Extending knowledge on the nucleophilicity of the {Pt2S2} core: Ph2PCH2CH2PPh2 as an alternative terminal ligand in [L2Pt(μ-S)2PtL2] metalloligands †

Capdevila, Mercè; Carrasco, Yolanda; Clegg, William; Coxall, Robert A.; González-Duarte, Pilar; Lledós, Agustı́; Ramírez, José A.; Ramı́rez, Antonio

doi:10.1039/a903899j

Cited by 43 publications

(37 citation statements)

References 28 publications

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“…This decomposition is probably facilitated by nucleophilic attack of chlorinated solvent [29]. (6) -2.4919(6) Å) [40].The Pt-C (2.015(10) Å) distance is in agreement with the one reported for [PtX(Ph)(PPh3)2] (X = Cl, I) (Pt-C = 2.01(1), 2.015(9) Å) [35,36]. The Zn-N and Zn-Cl distances are as expected [29,36,[43][44][45][46].…”

Section: Resultssupporting

confidence: 79%

“…While latter resonance ~ -11 ppm with the coupling constant ~3150Hz is phenomenal agreement with reported heterometallic complexes [M{Pt2(dppe)2(μ3-S)2}X2] (M = Zn, Cd and Hg) [29,36]. Hence, this resonance belongs to selenolate ligand which is attached to platinum as well as with Cd, Hg, Cu also.…”

Section: Resultssupporting

confidence: 72%

“…The geometry around the Pt metal center is confined with 'P2Se2' fragments with distorted square planner geometry however Cd atom opts distorted octahedral shape which is defined with 'N2O2Cl' frame with Cl and Se atom at axial position. The Pt-P and Pt-Se distances are as expected [29,36] (Cd….S = 2.561(2) -2.553(2) Å) [36]. Because of these interactions Cd….Se pyridyl selenolate group move out from metal plane.…”

Section: Crystal Structuresmentioning

confidence: 68%

“…Due to bonding with latter metal centres, electron density around selenium atom gets reduced. As a result it showed shielded resonance compares to other one [36]. The Hz)] [37][38].…”

Section: Resultsmentioning

confidence: 99%

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Synthesis and characterization of heterobimetallic complexes with pyridyl selenolato ligands. Crystal structure of [{Pt(C5H4N)(SeC5H4N)(dppp)}ZnCl2]

Chauhan

Shivran

Slawin

et al. 2017

Journal of Organometallic Chemistry

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Reactions of [Pt(SeC5H4N)2(P∩P)] with M(OAc)2.2H2O/MX2 (P∩P = dppm, dppp; M = Zn, Cd, Hg, Cu; X = Cl) resulted various products depend upon the nature of the phosphine. In case of dppm, reaction between [Pt(SeC5H4N)2(dppm)] and M(OAc)2.2H2O/MX2 (M = Zn, Cd, Hg) afforded an exchange product of composition [PtCl2(dppm)]. Similarly, the reaction with 'dppp' analog yielded an adduct [{Pt(SeC5H4N)2(dppp)}MX2] (M = Cd, Hg, Cu; X = Cl, OAc).Whereas, reaction with Zn(OAc)2, on extraction with dichloromethane resulted the product with the loss of one selenium atom of composition [{Pt(C5H4N)(SeC5H4N)(dppp)}ZnCl2]. These complexes were characterized by elemental analyses and NMR ( 1 H, 31 P, 77 Se, 195 Pt) spectroscopy. The molecular structure of [{Pt(C5H4N)(SeC5H4N)(dppp)}ZnCl2] was established by single crystal X-ray diffraction analyses.

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Section: Resultssupporting

confidence: 79%

Section: Resultssupporting

confidence: 72%

Section: Crystal Structuresmentioning

confidence: 68%

“…Due to bonding with latter metal centres, electron density around selenium atom gets reduced. As a result it showed shielded resonance compares to other one [36]. The Hz)] [37][38].…”

Section: Resultsmentioning

confidence: 99%

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Synthesis and characterization of heterobimetallic complexes with pyridyl selenolato ligands. Crystal structure of [{Pt(C5H4N)(SeC5H4N)(dppp)}ZnCl2]

Chauhan

Shivran

Slawin

et al. 2017

Journal of Organometallic Chemistry

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“…Our approach has focused on the use of chelating diphosphanes as terminal L ligands, [12] with an emphasis on the chemistry of [L 2 Pt(µ-S) 2 tal electrophiles [9,10] and MLЈ y fragments. [11] This report surveys the present knowledge on the nucleophilicity of the {Pt(µ-S) 2 Pt} core in [L 2 Pt(µ-S) 2 PtL 2 ] compounds; the previous review by Fong and Hor is our starting point.…”

