A dinuclear Bi(III) complex of a 1,3-disubstituted imidazole-2-thione and its use as a transmetallation agent toward Pd(II)

Jagenbrein, Martin; Monakhov, Kirill Yu.; Braunstein, Pierre

doi:10.1016/j.jorganchem.2015.04.052

Cited by 8 publications

(18 citation statements)

References 57 publications

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“…The Pd–Cl bond lengths (2.060(1) to ∼2.3198(17) Å; Table ) are close to those found in [PdCl 2 (L) 2 ] (2.318(4) to ∼2.362(4) Å; L = 1,3-dimesitylimidazolidine-2-thione) . The Pd–S bond lengths (2.3194(18) to ∼2.3352(7) Å) in 2b , 2d ·2MeCN, and 2e are longer than those observed in [PdI( i Pr 2 C 3 N 2 S)(μ-I)(μ- i Pr 2 C 3 N 2 S)PdI 2 ] (2.318(2) Å) and [PdCl 2 (L)] (2.271(3) to ∼2.268(1) Å; L = 1-[1-(4-isopropyl-4,5-dihydrooxazol-2-yl)-1-methylethyl]-3-(2-isopropylphenyl)-1,3-dihydrobenzoimidazole-2-thione) …”

Section: Methodssupporting

confidence: 72%

“…60 The Pd−Cl bond lengths (2.060(1) to ∼2.3198(17) Å; Table 2) are close to those found in [PdCl 2 (L) 2 ] (2.318(4) to ∼2.362(4) Å; L = 1,3dimesitylimidazolidine-2-thione). 44 The Pd−S bond lengths (2.3194(18) to ∼2.3352(7) Å) in 2b, 2d•2MeCN, and 2e are longer than those observed in [PdI( i Pr 2 C 3 N 2 S)(μ-I)(μ-i Pr 2 C 3 N 2 S)PdI 2 ] (2.318(2) Å) 79 and [PdCl 2 (L)] (2.271(3) to ∼2.268 (1) 92 Compound 3a crystallizes in the triclinic space group P1̅ , and its asymmetric unit contains one discrete [(PdCl 2 ){μ-(Me 2 C 3 N 2 S)}] 2 molecule and one H 2 O lattice molecule. Compounds 3b−3e crystallize in the monoclinic space groups P2 1 /c (3b) and P2 1 /n (3c−3e), and their asymmetric units contain one independent molecule [(PdCl 2 ){μ-L}] 2 (L = i Pr 2 C 3 N 2 S (3b), Cy 2 C 3 N 2 S (3c), (C 6 Me 3 H 2 ) 2 C 3 N 2 S (3d), or MePhC 3 N 2 S (3e)).…”

Section: ■ Introductionmentioning

confidence: 94%

“…Currently, only a few reports deal with the synthesis of mono- and binuclear Pd(II) complexes with N,N′-disubstituted-imidazole-2-thiones − and their applications in the C–C bond formation. , For example, one mononuclear complex [(phbtuimt)PdCl] (Hphbtuimt = 3,3′-(1,3-phenylene)bis(1-butyl-1,3-dihydro-2 H -imidazole-2-thione) shows moderate catalytic activity for Heck, Suzuki–Miyaura, and Sonogashira coupling reactions . The coupling reactions of iodobenzene with phenyl boronic acid or p -tolyl boronic acid provide the desired coupling products in moderate yields (67% to ∼74%) in 48 h. Although it is known that the bimetallic complexes can improve their catalytic activity and/or selectivity due to the existence of cooperative effects, − there have been two dinuclear Pd(II) complexes of N,N′-disubstituted-imidazole-2-thiones, namely, cis -[(PdCl 2 ){μ-(Et 2 C 3 N 2 S)}] 2 and [PdI( i Pr 2 C 3 N 2 S)(μ-I)(μ- i Pr 2 C 3 N 2 S)PdI 2 ], and their catalytic performance has not been explored yet.…”

