Redox Reaction between Main‐Group Elements (Te, Sn, Bi) and N‐Heterocyclic‐Carbene‐Derived Selenium Halides: A Facile Method for the Preparation of Monomeric Halides

Manjare, Sudesh T.; Yadav, Sangeeta; Singh, Harkesh B.; Butcher, Ray J.

doi:10.1002/ejic.201300850

Cited by 25 publications

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References 130 publications

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“…2 The applications and coordination chemistry of thiones and selones with transition metals has been widely surveyed by Mitzel, 7a-b Spicer, 7c Raper, 8,9 Parkin, 10 Pettinari, 11 and Akrivos et al; 12 whereas there are very few examples of the coordination chemistry of main group metal-thiones, selones and tellones known in the literature. [14][15][16][17][18][19][20][21][22][23] The monomeric bismuth imidazole chalcogenone complexes, [LBi(NO 3 ) 2 ], L ¼ hydro-[tris(3-phenyl-2-thioimidazolyl)]borate, 15 [{Bi(Tt) 2 }Cl], Tt ¼ hydridotris(thioxotriazolyl)-borate, 16 [{Bi(Tr Ph,Me ) 2 }NO 3 ], Tr Ph,Me ¼ hydrotris(1,4-dihydro-3-methyl-4-phenyl-5-thioxo-1,2,4-triazolyl)borato, 17 [{Bi(Tr Et,Me ) 2 }NO 3 ], Tr Et,Me ¼ hydrotris(1,4-dihydro-3methyl-4-ethyl-5-thioxo-1,2,4-triazolyl)borato, 18 and [(Tm 2 Bi)-(Tp 2 Na)], Tm ¼ hydrotris(methimidazolyl)borate, Tp ¼ hydrotris-(pyrazolyl)borate 19 were derived from tripodal S 3 ligands of the tris(mercaptoimidazolyl)borate type ligands. 13 In particular, (Scheme S1, see ESI †) the heavier p-block element bismuth forms monomeric, dimeric and tetrameric complexes of imidazole-chalcogenones with different imidazole chalcogenone ligands.…”

Section: Introductionmentioning

confidence: 99%

“…The only monomeric bismuth imidazole chalcogenone complex known with bidendate ligand is [{CH 2 (HCN 2 Me) 2 C(S)}BiCl 3 ]. 23 The bismuth centers in known bismuth imidazole chalcogenone complexes are hexa-coordinated with octahedral or distorted octahedral geometry, where the bismuth : chalcogen ratio is [1 : 1], [1 : 2], [1 : 3] or [1 : 6]. Notable exception was [(Tm)BiCl(m-Cl)] 2 obtained from tridendate hydrotris(methimidazolyl)borate.…”

Section: Introductionmentioning

confidence: 99%

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Heavier chalcogenone complexes of bismuth(iii)trihalides: potential catalysts for acylative cleavage of cyclic ethers

et al. 2015

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Heavier chalcogenones (S, Se and Te) of imidazole act as versatile ligands to yield a series of mononuclear and dinuclear bismuth(III)complexes of heavier chalcogenones in excellent yield. These new bismuth heavier chalcogen derivatives are the first structurally characterized molecules, where the bismuth and heavier chalcogen ratio is 1 : 1. There is only one previous report of a crystal structure of a bismuth(III)imidazol selone compound and none with bismuth(III)-imidazol tellone. The bismuth center in monomeric bismuth chalcogen trihalides depicts pseudo trigonal bipyramidal geometry, while the dimeric bismuth chalcogen trihalides demonstrate distorted square pyramidal geometry. The solid state structures of bismuth chalcogenone derivatives feature rare Bi/p(aryl) interactions. Thus, the centroid of the C6-ring suggests a half sandwich type of bismuth environment in mononuclear and dinuclear bismuth(III) chalcogenone complexes. Notably, the Bi/p(aryl) interaction is not often noticed for mononuclear bismuth chalcogen compounds. Some of the bismuth(III) chalcogenone complexes also exhibit C-H/p(aryl), C-H/S and C-H/Cl types of hydrogen bonding. The bismuth-chalcogen bond distance in mononuclear bismuth(III)tribromide chalcogenone complexes is slightly longer than in mononuclear bismuth(III)trichloride chalcogenone complexes. A gradual increase in carbon-chalcogen bond distance was observed from the free imidazole-chalcogenone to mononuclear bismuth(III)trichloride chalcogenones, dinuclear bismuth(III)trichloride chalcogenones and mononuclear bismuth(III)tribromide chalcogenones and dinuclear bismuth(III)tribromide chalcogenones. The UV-vis absorption properties and thermal decomposition properties of imidazol chalcogenones and their bismuth derivatives were investigated. Furthermore, the O-acylative cleavage of cyclic ethers was demonstrated using mononuclear and dinuclear bismuth(III)complexes of heavier chalcogenones as catalysts. In contrast to bismuth(III)trichloride and bismuth(III)tribromide catalysts, mononuclear and dinuclear bismuth(III)complexes of heavier chalcogenones are very active towards an acylative cleavage of cyclic ethers through a mild and regioselective strategy. In particular, mononuclear imidazolthione-bismuth(III)trichloride is very active towards O-acylative cleavage of 2-methyl tetrahydrofuran.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Heavier chalcogenone complexes of bismuth(iii)trihalides: potential catalysts for acylative cleavage of cyclic ethers

et al. 2015

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“…17 To study the reactivity of dihaloselones with transition metals, first dichloroselone (4b) was reacted with iron metal powder in dry diethyl ether (route A, Scheme 2). 17 To study the reactivity of dihaloselones with transition metals, first dichloroselone (4b) was reacted with iron metal powder in dry diethyl ether (route A, Scheme 2).…”

