Heteropolytopic Arsanylarylthiolato Ligands: Cis–Trans Isomerism of Nickel(II), Palladium(II), and Platinum(II) Complexes of 1-AsPh2-2-SHC6H4

Hildebrand, Alexandra; Sárosi, Imola; Lönnecke, Peter; Silaghi‐Dumitrescu, Luminiţa; Sárosi, Menyhárt B.; Silaghi‐Dumitrescu, Ioan; Hey‐Hawkins, Evamarie

doi:10.1021/ic300002p

Cited by 19 publications

(14 citation statements)

References 84 publications

(51 reference statements)

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“…The crystal structure reveals a sulfur‐bridging edge‐sharing cyclic trinuclear complex with square‐planar coordination geometry around the platinum atoms (Figure ). Related structures were found for aminoalkylthiolato, [PtBr(μ‐SCH 2 CH 2 NMe 2 ‐κ 2 N , S )] 3 , phosphanylarylthiolato, [PtI(μ‐SC 6 H 4 ‐2‐PPh 2 ‐κ 2 P , S )] 3 and [PtI{μ‐SC 6 H 4 ‐2‐P(1,1′‐biphenyl)‐κ 2 P , S }] 3, and arsanylarylthiolato ligands, [PtI(μ‐SC 6 H 4 ‐2‐PAs 2 ‐κ 2 As , S )] 3 , but complex 2 is, to our knowledge, the first example with phosphanylalkylthiolato ligand.…”

Section: Resultssupporting

confidence: 70%

Structural Preferences in Phosphanylthiolato Platinum(II) Complexes

et al. 2015

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The transition‐metal complexes of heterotopic phosphanylthiolato ligands are useful in various reactions which depend on the stereochemistry of the complexes. Bis‐chelate complex [Pt(SCH2CH2PPh2‐κ2 P,S)2] (1) was obtained in good yields by direct base‐free substitution reaction of the corresponding phosphanylthiol (HSCH2CH2PPh2) with K2PtCl4 or by oxidative addition of the same phosphanylthiol to Pt(PPh3)4. In agreement with the antisymbiosis rule, complex 1 shows a cis‐P,P arrangement in solid state crystallizing in the monoclinic system (C2/c). Density functional theory (DFT) calculations on 1 reveal the right characteristics for the preferred cis‐P,P arrangement, rationalizing its formation. Direct base‐free reaction of [PtCl2(1,5‐cyclooctadiene)] with one equivalent of the same phosphanylthiol produce the trinuclear complex [PtCl(μ‐SCH2CH2PPh2‐κ2 P,S)]3 (2) instead of the binuclear structure common in palladium and nickel derivatives. Crystals of 2 are triclinic (P true1‾ ) showing a sulfur‐bridging edge‐sharing cyclic trinuclear complex with square‐planar coordination geometry around the platinum atoms and a Pt3S3 cycle in skew‐boat conformation. This preference for the trinuclear structure was rationalized mechanistically and through conceptual DFT.

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Section: Resultssupporting

confidence: 70%

Structural Preferences in Phosphanylthiolato Platinum(II) Complexes

et al. 2015

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“…Density functional calculations support the assumption that this is probably due to intramolecular π-π interaction of the biphenyl groups, which results in enhanced stability of the cis isomer. culations supported a dissociative mechanism for the isomerisation of the palladium(II) complexes [73].…”

Section: Iron and Ruthenium Complexesmentioning

confidence: 85%

“…The bidentate ligand HSC 6 H 4 -2-PPh 2 (PSH) was reported by E. Block et al, along with the tri-and tetradentate phosphinoarylthiols (HSC 6 H 4 -2) 2 PPh (PS 2 H 2 ) and (HSC 6 H 4 -2) 3 P (PS 3 H 3 ) [72]. The chemistry of the analogous AsSH, AsS 2 H 2 and AsS 3 H 3 arsinoarylthiols is less explored, the synthesis of these ligands has been recently reported by our group [73]. Scheme 12 shows the above-mentioned phosphino-and arsinoarylthiols.…”

Section: Preparation Of Hsc 6 H 4 -2-ephmentioning

confidence: 96%

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Synthesis and coordination chemistry of thiophenol-based heterodonor ligands containing P,S, As,S and P,SAs donor atoms

Sárosi

Silaghi‐Dumitrescu

Hey‐Hawkins

2013

Maced. J. Chem. Chem. Eng.

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This review article describes the synthesis and coordination chemistry of three types of thiophenol-based heterodonor ligands containing tertiary phosphine and/or arsine groups in combination with sulfur. Phenylthio(diphenyl)phosphine and -arsine ligands, EPh2(SPh) (E = P, As), incorporate an E–S bond in their structures. Upon reaction with different metal carbonyls, metal-mediated cleavage of the E–S bonds of these ligands has been observed, leading to a variety of sulfur- and phosphorus- or arsenic-containing metallacycles. The structurally isomeric phosphino- and arsinoarylthiols HSC6H4-2-EPh2 (ESH) combine a phosphine or arsine centre with a thiol functionality, which is usually deprotonated on coordination. These compounds have been shown to be very versatile ligands that form stable complexes with a wide range of transition metals. The heterotopic ligand 1-Ph2AsSC6H4-2-PPh2 (P,SAs) not only combines the properties of phenylthio(diphenyl)arsine and 2-diphenylphosphanylbenzenethiol by incorporating all three donor atoms in its structure, but also allows the effect of the PPh2 group in the ortho position on the cleavage of the As–S bond to be studied.

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“…In the case of Pt(II) the trimer [Pt(8)I] 3 was also isolated. 60 Pt(II) and Pd(II) complexes of the trithiacrown [9]aneS 3 with the general formula [M( [9]aneS 3 )(L 2 )] n+ , where L represents at least one Group 15 donor, have been reviewed. 61 The metal-ligand cooperative effect of PNP and PCP pincer ligands relevant to catalytic applications has been explored.…”

Section: Coordination and Organometallic Chemistrymentioning

confidence: 99%

Nickel, palladium and platinum

Dervisi

2013

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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This report summarizes the literature from 2012 relevant to the chemistry of the group 10 transition elements. Novel coordination and organometallic compounds of these elements are presented and selected applications in the areas of catalysis, bioinorganic/ medicinal chemistry are discussed. HighlightsNotable highlights from 2012 include advances in the fundamental chemistry and applications of high-valent Pd(III/IV) complexes in catalytic transformations 46 and the palladium-catalysed oxidation reactions using simple oxidants such as molecular oxygen.

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Heteropolytopic Arsanylarylthiolato Ligands: Cis–Trans Isomerism of Nickel(II), Palladium(II), and Platinum(II) Complexes of 1-AsPh₂-2-SHC₆H₄

Cited by 19 publications

References 84 publications

Structural Preferences in Phosphanylthiolato Platinum(II) Complexes

Structural Preferences in Phosphanylthiolato Platinum(II) Complexes

Synthesis and coordination chemistry of thiophenol-based heterodonor ligands containing P,S, As,S and P,SAs donor atoms

Nickel, palladium and platinum

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