Section: Introductionmentioning

confidence: 99%

“…61,63 For example, one mononuclear complex [(phbtuimt)PdCl] (Hphbtuimt = 3,3′-(1,3- 11.4686 (10) 18.4381 (14) 10.1167 (19) 14.8767 (14) 10.8251 (6) 11.081 (5) 9.3885 (8) b (Å) 14.8395 (9) 14.3926 (12) 7.2111 (6) 10.1473 (19) 15.2927( 14)) 13.1112 (7) 13.053 (5) 9.2479 (8) c (Å) 9.6399 (5) 13.4645 (11) 16.8732 (13) 11.483 (2) 13.7564 (13) 13.4812 (8) 15.276 (7) 14.5435 (12) α (deg) 913.66 (12) 1842.19 (18) 2150.4 (16) 1259.41 (18) ρ calc (g/cm 3 shows moderate catalytic activity for Heck, Suzuki−Miyaura, and Sonogashira coupling reactions. 61 The coupling reactions of iodobenzene with phenyl boronic acid or p-tolyl boronic acid provide the desired coupling products in moderate yields (67% to ∼74%) in 48 h. Although it is known that the bimetallic complexes can improve their catalytic activity and/or selectivity due to the existence of cooperative effects, 64−78 79 and their catalytic performance has not been explored yet. However, we have involved in the syntheses and structures of various metal thiolate complexes and their catalytic performances in the above-mentioned cross-coupling reactions.…”

Section: ■ Introductionmentioning

confidence: 99%

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Palladium(II) Chloride Complexes of N,N′-Disubstituted Imidazole-2-thiones: Syntheses, Structures, and Catalytic Performances in Suzuki–Miyaura and Sonogashira Coupling Reactions

Zhang

et al. 2017

Inorg. Chem.

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Reactions of PdCl with 2 equiv of N,N'-disubstituted-imidazole-2-thiones RRCNS (R = R = Me (1a), Pr (1b), Cy (1c), CMeH (1d); R = Me, R = Ph (1e)) under the different conditions afford five mononuclear complexes trans-[(RRCNS)PdCl] (R = R = Me (2a), Pr (2b), Cy (2c), CMeH (2d); R = Me, R = Ph (2e)) and five binuclear Pd(II) complexes [(PdCl){μ-(RRCNS)}] (R = R = Me (3a), Pr (3b), Cy (3c), CMeH (3d); R = Me, R = Ph (3e)), respectively. Complexes 2a-2e are easily converted into the corresponding 3a-3e by adding equimolar PdCl in refluxing MeOH, while the reverse reaction is achieved at room temperature by addition of 2 equiv of 1a-1e. In 2b, 2d, and 2e, each Pd(II) holds a distorted square planar geometry completed by two trans Cl atoms and two trans S atoms. Complexes 3a-3e have a dimeric [PdS] structure in which two {PdCl} units are interlinked by two N,N'-disubstituted-imidazole-2-thiones. Each Pd(II) adopts a distorted square planar geometry accomplished by two cis Cl atoms and two cis bridging S atoms. Among them, complex 3d has the two largest CMeH groups on the 2 and 5 positions of imidazole-2-thione, the longest Pd-μ-S bond, the largest S-Pd-S angle, and displays the highest catalytic activity toward Suzuki-Miyaura and copper-free Sonogashira cross-coupling reactions, which are confirmed by density functional theory calculations. The results provide an interesting insight into the introduction of various substituent groups into the periphery ligands of coordination complex-based catalysts, which could tune their geometric structures to acquire the best catalytic activity toward organic reactions.

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Section: Methodssupporting

confidence: 72%

Section: ■ Introductionmentioning

confidence: 94%

Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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Palladium(II) Chloride Complexes of N,N′-Disubstituted Imidazole-2-thiones: Syntheses, Structures, and Catalytic Performances in Suzuki–Miyaura and Sonogashira Coupling Reactions

Zhang

et al. 2017

Inorg. Chem.

