Protolytic Cleavage of Hg–C Bonds Induced by 1-Methyl-1,3-dihydro-2<i>H</i>-benzimidazole-2-selone: Synthesis and Structural Characterization of Mercury Complexes

Palmer, Joshua H.; Parkin, Gerard

doi:10.1021/jacs.5b00840

Cited by 35 publications

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References 184 publications

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“…In all the cases, formation of dicationic diselenides (8)(9)(10)(11)(12) was observed (Scheme 2). In all the cases, formation of dicationic diselenides (8)(9)(10)(11)(12) was observed (Scheme 2).…”

Section: Resultsmentioning

confidence: 96%

“…1,2 Compared to the carbene derivatives of group 13-15, the carbene derivatives of chalcogens have not been studied in detail. 10 Very recently, Roy and coworkers 11 Both selones and dihaloselones are excellent precursors for dicationic diselenides. 7 While attempting to prepare diaryl diselenides stabilized by intramolecular coordination with carbene (2) from compound 1, we observed a facile formation of selones (3a) (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

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Transition metal mediated formation of dicationic diselenides stabilised by N-heterocyclic carbenes: designed synthesis

et al. 2016

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Reactions of the N-heterocyclic carbene derivatives of selenium(ii) dihalides, LSeX2 (X = Cl, Br; L = 1,3-dibutylbenzimidazol-2-ylidene, C15H22N2) (4b, 4b'), L'SeX2 (X = Cl, Br; L' = 1,3-di(n)propylbenzimidazol-2-ylidene, C13H18N2) (4c, 4c') and L''SeX2 (X = Cl, Br; L'' = 1,3-di(i)propylbenzimidazol-2-ylidene, C13H18N2) (4d, 4d') with iron led to the formation of dicationic diselenides, [L2Se2(2+)]2[{FeCl4}(-)]3Cl(-) (7), [L2Se2(2+)][FeBr4](-)Br(-) (8), [L'2Se2(2+)][FeCl4](-)Cl(-) (9), [L'2Se2(2+)][FeBr4](-)Br(-) (10), [L''2Se2(2+)][FeCl4](-)Cl(-) (11) and [L''2Se2(2+)][FeBr4](-)Br(-) (12). The reactions of LSeX2 with copper gave selone (LSe) complexes of cuprous halides, [(LSe)2CuBr] (13) and [(LSe)2(CuI)2] (14) respectively. However, LSeX2 (X = Cl, Br, I) (4b-4b'') on treatment with zinc gave both the dicationic diselenides, [L2Se2(2+)]Y [Y = {ZnCl3(H2O)2}(2-) (15), {ZnBr4}(2-) (17)] and complexes, [(LSe)2ZnX2] (16, 18, 20). The plausible mechanism for the formation of dicationic diselenides, [L2Se2(2+)], has been proposed and is supported by performing various test reactions. To validate these mechanisms, DFT calculations have been carried out. Interestingly, the reactions of the mixture of LSeX2/L'SeX2/L''SeX2 and L'Se(0)/L'Se(0)/L''Se(0) with metal halides (FeCl3, ZnX2; X = Cl, Br, I; CdI2, HgI2, PdCl2, and PtCl2) produced dicationic diselenides, 7-12, 15, 17 and [L2Se2(2+)]Y [Y = {ZnI4}(2-) (19), {CdI4}(2-) (22), {HgI4}(2-) (25), {PdCl4}(2-) (26), {PtCl4}(2-) (27)]. The methodology is more general than the previous method and gives better yields of [L2Se2(2+)]Y. The controlled oxidation of complexes, [(LSe)2MX2] (M = Zn, Cd, Hg; X = Cl, Br, I) (16, 18, 20, 28-32) with halogenating agents (SOCl2/Br2/I2) also gave dicationic diselenides, 15, 17, 19, 22, 25 and [L2Se2(2+)]Y [Y = {CdCl4}(2-) (21), {Hg2Cl6}(2-) (23), {HgBr4}(2-) (24)], proving to be the most general method for the synthesis of [L2Se2(2+)]. Attempted syntheses of unsymmetrical dicationic diselenides, [LSe-SeL'](2+)[FeCl4](-)Cl(-) and dicationic ditelluride, [L2Te2(2+)]2[{FeCl4}(-)]3Cl(-) by the reaction of LSeX2/LTeX2 (X = Cl, Br, I) with Fe metal were unsuccessful. This observation has been corroborated with DFT calculations.

