Reaktivität von Monophosphan‐Platin(0)‐Verbindungen gegenüber Schwefeldioxid

Heyke, O.; Maichle, C.; Hübener, Rainer; Lorenz, Ingo‐Peter

doi:10.1002/zaac.19936191028

Cited by 5 publications

(1 citation statement)

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“…The 42e – species of general formula Pt 3 (μ-L) 3 L′ 3 contain terminal L′ ligands such as CO, RNC, PR 3 and three neutral π-acceptor bridges (L = CO, RNC, SO 2 , R 2 E, with E = C, Si, Sn). The formal Pt 0 3 skeleton is normally equilateral with three short Pt–Pt linkages (2.61–2.82 Å). ,− , Other 42e – species instead involve three Pt(II) ions which, given their preference for the local 16 electron configuration, allow single Pt–Pt bonds consistently with an adjusted EAN rule . A matchless type of 42e – TPC is [Pt 3 (μ-dppm) 3 (μ 3 -CO)] 2+ (dppm = bis-diphenylphosphinomethane), which is the precursor of many tris-dppm bridged derivatives with a higher electron count.…”

Section: Introductionmentioning

confidence: 99%

Unprecedented Tris-Phosphido-Bridged Triangular Clusters with 42 Valence Electrons. Chemical, Electrochemical and Computational Studies of their Formation and Stability

et al. 2013

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This paper presents the synthesis and structural characterization of the unprecedented tris-phosphido-bridged compounds Pt3(μ-PBu(t)2)3X3 (X = Cl, Br, I), having only 42 valence electrons, while up to now analogous clusters typically have 44e(-). The new species were obtained by an apparent bielectronic oxidation of the 44e(-) monohalides Pt3(μ-PBu(t)2)3(CO)2X with the corresponding dihalogen X2. Their X-ray structures are close to the D3h symmetry, similarly to the 44e(-) analogues with three terminal carbonyl ligands. The products were also obtained by electrochemical oxidation of the same monohalides in the presence of the corresponding halide. In a detailed study on the formation of Pt3(μ-PBu(t)2)3I3, the redox potentials indicated that I2 can only perform the first monoelectronic oxidation but is unsuited for the second one. Accordingly, the 43e(-) intermediate [Pt3(μ-PBu(t)2)3(CO)2I](+) was ascertained to play a key role. Another piece of information is that, together with the fully oxidized product Pt3(μ-PBu(t)2)3I3, the transient 44e(-) species [Pt3(μ-PBu(t)2)3(CO)3](+) is formed in the early steps of the reaction. In order to extract detailed information on the formation pathway, involving both terminal ligand substitutions and electron transfer processes, a DFT investigation has been performed and all the possible intermediates have been defined together with their associated energy costs. The profile highlights many important aspects, such as the formation of an appropriate couple of 43e(-) intermediates having different sets of terminal coligands, and suitable redox potentials for the transfer of one electron. Optimizations of 45e(-) associative intermediates in the ligand substitution reactions indicate their possible involvement in the redox process with reduction of the overall energy cost. Finally, according to MO arguments, the unique stability of the 42e(-) phosphido-bridged Pt3 clusters can be attributed to the simultaneous presence of three terminal halides.

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Section: Introductionmentioning

confidence: 99%

Unprecedented Tris-Phosphido-Bridged Triangular Clusters with 42 Valence Electrons. Chemical, Electrochemical and Computational Studies of their Formation and Stability

et al. 2013

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Ligands’ σ-donation and π-backdonation effects on metal-metal bonding in trinuclear [M3(Tr)2(L)3]2+ (M = Fe, Ni, Pd, Pt, Tr = tropylium and L = CO, HCN and C2H4) sandwich compounds: Theoretical investigation

Zouchoune

Saiad

2018

Inorganica Chimica Acta

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Reactivity of the palladium dimer [Pd2(μ-SO2)(μ-dba)(PBz3)2]. Syntheses and structural characterisation of [Pd3(μ-SO2)3(PBz3)3], [Pd2(μ-SO2)(μ-dppm)(PBz3)2], [Pd(SO2)(PBz3)2], [Pd3(μ-CO)2(μ-SO2)(PBz3)3] and [Pd3(μ-SO2)2(CNBut )2(PBz3)3] (Bz = benzyl) †

Arifhodzic-Radojevic¹,

Burrows²,

Choi³

et al. 1999

J. Chem. Soc., Dalton Trans.

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Reaktivität von Monophosphan‐Platin(0)‐Verbindungen gegenüber Schwefeldioxid

Cited by 5 publications

References 15 publications

Unprecedented Tris-Phosphido-Bridged Triangular Clusters with 42 Valence Electrons. Chemical, Electrochemical and Computational Studies of their Formation and Stability

Unprecedented Tris-Phosphido-Bridged Triangular Clusters with 42 Valence Electrons. Chemical, Electrochemical and Computational Studies of their Formation and Stability

Ligands’ σ-donation and π-backdonation effects on metal-metal bonding in trinuclear [M3(Tr)2(L)3]2+ (M = Fe, Ni, Pd, Pt, Tr = tropylium and L = CO, HCN and C2H4) sandwich compounds: Theoretical investigation

Reactivity of the palladium dimer [Pd2(μ-SO2)(μ-dba)(PBz3)2]. Syntheses and structural characterisation of [Pd3(μ-SO2)3(PBz3)3], [Pd2(μ-SO2)(μ-dppm)(PBz3)2], [Pd(SO2)(PBz3)2], [Pd3(μ-CO)2(μ-SO2)(PBz3)3] and [Pd3(μ-SO2)2(CNBut )2(PBz3)3] (Bz = benzyl) †

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Reaktivität von Monophosphan‐Platin(0)‐Verbindungen gegenüber Schwefeldioxid

Cited by 5 publications

References 15 publications

Unprecedented Tris-Phosphido-Bridged Triangular Clusters with 42 Valence Electrons. Chemical, Electrochemical and Computational Studies of their Formation and Stability

Unprecedented Tris-Phosphido-Bridged Triangular Clusters with 42 Valence Electrons. Chemical, Electrochemical and Computational Studies of their Formation and Stability

Ligands’ σ-donation and π-backdonation effects on metal-metal bonding in trinuclear [M3(Tr)2(L)3]2+ (M = Fe, Ni, Pd, Pt, Tr = tropylium and L = CO, HCN and C2H4) sandwich compounds: Theoretical investigation

Reactivity of the palladium dimer [Pd2(μ-SO2)(μ-dba)(PBz3)2]. Syntheses and structural characterisation of [Pd3(μ-SO2)3(PBz3)3], [Pd2(μ-SO2)(μ-dppm)(PBz3)2], [Pd(SO2)(PBz3)2], [Pd3(μ-CO)2(μ-SO2)(PBz3)3] and [Pd3(μ-SO2)2(CNBut )2(PBz3)3] (Bz = benzyl) †

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Ligands’ σ-donation and π-backdonation effects on metal-metal bonding in trinuclear [M3(Tr)2(L)3]2+ (M = Fe, Ni, Pd, Pt, Tr = tropylium and L = CO, HCN and C2H4) sandwich compounds: Theoretical investigation