Section: Resultsmentioning

confidence: 99%

“…Selone adducts of metal halides (16,18,20,(28)(29)(30)(31)(32) were prepared by the reactions of metal halides (ZnCl 2 , ZnBr 2 , ZnI 2 , CdCl 2 , CdI 2 , HgCl 2 , HgBr 2 and HgI 2 ) with selone (3b) in diethyl ether. Similarly, the oxidation of complexes 18, 20, 28-34 with one or two equivalents of respective halogenating agent (SOCl 2 , Br 2 or I 2 ) at 0 o C in dichloromethane gave dicationic diselenides (17,19,(21)(22)(23)(24)(25)(26)(27) or dihaloselones (4b-4b") respectively. When the oxidation of 16 was carried out with two equivalents of thionyl chloride, it produced dichloroselone (4b).…”

Section: Plausible Mechanism For the Synthesis Of Dicationic Diselenimentioning

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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Synthesis and Reactivity of Selones and Dihaloselones: Complexation of Selones with d⁸‐ and d¹⁰‐Metal Ions

2017

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The reactivities of the monodentate selone LSe (L = 1,3-dibutylbenzimidazol-2-ylidene; 10a), the bidentate pyridine-functionalized selone L′Se (L′ = 1-pyridyl-3-butylimidazol-2ylidene; 10b) and the multidentate ether-functionalized selone L′′Se {L′′ = 1,3-bis[2-(2-methoxyethoxy)ethyl]benzimidazol-2-ylidene; 10c} with soft transition-metal halides (PdX 2 , PtX 2 , ZnX 2 , CdX 2 and HgX 2 ; X = Cl, Br, I) are probed. Compounds 10a and 10c react with metal halides to give complexes of the type [Cu 2 (μ-X) 2 (LSe) 2 ] (X = Br, I; 11, 12), [MX 2 (LSe) 2 ] (13-22) or [M 2 X 2 (μ-X) 2 (L′′Se) 2 ] (X = Cl, Br, I; 26-32), whereas 10b and HgX 2 (X = Cl, Br, I) form 1:1 complexes HgX 2 (L′Se) (21-23), in which the pyridine moiety coordinates to the metal centre to form a [a] 2968 Scheme 2. Synthesis and reactivity of mono-, bi-and multidentate selone ligands (10a-10c).Compounds 8a and 8c were prepared in ca. 80 % yield through the N-alkylation reactions of benzimidazole (6) with n-butyl bromide (7a) and 1-bromo-2-(2′-methoxyethoxy)ethane (7c), respectively, in 30 % NaOH in the presence of a phase-transfer catalyst (tetrabutylammonium bromide, TBAB; Scheme 2) [7] Compounds 8a and 8c were purified by column chromatography (petroleum ether/ethyl acetate, 3:1) and characterized by NMR spectroscopic techniques. Compound 8b was prepared by the reported procedure. [17] Compounds 8a-8c were heated under reflux with alkyl bromides (7a-7c) in dry 1,4-dioxane under nitrogen for 12 h to produce white precipitates of the 1,3dialkylbenzimidazolium salts 9a-9c in yields of ca. 90 % (Scheme 2). [7,16] Compounds 9a-9c were collected by filtration, Eur.Compound 27: The reagents used were selone 10c (0.15 g, 0.37 mmol) and zinc chloride (0.05 g, 0.37 mmol). Yield: 0.21 g, (68 %). UV/Vis (CH 3 CN, 0.1 mmol dm -1 ): λ max = 263, 311, 321 nm. 1 H NMR (400 MHz, CDCl 3 ): δ = 7.54 (d, 4 H), 7.31 (d, 4 H), 4.71 (t,

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Redox Reaction between Main‐Group Elements (Te, Sn, Bi) and N‐Heterocyclic‐Carbene‐Derived Selenium Halides: A Facile Method for the Preparation of Monomeric Halides

Cited by 25 publications

References 130 publications

Heavier chalcogenone complexes of bismuth(iii)trihalides: potential catalysts for acylative cleavage of cyclic ethers

Heavier chalcogenone complexes of bismuth(iii)trihalides: potential catalysts for acylative cleavage of cyclic ethers

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

Synthesis and Reactivity of Selones and Dihaloselones: Complexation of Selones with d⁸‐ and d¹⁰‐Metal Ions

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Redox Reaction between Main‐Group Elements (Te, Sn, Bi) and N‐Heterocyclic‐Carbene‐Derived Selenium Halides: A Facile Method for the Preparation of Monomeric Halides

Cited by 25 publications

References 130 publications

Heavier chalcogenone complexes of bismuth(iii)trihalides: potential catalysts for acylative cleavage of cyclic ethers

Heavier chalcogenone complexes of bismuth(iii)trihalides: potential catalysts for acylative cleavage of cyclic ethers

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

Synthesis and Reactivity of Selones and Dihaloselones: Complexation of Selones with d8‐ and d10‐Metal Ions

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Synthesis and Reactivity of Selones and Dihaloselones: Complexation of Selones with d⁸‐ and d¹⁰‐Metal Ions