(6) (1) [Fc = (eta(5)-C(5)H(4))Fe(eta(5)-C(5)H(5))] and [Pt(2)(PPh(3))(4)(mu(3)-S)(2)Hg(2)Fc'](PF(6))(2) (2) [Fc' = Fe(eta(5)-C(5)H(4))(2)], have been synthesized under the guide of electrospray mass spectrometry. The electrochemistry of these ferrocene funtionalized compounds together with the reported [Pt(2)(PPh(3))(4)(mu(3)-S)(2)HgPPh(3)](PF(6))(2) (3), [Pt(2)(PPh(3))(4)(mu(2)-S)(mu(3)-S)HgPh]PF(6) (4), and [Pt(2)(PPh(3))(4)(mu(2)-S)(mu(3)-S)AuPPh(3)]PF(6) (5) have been investigated using cyclic voltammetry and DFT calculations. These results point to a prominent ligand-based oxidation.

Extending The Reaction Landscape of the {Pt(μ‐S)2Pt} Core: From Metal Centers to Non‐Metallic Electrophiles

“…In [(PPh 3 ) 2 Pt(µ-S)(µ-SHgR))Pt(PPh 3 ) 2 ] ϩ , the observed process consists of the monoelectronic oxidation of the sulfide ligand that is not coordinated to the mercury atom. [39] However, the poor solubility of [(PPh 3 ) 2 Pt(µ-S) 2 Pt(PPh 3 ) 2 ] hampered comparison between the redox properties of the {Pt(µ-S) 2 Pt} and {Pt(µ-S)(µ-SHg)Pt} ϩ cores. Notwithstanding this, results obtained with the highly soluble [L 2 Pt(µ-S) 2 PtL 2 ] (L 2 ϭ dppe or dppp) are consistent with the hypothesis presented by Hor et al, indicating that the sulfide ligands in the {Pt(µ-S) 2 Pt} fragment are electroactive.…”

Structure‐Dependent Electrochemical Behavior of Thienylplatinum(II) Complexes of N,N‐Heterocycles

“…1 H and 31 P NMR chemical shifts are quoted in ppm downfield of Me 4 Si and externally referenced to 85% H 3 PO 4 , respectively.…”

“…The product was purified by recrystallization from CH 2 Cl 2 /hexane to give pale yellow crystals. C 44 H 37 BF 4 …”

“…Our recent interest has been focused on novel electroactive metal-organic complexes. [4] Our current interest in d 8 thienyl complexes [5] stems from their geometric directionality and conductive potential [6] upon polymerization. Recently, we have extended this study to the construction of N-and Pbridged transition metal thienyl complexes.…”

Spanning [Pt2(μ-S)2(PPh3)4] metalloligands with 1,4-dimercurated durene

“…A range of organomercury complexes has previously been reacted with [Pt 2 (l-S) 2 (PPh 3 ) 4 ], using electrospray ionisation mass spectrometry (ESI MS) as a powerful tool to screen reactions for the successful formation of (cationic) products [8]. Isolated complexes include the simple adducts [Pt 2 (l-S) 2 (PPh 3 ) 4 HgPh]BPh 4 2 [8], [Pt 2 (l-S) 2 (PPh 3 ) 4 HgEt]PF 6 [8], [Pt 2 (l-S) 2 (PPh 3 ) 4 HgFc]PF 6 [9] [Fc = Fe(g 5 -C 5 H 5 ) (g 5 -C 5 H 4 )], the dimercurated ferrocene derivative [Pt 2 (l-S) 2 -(PPh 3 ) 4 Hg 2 Fc * ](PF 6 ) 2 [9] [Fc * = Fe(g 5 -C 5 H 4 ) 2 ] and the organomercury adducts of the monobenzylated {Pt 2 S 2 } core, [Pt 2 (l-SCH 2 Ph)-(l-SHgR)(PPh 3 ) 4 ](PF 6 ) 2 (R = Ph, Fc). [10] In this paper, we describe the reactivity of [Pt 2 (l-S) 2 (PPh 3 ) 4 ] towards dimercurated durene (1,2,4,5-tetramethylbenzene), AcOHgC 6 Me 4 HgOAc 3, which leads to the formation of hexametallic assemblies of two {Pt 2 S 2 } units spanned by the dimercurated arene moiety [HgC 6 Me 4 Hg] 2+ .…”