Preparation of Organomercury Compounds

Larock, Richard C.

doi:10.1007/978-3-642-70004-0_2

Cited by 7 publications

(6 citation statements)

References 886 publications

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“…199 which appears at δ = -1109 ppm. Symmetrisation is a well known reaction in organometallic mercury compounds [27][28][29] and the occurrence of such a process would be consistent with the tendency for organomercury compounds to maintain linearity in R 2 Hg or RHgX systems. The overall reaction can be represented as follows:…”

Section: Spectral Datamentioning

confidence: 52%

Symmetrisation in the Interaction of Chloro[2‐(dimethylaminomethyl)phenyl‐C¹]mercury(II) with Thiosemicarbazone Derivatives of Pyridine‐2‐carboxamide and Pyrazin‐2‐carboxamide

et al. 2006

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Pyridine‐ and pyrazine‐2‐carboxamide thiosemicarbazones (HAm4DH and HAmpz4DH) or their N4,N4‐dimethyl derivatives (HAm4DM and HAmpz4DM) react with chloro[2‐(dimethylaminomethyl)phenyl‐C1]mercury(II), [Hg(damp)Cl], to give the tetrahedral [Hg(TSC)2] complexes [TSC = Am4DH (1), Am4DM (2), Ampz4DH (3) or Ampz4DM (4)]. Spectroscopic studies and a X‐ray structural analysis show that the potentially tridentate thiosemicarbazones adopt S,N coordination modes, with each deprotonated thiosemicarbazone binding to the HgII centre through the azomethine nitrogen and the thiolate sulfur atoms, whereas the heterocyclic nitrogen atoms are free of coordination. Intra‐ and intermolecular hydrogen bonding in all complexes and specific C–H···π interactions with the chelate or pyridyl rings of the complexes 1 and 2 were found in the crystal structures. Furthermore, [Hg(damp)Cl] undergoes symmetrisation to give the symmetric unit [Hg(Hdamp)2]2+ in which the Hdamp is protonated at the nitrogen. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

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Section: Spectral Datamentioning

confidence: 52%

Symmetrisation in the Interaction of Chloro[2‐(dimethylaminomethyl)phenyl‐C¹]mercury(II) with Thiosemicarbazone Derivatives of Pyridine‐2‐carboxamide and Pyrazin‐2‐carboxamide

et al. 2006

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“…This is a well-known synthesis of iodoarenes. 52 By reacting 6 with HS(CH 2 ) 2 SH, the desired IAr a (7a) was obtained. Similarly, from IC 6 H(OMe) 3 -2,3,4-CHO-6 (8) 48 other iododithioacetal arenes such as IC 6 H(OMe) 3 -2,3,4-{CH(SCH 2 CH 2 S)}-6 (7b) or IC 6 H(OMe) 3 -2,3,4-{CH-(STo) 2 }-6 (9) 41 were prepared.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Reactivity of Ortho-Mercuriated and Ortho-Palladated Arylacetals and Cyclic and Acyclic Aryldithioacetals. New Examples of the Rearrangement of Acyclic Dithioacetal Aryl- to Dithioether Alkyl-Palladium Complexes

et al. 2004

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The arylmercurial [Hg{C6H3(CHO)2-2,5}Cl] (1) reacts with CH(OMe)3 or HS(CH2)2SH to give [Hg{C6H3{CH(OMe)2}2-2,5}Cl] (2) or [Hg(Ara)Cl] [Ara = C6H3{CH(SCH2CH2S)}2-2,5 (3a)], respectively. The mercurial 2 or 3a reacts with (NMe4)2[Pd2Cl6] and 2,2‘-bipyridine (bpy) or with trans-[PdCl2(PPh3)2] to give the aryl-palladium complex [Pd{C6H3{CH(OMe)2}2-2,5}Cl(bpy)] (4) or [Pd(κ2-C,S-Ara)Cl(PPh3)] (5a*), respectively. The reaction of 1 with NaI3 renders IC6H3(CHO)2-2,5 (6), which reacts with HS(CH2)2SH to give IAra (7a). Similarly, IC6H(OMe)3-2,3,4-(CHO)-6 (8) reacts with HS(CH2)2SH or ToSH (To = C6H4Me-4) to give the corresponding dithioacetals IArb [Arb = C6H(OMe)3-2,3,4-{CH(SCH2CH2S)}-6 (7b)] or IC6H(OMe)3-2,3,4-CH(STo)2-6 (9). The iodoarene 7a or 7b adds oxidatively to “Pd(dba)2” (dba = dibenzylideneacetone) to give [Pd(κ2-C,S-Ar)(μ-I)]2 [Ar = Ara (10a), Arb (10b)], which, in turn, reacts (i) with 1 equiv of PPh3 to give [Pd(κ2-C,S-Ar)I(PPh3)] [Ar = Ara (5a), Arb (5b)], (ii) with Tl(TfO) (TfO = CF3SO3) and PPh3 (1:2:4 molar ratio) to give [Pd(κ2-C,S-Arb)(PPh3)2]TfO (11b), or (iii) with 1 equiv of Tl(TfO) and bpy (1:2:2 molar ratio) to give [Pd(κ2-C,S-Arb)(bpy)]TfO (11b*). Complexes 10 react with 1 equiv of isonitriles to give, after a short period of reaction, the complexes [Pd(κ2-C,S-Ar)I(CNR)] [Ar = Ara, R = Xy = 2,6-dimethylphenyl (12a), tBu (12a‘); Ar = Arb, R = tBu (12b‘)]. The iminoacyl complexes [Pd(κ 2 -C,S-Im)(μ-I)]2 [Im = Ima (13a), Imb (13b)] can be obtained by stirring a solution of 12a for 5 days to give 13a or by reacting 10b with XyNC in 1:1 molar ratio during 22 h to give 13b. Complexes 10 react with 2 equiv of isonitriles to give the iminoacyl complexes [Pd(κ2-C,S-Im)I(CNR)] [Im = C(NR)C6H3{CH(SCH2CH2S)}2-2,5, R = Xy, Im = Ima (14a), R = tBu, Im = Ima ‘ (14a‘); Im = C(NR)C6H(OMe)3-2,3,4-(SCH2CH2S)-6, R = Xy, Im = Imb (14b), R = tBu, Im = Imb ‘ (14b‘)]. Complexes 14a,b react with 10a,b in 2:1 molar ratio to give 13a,b. Complexes 10a,b react with XyNC and Tl(TfO) (1:4:1) to give the dimeric cations [Pd{(κ 2-C,S-Im)(CNXy)}2(μ-I)]TfO [R = Xy, Im = Ima (15a), Imb (15b)]. The compound [Pd{κ 2-C,S-Arc}(μ-I)]2 (16) reacts (i) with PPh3 and Tl(TfO) in 1:4:2 molar ratio to give [PdII(κ 2-C,S-Arc)(PPh3)2]TfO ↔ [Pd0{η 2 -κ3-C,S,S-S(To)CHC6H(STo)-2-(OMe)3-3,4,5}(PPh3)2]TfO (17), (ii) with isonitriles in 1:2 or 1:4 molar ratio yielding complexes [Pd(κ 2-C,S-Arc)I(CNR)] [R = Xy (18), R = tBu (18‘)] or trans-[Pd(κ 1 -C-Arc)I(CNR)2] [R = Xy (19), R = tBu (19‘)], respectively, and (iii) with PPh3 in 1:2 molar ratio yielding [Pd(κ2-C,S-Arc)I(PPh3)] (20). The iodoarene 9 reacts with Pd(dba)2 (i) and PPh3 (1:1:1 molar ratio) to give [Pd{κ 2-C,S-Arc)I(PPh3)] [Arc = CH(STo)C6H(STo)-2- (OMe)3-3,4,5 (20)] and (ii) PPh3 and Tl(TfO) (1:1:2:1 molar ratio) to give 17. The crystal and molecular structures of 4, 5a*, 14a, and 14b have been determined by X-ray diffraction studies.