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Section: Resultsmentioning

confidence: 96%

Section: Introductionmentioning

confidence: 99%

Transition metal mediated formation of dicationic diselenides stabilised by N-heterocyclic carbenes: designed synthesis

et al. 2016

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“…29 It is, nevertheless, appropriate to point out that significantly longer Hg–Se bond lengths have been reported for compounds that feature Hg←Se dative covalent L-type interactions. 30 For example, the benzimidazole-2-selone derivative, [H(sebenzim Me )] 2 HgCl 2 has bond lengths of 2.5732(5) Å and 2.6090(5) Å, 31 while those in [Hg 2 (SePh 2 ) 4 ][ClO 4 ] 2 range from 2.65 Å to 2.92 Å. 32 Such variability in bond lengths is by no means unique to Hg–Se interactions and is a common feature of dative covalent bonds.…”

Section: Resultsmentioning

confidence: 99%

Phenylselenolate mercury alkyl compounds, PhSeHgMe and PhSeHgEt: Molecular structures, protolytic Hg–C bond cleavage and phenylselenolate exchange

et al. 2016

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The phenylselenolate mercury alkyl compounds, PhSeHgMe and PhSeHgEt, have been structurally characterized by X-ray diffraction, thereby demonstrating that both compounds are monomeric with approximately linear coordination geometries; the mercury centers do, nevertheless, exhibit secondary Hg•••Se intermolecular interactions that serve to increase the coordination number in the solid state. The ethyl derivative, PhSeHgEt, undergoes facile protolytic cleavage of the Hg–C bond to release ethane at room temperature, whereas PhSeHgMe exhibits little reactivity under similar conditions. Interestingly, the cleavage of the Hg–C bond of PhSeHgEt is also more facile than that of the thiolate analogue, PhSHgEt, which demonstrates that coordination by selenium promotes protolytic cleavage of the mercury-carbon bond. The phenylselenolate compounds PhSeHgR (R = Me, Et) also undergo degenerate exchange reactions with, for example, PhSHgR and RHgCl. In each case, the alkyl groups preserve coupling to the 199Hg nuclei, thereby indicating that the exchange process involves metathesis of the Hg–SePh/Hg–X groups rather than metathesis of the Hg–R/Hg–R groups.

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“…Selones, the Se-analogues of ketones, have generated considerable interest due to their promising utility in many domains, including homogeneous catalysis (see for example: Prabhu et al, 2014;Babu et al, 2016;Sharma et al, 2017), photocatalysis (Jin et al, 2013), and biological fields (see for example: Roy et al, 2013;Palmer & Parkin, 2015;Banerjee et al, 2015).…”

Section: Structure Descriptionmentioning

confidence: 99%

3,3′-[(2-Bromo-1,3-phenylene)bis(methylene)]bis(1-butyl-2,3-dihydro-1H-imidazole-2-selone)

2017

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In the title compound, C 22 H 29 BrN 4 Se 2 , the two Se atoms are directed in opposite directions with respect to the central benzene ring. The C Se bond lengths at 1.848 (5) and 1.851 (5) Å are on the long side for a double bond but shorter than expected for a C-Se single bond. In the crystal, BrÁ Á ÁBr intermolecular interactions [3.4685 (12) Å ] link the molecules into a zigzag chain propagating along the b-axis direction. In addition, there are C-HÁ Á ÁSe intermolecular interactions present, linking the chains to form slabs parallel to the ab plane. One of the two butyl side chains is disordered over two conformations with occupancies of 0.777 (9) and 0.223 (9). Structure descriptionSelones, the Se-analogues of ketones, have generated considerable interest due to their promising utility in many domains, including homogeneous catalysis (see for example: Prabhu et al. Recently, our group has reported the syntheses and crystal structures of [2 + 2] binuclear palladium(II) and platinum(II) self-assembled 24-membered metallomacrocycles resulting from the reaction Pd(COD)Cl 2 and Pt(COD)Cl 2 with 3,3 0 -[(2-bromo-1,3-phenylene)bis(methylene)]bis(1-mesityl-1,3-dihydro-2H-imidazole-2-selone), and of a mononuclear gold(III) complex formed with AuCl(SMe 2 ) (Rani et al., 2017). Herein, we report on the synthesis and crystal structure of the related title compound, 3,3 0 -[(2-bromo-1,3-phenylene)bis(methylene)]bis(1-butyl-2,3-dihydro-1H-imidazole-2-selone).In the title compound, Fig. 1, one of the two butyl side chains (atoms C11-C14) is disordered over two conformations with occupancies of 0.777 (9)/0.223 (9). The molecule

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Protolytic Cleavage of Hg–C Bonds Induced by 1-Methyl-1,3-dihydro-2H-benzimidazole-2-selone: Synthesis and Structural Characterization of Mercury Complexes

Cited by 35 publications

References 184 publications

Transition metal mediated formation of dicationic diselenides stabilised by N-heterocyclic carbenes: designed synthesis

Transition metal mediated formation of dicationic diselenides stabilised by N-heterocyclic carbenes: designed synthesis

Phenylselenolate mercury alkyl compounds, PhSeHgMe and PhSeHgEt: Molecular structures, protolytic Hg–C bond cleavage and phenylselenolate exchange

3,3′-[(2-Bromo-1,3-phenylene)bis(methylene)]bis(1-butyl-2,3-dihydro-1H-imidazole-2-selone)

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