Electron-Ligand Interchange Reactions between Palladium(II) Complexes and Mercury and Single-Crystal X-ray Characterization of the d10-d10 Binuclear [Hg2(dppm)2Cl3]Cl Complex

Harvey, Pierre D.; Aye, Khin Than; Hierso, Karine; Isabel, Élise; Lognot, Isabelle; Mugnier, Yves; Rochon, Fernande D.

doi:10.1021/ic00104a002

Cited by 18 publications

(18 citation statements)

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“…So far, examples of strong Hg +II −Hg +II interactions are relatively rare [40–42] . Only a small number of crystal structures contain shorter contacts than the here reported 3.353(1) Å [36, 43–47] . Furthermore, only a few examples of crystal structures of permercurated compounds are known so far [48–50] …”

Section: Methodsmentioning

confidence: 63%

“…[40][41][42] Only as mall number of crystal structures contains horter contacts than theh erer eported 3.353(1) . [36,[43][44][45][46][47] Furthermore, only af ew examples of crystal structures of permercuratedc ompounds arek nown so far. [48][49][50] The soluble compounds 2 (butyrate) and 3 (trihaloacetate) were characterizedv ia NMR spectroscopy.T he 13 CNMR spectra of 3a and 3b displayt hree signals, respectively.C ompound 2 shows five signals.…”

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confidence: 99%

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Tenfold Metalation of Ferrocene: Synthesis, Structures, and Metallophilic Interactions in FeC₁₀(HgX)₁₀

Rupf

Schröder

Sievers

et al. 2021

Chemistry A European J

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The permercuration of ferrocene was achieved by reacting ferrocene with 10 equivalents of mercury(II) butyrate Hg(O2CC3H7)2 in a facile one‐pot reaction in multi‐gram scale and high yields. The butyrate groups in FeC10(HgX)10 (X=O2CC3H7) can be exchanged by treatment with trifluoro‐ or trichloroacetic acid (X=O2CCF3, O2CCCl3). Substitution of the trifluoroacetate groups by halides (X=Cl, F) proceeds easily in aqueous THF. The completeness of metalation was confirmed by NMR and vibrational spectroscopy, mass spectrometry, as well as elemental analysis. Additionally, the first crystal structures of permetallated metallocenes are presented: FeC10(HgX)10 (X=Cl, O2CCF3, O2CCCl3).

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Section: Methodsmentioning

confidence: 63%

mentioning

confidence: 99%

Tenfold Metalation of Ferrocene: Synthesis, Structures, and Metallophilic Interactions in FeC₁₀(HgX)₁₀

Rupf

Schröder

Sievers

et al. 2021

Chemistry A European J

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“…Surprisingly, despite the reports concerning problems with the mercury test − and a substantial number of publications describing sufficiently high reactivity of various palladium, platinum, and other organometallic compounds toward metallic mercury, − ,− numerous research groups have continued to apply the mercury test in catalytic studies even though the accuracy of the method is questionable.…”

Section: Introductionmentioning

confidence: 99%

Pd and Pt Catalyst Poisoning in the Study of Reaction Mechanisms: What Does the Mercury Test Mean for Catalysis?

et al. 2019

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The mercury test is a rapid and widely used method for distinguishing truly homogeneous molecular catalysis from nanoparticle metal catalysis. In the current work, using various M 0 and M II complexes of palladium and platinum that are often used in homogeneous catalysis as examples, we demonstrated that the mercury test is generally inadequate as a method for distinguishing between homogeneous and cluster/nanoparticle catalysis mechanisms for the following reasons: (i) the general and facile reactivity of both molecular M 0 and M II complexes toward metallic mercury and (ii) the very high and often unpredictable dependence of the test results on the operational conditions and the inability to develop universal quantitatively defined operational parameters. Two main types or mercury-induced transformations, the cleavage of M 0 complexes and the oxidative−reductive transmetalation of M II complexes, including a reaction of highly popular M II /NHC complexes, were elucidated using NMR, ESI-MS, and EDXRF techniques. A mechanistic picture of the reactions involving metal complexes was revealed with mercury, and representative metal species were isolated and characterized. Even in an attempt to not overstate the results, one must note that the use of the mercury tests often leads to inaccurate conclusions and complicates the mechanistic studies of these catalytic systems. As a general concept, distinguishing reaction mechanisms (homogeneous vs cluster/nanoparticle) by using catalyst poisoning requires careful rethinking in the case of dynamic catalytic systems.