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“…The concentrations of LOOH and RHgX, R 2 Hg are comparable, and the organomercury compounds act as reagents in protolytic reactions [17]:…”

Section: The Promoting Effect Of Organomercurials In the Peroxidationmentioning

confidence: 99%

“…The chain radical oxidation of the unsaturated fatty acids LH (oleic, linoleic, linolenic, arachidonic acids) in lipid bilayer is the source of highly reactive intermediates L Å , LO Å , LOO Å that leads to the oxidative destruction of lipids and to the membranes damage. Since organomercury compounds RHgX and R 2 Hg are lipophilic and membrane active species they are capable to interact with free radicals L Å , LO Å , LOO Å [17] and act as prooxidants initiating the sequence of chain reactions by producing R Å .…”

Section: The Impact Of Organomercurials Upon the Peroxidation Of Lipimentioning

confidence: 99%

The role of radical reactions in organomercurials impact on lipid peroxidation

Милаева

2006

Journal of Inorganic Biochemistry

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Preparation of Organomercury Compounds

Cited by 7 publications

References 886 publications

Symmetrisation in the Interaction of Chloro[2‐(dimethylaminomethyl)phenyl‐C¹]mercury(II) with Thiosemicarbazone Derivatives of Pyridine‐2‐carboxamide and Pyrazin‐2‐carboxamide

Symmetrisation in the Interaction of Chloro[2‐(dimethylaminomethyl)phenyl‐C¹]mercury(II) with Thiosemicarbazone Derivatives of Pyridine‐2‐carboxamide and Pyrazin‐2‐carboxamide

Synthesis and Reactivity of Ortho-Mercuriated and Ortho-Palladated Arylacetals and Cyclic and Acyclic Aryldithioacetals. New Examples of the Rearrangement of Acyclic Dithioacetal Aryl- to Dithioether Alkyl-Palladium Complexes

The role of radical reactions in organomercurials impact on lipid peroxidation

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Preparation of Organomercury Compounds

Cited by 7 publications

References 886 publications

Symmetrisation in the Interaction of Chloro[2‐(dimethylaminomethyl)phenyl‐C1]mercury(II) with Thiosemicarbazone Derivatives of Pyridine‐2‐carboxamide and Pyrazin‐2‐carboxamide

Symmetrisation in the Interaction of Chloro[2‐(dimethylaminomethyl)phenyl‐C1]mercury(II) with Thiosemicarbazone Derivatives of Pyridine‐2‐carboxamide and Pyrazin‐2‐carboxamide

Synthesis and Reactivity of Ortho-Mercuriated and Ortho-Palladated Arylacetals and Cyclic and Acyclic Aryldithioacetals. New Examples of the Rearrangement of Acyclic Dithioacetal Aryl- to Dithioether Alkyl-Palladium Complexes

The role of radical reactions in organomercurials impact on lipid peroxidation

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Symmetrisation in the Interaction of Chloro[2‐(dimethylaminomethyl)phenyl‐C¹]mercury(II) with Thiosemicarbazone Derivatives of Pyridine‐2‐carboxamide and Pyrazin‐2‐carboxamide

Symmetrisation in the Interaction of Chloro[2‐(dimethylaminomethyl)phenyl‐C¹]mercury(II) with Thiosemicarbazone Derivatives of Pyridine‐2‐carboxamide and Pyrazin‐2‐carboxamide