73491-36-8Relevant articles and documents
Structure of the solvated thallium(I) ion in aqueous, dimethyl sulfoxide, N,N'-dimethylpropyleneurea, and N,N-dimethylthioformamide solution.
Persson, Ingmar,Jalilehvand, Farideh,Sandstroem, Magnus
, p. 192 - 197 (2002)
The structure of the solvated thallium(I) ion in aqueous, dimethyl sulfoxide, N,N'-dimethylpropyleneurea, and N,N-dimethylthioformamide solution has been studied by means of large-angle X-ray scattering (LAXS) and complemented by EXAFS studies on two systems. The first solvation shell around the thallium(I) ion comprises significantly different bond distances to the solvent molecules in solution, indicating a stereochemically active lone electron pair. The first hydration shell around the thallium(I) ion in aqueous solution can be modeled by two Tl-O bond distances at 2.73(2) A and about two more at 3.18(6) A. Thallium(I) ions solvated by dimethyl sulfoxide, N,N'-dimethylpropyleneurea, and N,N-dimethylthioformamide seem to have two short and four long Tl-solvent bond distances. The mean Tl-O bond distances of the two groups were 2.66(4) and 3.18(6) A for dimethyl sulfoxide and 2.73(4) and 3.27(8) A for N,N'-dimethylpropyleneurea. For the sulfur donor solvent N,N-dimethylthioformamide the corresponding groups of Tl-S bond distances were refined to 2.96(2) and 3.33(3) A.
Mono- and Dipalladated Derivatives of 2,5-Distyrylbenzene. Reactivity toward XyNC and Alkynes. Synthesis of Complexes with Indacenediide Ligands
Fernández-Rodríguez, María-José,Martínez-Viviente, Eloísa,Vicente, José,Jones, Peter G.
, p. 2240 - 2254 (2015)
The dinuclear complexes [C6H2{PdBr-(N^N)}2-1,4-((E)-CH=CHPh)2-2,5] (N^N = tbbpy = 4,4′-di-tert-butyl-2,2′-bipyridine (1a), tmeda = N,N,N′,N′-tetramethylethylenediamine (1b)) have been synthesized by oxidative addition of trans,trans-2,5-distyryl-2,4-dibromobenzene to 2 equiv of "[Pd(dba)2]" (dba = dibenzylideneacetone) in the presence of the N^N ligands. A similar reaction with N^N = bpy = 2,2′-bipyridine afforded the mononuclear complex [PdBr{C6H2(Br-4){((E)-CH=CHPh)2-2,5}(bpy)] (2). The reaction of 1a,b with PhC≡CPh, MeC≡CMe, and PhC≡CMe in the presence of TlOTf or AgClO4 gave the dipalladated indacenediide complexes [(μ-η,η-C12H2Bn2-1,5-R4-2,3,6,7){Pd(N^N)}2](OTf)2 (Bn = benzyl, R = Ph, N^N = tbbpy (3a), tmeda (3b); R = Me, N^N = tbbpy (4a), tmeda (4b)) and [(μ-η,η-C12H2Bn2-1,5-Ph2-2,6-Me2-3,7){Pd(N^N)}2](A)2 (N^N = tbbpy, A = OTf (5a), ClO4 (5a′); N^N = tmeda, A = OTf (5b)). The reactions of 2 with the same alkynes afforded the indenyl complexes [Pd(η-C9H2Bn-1-R2-2,3-((E)-CH=CHPh)-5-Br-6)(bpy)](A) (R = Ph, A = OTf (6), ClO4 (6′); R = Me, A = OTf (7)) and [Pd(η-C9H2Bn-1-Ph-2-Me-3-((E)-CH=CHPh)-5-Br-6)(bpy)]OTf (8). By reaction of either 1a or 1b with XyNC (Xy = 2,6-dimethylphenyl) the dinuclear complex [C6H2{C(=NXy){PdBr(CNXy)2}2-1,4-((E)-CH=CHPh)2-2,5] (9) was obtained, while the oxidative addition of trans,trans-2,5-distyryl-2,4-dibromobenzene to [Pd(dba)2] in the presence of 8 equiv of XyNC afforded the dinuclear complexes [C6H2{C(=NXy){C(=NXy)}2{PdBr(CNXy)}}2-1,4-((E)-CH=CHPh)2-2,5] (10, 10?) as a mixture of isomers (1:0.3 ratio) which are in slow exchange in solution, as shown by an EXSY spectrum. The crystal structures of a-3a·7CDCl3, s-3b·CH2Cl2, a-5a′·4CH2Cl2, 6, and 8 have been determined by X-ray diffraction studies.