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“…A closer nonbonding Hg···Hg contact has been reported in [Hg 2 (1,8-C 10 H 6 ) 2 ] [2.797(1) Å], [34] 4 ] is not considered bonding. [27] It has been claimed on the basis of a low frequency [33] We find this difficult to sustain for an Hg II ···Hg II interaction, unless electron density is transmitted from Hg-Cl bonds.…”

Section: X-ray Crystal Structures and Characterisationmentioning

confidence: 65%

“…The Hg(1)-Cl(1) terminal bond length in 4·3/ 2 CDCl 3 , 2.624(2) Å, is considerably extended relative to those in [HgCl 4 ] 2-complexes, which possess an average HgCl bond length of 2.472 Å, [32] but well inside the sum (3.58 Å) of the van der Waals radii of Hg and Cl. In [Hg 2 [33] which has a somewhat similar structural core to 4·3/2 CDCl 3 , the mean terminal Hg-Cl bond length is 2.587 Å, similar to that of 4·3/2 CDCl 3 .…”

Section: X-ray Crystal Structures and Characterisationmentioning

confidence: 81%

Novel Mercury Phosphanylamides

et al. 2005

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The reactions of bis(pentafluorophenyl)mercury, bis(diphenylphosphanyl)amine and neodymium or erbium metal in toluene yielded the subvalent mercury(1.33) complex [Hg3{μ2‐(Ph2P)2N}4]·3 C7H8 (1·3 C7H8) as a toluene solvate. Thecomplex was also prepared in high yield from Hg(C6F5)2, (PPh2)2NH and mercury metal in toluene at room temperature. From reaction of Hg(C6F5)2 and HN(PPh2)2 in toluene with no added metal, [Hg2{μ2‐(Ph2P)2N}2{(Ph2P)(OPPh2)N}2]·2 C7H8 (3·2 C7H8) has been obtained, and 3·2 C4H10O2 has also been isolated in low yield. From a related reaction, a solution of the product in CDCl3 deposited [Hg2{μ2‐(Ph2P)2N}3Cl]·3/2 CDCl3 (4·3/2 CDCl3). The structure of 1·3 C7H8 contains a Hg–Hg bonded Hg3 triangle with adja‐cent metals bridged (P,P′) by either one or two phosphanyl‐amide ligands. One mercury is four coordinate, and the other two are five coordinate. In [Hg2{μ2‐(Ph2P)2N}2{(Ph2P)(OPPh2)‐N}2]·2 S [S = C7H8 or C4H10O2 (1,2‐dimethoxyethane)], the mercury atoms are bridged (P,P′) by two phosphanylamide ligands, whilst the hemi‐oxidised ligands are chelating (O,P) in a transoid disposition to each other leading to four coordination. There is unsymmetrical ligation in [Hg2{μ2‐(Ph2P)2N}3Cl]·3/2 CDCl3 (4·3/2 CDCl3) with one mercury four coordinate and the other three. Three phosphanylamide ligands bridge (P,P′) the metals with a non‐bonding Hg···Hg separation of 3.0042(7) Å. Each HgP3 array has a triangular arrangement, little affected in one case by the attachment of a chloride approximately normal to HgP3. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

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Electron-Ligand Interchange Reactions between Palladium(II) Complexes and Mercury and Single-Crystal X-ray Characterization of the d10-d10 Binuclear [Hg2(dppm)2Cl3]Cl Complex

Cited by 18 publications

References 0 publications

Tenfold Metalation of Ferrocene: Synthesis, Structures, and Metallophilic Interactions in FeC₁₀(HgX)₁₀

Tenfold Metalation of Ferrocene: Synthesis, Structures, and Metallophilic Interactions in FeC₁₀(HgX)₁₀

Pd and Pt Catalyst Poisoning in the Study of Reaction Mechanisms: What Does the Mercury Test Mean for Catalysis?

Novel Mercury Phosphanylamides

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Electron-Ligand Interchange Reactions between Palladium(II) Complexes and Mercury and Single-Crystal X-ray Characterization of the d10-d10 Binuclear [Hg2(dppm)2Cl3]Cl Complex

Cited by 18 publications

References 0 publications

Tenfold Metalation of Ferrocene: Synthesis, Structures, and Metallophilic Interactions in FeC10(HgX)10

Tenfold Metalation of Ferrocene: Synthesis, Structures, and Metallophilic Interactions in FeC10(HgX)10

Pd and Pt Catalyst Poisoning in the Study of Reaction Mechanisms: What Does the Mercury Test Mean for Catalysis?

Novel Mercury Phosphanylamides

Contact Info

Product

Resources

About

Tenfold Metalation of Ferrocene: Synthesis, Structures, and Metallophilic Interactions in FeC₁₀(HgX)₁₀

Tenfold Metalation of Ferrocene: Synthesis, Structures, and Metallophilic Interactions in FeC₁₀(HgX)₁₀