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“…The molecular structure of [μ-{(IMes)S}PdCl 2 ] 2 ( 603 ) is shown in Figure . It is interesting to note that a binuclear palladium(II) complex with terminal and bridging (I i Pr)S ligands had already been previously reported . The binuclear complexes showed much better catalytic performance, with a strong dependency on the size of the N-substituents; the (IMes)S complex proved particularly efficient .…”

Section: N-heterocyclic Carbene Adducts Of Group 16 Elementsmentioning

confidence: 99%

N-Heterocyclic Carbene Adducts of Main Group Elements and Their Use as Ligands in Transition Metal Chemistry

2019

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N-Heterocyclic carbenes (NHC) are nowadays ubiquitous and indispensable in many research fields, and it is not possible to imagine modern transition metal and main group element chemistry without the plethora of available NHCs with tailor-made electronic and steric properties. While their suitability to act as strong ligands toward transition metals has led to numerous applications of NHC complexes in homogeneous catalysis, their strong σ-donating and adaptable π-accepting abilities have also contributed to an impressive vitalization of main group chemistry with the isolation and characterization of NHC adducts of almost any element. Formally, NHC coordination to Lewis acids affords a transfer of nucleophilicity from the carbene carbon atom to the attached exocyclic moiety, and low-valent and lowcoordinate adducts of the p-block elements with available lone pairs and/or polarized carbon-element π-bonds are able to act themselves as Lewis basic donor ligands toward transition metals. Accordingly, the availability of a large number of novel NHC adducts has not only produced new varieties of already existing ligand classes but has also allowed establishment of numerous complexes with unusual and often unprecedented element−metal bonds. This review aims at summarizing this development comprehensively and covers the usage of N-heterocyclic carbene adducts of the p-block elements as ligands in transition metal chemistry.

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Chalcogen‐Pnictogen Complexes of Anionic N‐Heterocyclic Carbenes with a Weakly Coordinating Borate Moiety

Tamm

2022

Eur J Inorg Chem

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Chalcogen-pnictogen dihalide complexes which bear an anionic N-heterocyclic carbene ligand with a tethered weakly coordinating borate moiety (WCA-IDipp, WCA = B(C 6 F 5 ) 3 , IDipp = 1,3bis(2,6-diisopropyphenyl)imidazolin-2-ylidene) were isolated and fully characterized. The metathesis reaction between the lithium salts [{(WCA-IDipp)E}Li(toluene)] (E = S, Se) and pnictogen trihalides E'X 3 (E = P, As, Sb; X = Cl, Br) afforded the complexes of the general type (WCA-IDipp)EÀ E'X 2 (E = S, Se; E = P, As, Sb; X = Cl, Br). In contrast, lithium chloride elimination was not observed with BiCl 3 under the same reaction conditions and instead, the lithium complexes [{(WCA-IDipp)EÀ BiCl 3 }Li(thf) 4 ] (E=S, Se) were obtained. However, the corresponding bismuth dichloride derivatives (WCA-IDipp)EÀ BiCl 2 were accessible from the reaction of (WCA-IDipp)ESiMe 3 with BiCl 3 upon Me 3 SiCl elimination.

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A dinuclear Bi(III) complex of a 1,3-disubstituted imidazole-2-thione and its use as a transmetallation agent toward Pd(II)

Cited by 8 publications

References 57 publications

Palladium(II) Chloride Complexes of N,N′-Disubstituted Imidazole-2-thiones: Syntheses, Structures, and Catalytic Performances in Suzuki–Miyaura and Sonogashira Coupling Reactions

Palladium(II) Chloride Complexes of N,N′-Disubstituted Imidazole-2-thiones: Syntheses, Structures, and Catalytic Performances in Suzuki–Miyaura and Sonogashira Coupling Reactions

N-Heterocyclic Carbene Adducts of Main Group Elements and Their Use as Ligands in Transition Metal Chemistry

Chalcogen‐Pnictogen Complexes of Anionic N‐Heterocyclic Carbenes with a Weakly Coordinating Borate Moiety

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