Section: Introductionmentioning

confidence: 99%

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

2004

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The outstanding nucleophilicity of the {Pt(μ‐S)2Pt} core in compounds [L2Pt(μ‐S)2PtL2] (L2 = phosphane) accounts for their ability to act as metalloligands towards main group and transition metals, and thus for the high number of [{L2Pt(μ3‐S)2PtL2}xML′y]z aggregates already described. However, the electronic and molecular features underpinning this behavior anticipate a landscape of comparable richness for the reactions of [L2Pt(μ‐S)2PtL2] with non‐metal electrophiles. Exploration of the chemistry of [L2Pt(μ‐S)2PtL2] (L2 = chelating diphosphane) towards various electron‐acceptor species has been the aim of our research for the past years. In this microreview we survey the synthetic strategies of [L2Pt(μ‐S)2PtL2] compounds, their distinguishing electronic and molecular features, the dynamic processes and electron‐donor properties of the {Pt(μ‐S)2Pt} core, and its binding ability towards metal centers. Moreover, particular attention is given to the reaction chemistry of [L2Pt(μ‐S)2PtL2] with organic electrophiles and protic acids, as well as to the influence of the {Pt(μ‐S)2Pt} core on the reactivity of inorganic or organic L′ ligands in [{L2Pt(μ3‐S)2PtL2}xML′y]z aggregates. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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The Evolution of [{Ph₂P(CH₂)_nPPh₂}Pt(μ‐S)₂Pt{Ph₂P(CH₂)_nPPh₂}] (n=2, 3) Metalloligands in Protic Acids: A Cascade of Sequential Reactions

Aullón¹,

Champkin²,

Clegg³

et al. 2003

Chemistry A European J

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Given the nucleophilicity of the [Pt(2)S(2)] ring, the evolution of [Pt(2)(mu-S)(2)(P intersection P)(2)] (P intersection P=1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp)) metalloligands in the presence of the simplest electrophilic species, the proton, has been studied. Combined use of experimental and theoretical data has allowed the whole set of reactions ensuing the protonation of the [Pt(2)S(2)] core to be established. The titration of [Pt(2)(mu-S)(2)(P intersection P)(2)] with HCl or HClO(4) was monitored mainly by (31)P[(1)H] NMR and mass techniques. Characterization of all the species involved was completed with the determination of the crystal structure of [Pt(SH)(2)(P intersection P)], for dppe and dppp, and [Pt(3)(mu(3)-S)(2)(dppp)(3)](PF(6))(2). The first protonation step of the [Pt(2)S(2)] core leads to the stable [Pt(2)(mu-S)(mu-SH)(P intersection P)(2)](+) complex, but the second step implies disintegration of the ring, thus giving rise to various mononuclear species. The subsequent evolution of some of these species allows regeneration of [Pt(2)(mu-S)(mu-SH)(P intersection P)(2)](+), evidencing the cyclic nature of this process. Whereas the reaction pathway is essentially common for both phosphine ligands, dppe and dppp, the different coordinating ability of Cl(-) or ClO(4) (-) determines the nature of the final products, [PtCl(2)(P intersection P)], [Pt(3)(mu(3)-S)(2)(P intersection P)(3)]Cl(2) or [Pt(3)(mu(3)-S)(2)(P intersection P)(3)](ClO(4))(2). DFT calculations have corroborated the thermodynamic feasibility of the reactions proposed on the basis of experimental data.

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Extending knowledge on the nucleophilicity of the {Pt2S2} core: Ph2PCH2CH2PPh2 as an alternative terminal ligand in [L2Pt(μ-S)2PtL2] metalloligands †

Cited by 43 publications

References 28 publications

Synthesis and characterization of heterobimetallic complexes with pyridyl selenolato ligands. Crystal structure of [{Pt(C5H4N)(SeC5H4N)(dppp)}ZnCl2]

Synthesis and characterization of heterobimetallic complexes with pyridyl selenolato ligands. Crystal structure of [{Pt(C5H4N)(SeC5H4N)(dppp)}ZnCl2]

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

The Evolution of [{Ph₂P(CH₂)_nPPh₂}Pt(μ‐S)₂Pt{Ph₂P(CH₂)_nPPh₂}] (n=2, 3) Metalloligands in Protic Acids: A Cascade of Sequential Reactions

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Extending knowledge on the nucleophilicity of the {Pt2S2} core: Ph2PCH2CH2PPh2 as an alternative terminal ligand in [L2Pt(μ-S)2PtL2] metalloligands †

Cited by 43 publications

References 28 publications

Synthesis and characterization of heterobimetallic complexes with pyridyl selenolato ligands. Crystal structure of [{Pt(C5H4N)(SeC5H4N)(dppp)}ZnCl2]

Synthesis and characterization of heterobimetallic complexes with pyridyl selenolato ligands. Crystal structure of [{Pt(C5H4N)(SeC5H4N)(dppp)}ZnCl2]

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

The Evolution of [{Ph2P(CH2)nPPh2}Pt(μ‐S)2Pt{Ph2P(CH2)nPPh2}] (n=2, 3) Metalloligands in Protic Acids: A Cascade of Sequential Reactions

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

The Evolution of [{Ph₂P(CH₂)_nPPh₂}Pt(μ‐S)₂Pt{Ph₂P(CH₂)_nPPh₂}] (n=2, 3) Metalloligands in Protic Acids: A Cascade of Sequential Reactions