Synthesis of palladium(II), -(III), and -(IV) complexes with acyclic diaminocarbene ligands
Martinez-Martinez, Antonio-Jesus,Chicote, Maria-Teresa,Bautista, Delia,Vicente, Jose
, p. 3711 - 3719 (2012)
The reaction of [PdI{C,N-C(=NHXy)C6H4NH 2-2}CNXy]TfO with XyNC (1:2, TfO = CF3SO3, Xy = C6H3Me2-2,6) gives the cationic carbene complex [PdI{C,C-C(=NHXy)C6H4{NHC(NHXy)}-2}CNXy]TfO (4), while that of [PdCl2{C(=NHXy)C6H4NH 2-2}] with isocyanides (1:1, 50-60 °C) gives the neutral carbene complexes [PdCl2{C,C-C(=NHXy)C6H4{NHC(NHR)}-2}] (R = tBu (8), Xy (9)), from which mono- and dicationic derivatives [PdCl{C,C-C(=NHXy)C6H4{NHC(NHXy)}-2}L]X (L = XyNC, X = TfO (10); L = PPh3, X = Cl (11)) and [Pd{C,C-C(=NHXy)C6H 4{NHC(NHXy)}-2}(CNXy)2](TfO)2 (12), respectively, have been isolated. Dehydrochlorination of complex 9 with TlTfO and NaOAc (1:2:2) or with NEt3 (1:1) affords the dinuclear complexes [(PdX)2{μ-N,C,C-C(=NXy)C6H4{NHC(NHXy)}-2} 2] (X = OAc (13), Cl (14)), which in turn react with PPh3 to give [PdX{C,C-C(=NXy)C6H4{NHC(NHXy)}-2}PPh3] (X = OAc (15), Cl (16)). Oxidative addition of 2-iodobenzoic acid to 13 leads to the Pd(IV) complex [{PdI(C6H4CO2-2)} 2{μ-N,C,C-C(=NXy)C6H4{NHC(NHXy)}-2} 2] (17), while the reaction of 14 with PhICl2 affords the Pd(III) derivative [(PdCl2)2{μ-N,C,C-C(=NXy)C 6H4{NHC(NHXy)}-2}2] (18). The crystal structures of 4, 9, and 12 have been determined, and the atomic connectivity in 18 has been established.
Insertion reactions on carbopalladated benzyne: From eight- to nine- and ten-membered palladacycles. Applications to the synthesis of N-heterocycles
Oliva-Madrid, Mara-Jos,Garca-Lpez, Jos-Antonio,Saura-Llamas, Isabel,Bautista, Delia,Vicente, Jos
, p. 6420 - 6430 (2014)
The ortho-metalated complexes [Pd{C,N-C6H2CH2CH2NH2-2,(OMe)2-4,5}(Br)]2 (A) and [Pd{C,N-C6H4CH2CMe2NH2-2}(Cl)]2 (B), derived from homoveratrylamine and phentermine, respectively, react with benzyne generated in situ, to afford the previously reported eight-membered palladacycles 1a and 1b, respectively, arising from the insertion of one molecule of the aryne into the Pd-Caryl bond. Complexes 1 react with isocyanides RNC (R = Xy, tBu) in 1:4 molar ratio to give the nine-membered iminoacyl palladacycles [Pd(C,N-C(=NR)-C6H4{C6H2CH2CH2NH2-2(OMe)2-4,5)-2})Br(CNR)] (R = Xy (2a), R = tBu (3a)) and [Pd(C,N-C(=NXy)-C6H4{C6H4CH2CMe2NH2-2)-2})Cl(CNR)] (R = Xy (2b), R = tBu (3b)). Complex 2a decomposes in refluxing toluene to afford palladium(0) and 7,8-dihydro-10,11-dimethoxy-5-[(2,6-dimethylphenyl)imino]dibenzo[c,e]azocinium triflate (4a). When 1b reacts with TlOTf and XyNC (molar ratio 1:2:2), 7,8-dihydro-5-[(2,6-dimethylphenyl)imino]-7,7-dimethyldibenzo[c,e]azocinium triflate (4b) is obtained, resulting from an isocyanide insertion/C-N reductive coupling sequence. The amidinium triflates 4a and 4b present E/Z isomerism in CHCl3 solution. The stoichiometric carbonylation of dinuclear complexes 1 renders, after depalladation, the lactams 7,8-dihydro-10,11-dimethoxydibenzo[c,e]azocin-5(6H)-one (5a) and 7,8-dihydro-7,7-dimethyldibenzo[c,e]azocin-5(6H)-one (5b) or the previously reported ester derivative [2-MeO2CC6H4C6H2CH2CH2NH3-2-(OMe)2-4,5]Br (6a) or [2-MeO2CC6H4C6H4CH2CMe2NH3-2]Cl (6b), depending on the reaction conditions. The eight-membered palladacycles 1 react with alkenes to afford complexes [PdCl2(biarylamine)2] (7a, 7b, 8b), containing the Heck-type functionalized phenethylamines. The reaction of 1b with tBuOK in toluene at 95 °C, under a N2 atmosphere, affords 6,7-dihydro-6,6-dimethyl-5H-dibenz[b,d]azepine (9b), resulting from a C-N reductive coupling process. The crystal structures of compounds [Pd(C,N-C(=NXy)-C6H4{C6H2CH2CH2NH2-2(OMe)2-4,5)-2})Br(CNXy)]·CH2Cl2·1/2H2O (2a·CH2Cl2·1/2H2O), [Pd(C,N-C(=NXy)-C6H4{C6H4CH2CMe2NH2-2)-2})Cl(CNXy)]·0.72Et2O·0.28CHCl3 (2b·0.72Et2O·0.28CHCl3), and 7,8-dihydro-10,11-dimethoxydibenzo[c,e]azocin-5(6H)-one (5a) have been determined by X-ray diffraction studies.
Synthesis of Arylpalladium(II) Complexes Derived from Benzyl Alcohol, Reactivity toward Alkyl Halides, and Synthesis of Dinuclear Arylpalladium(II) Complexes
Fernández-Rodríguez, María-José,Martínez-Viviente, Eloísa,Vicente, José,Jones, Peter G.
, p. 3282 - 3291 (2016/01/15)
The aryl palladium complexes [PdI(C6H4CH2OH-2)(N^N)] (N^N = bpy = 2,2′-bipyridyl (1a), tbbpy = 4,4′-di-tert-butyl-2,2′-bipyridine (1b), tmeda = N,N,N′,N′-tetramethylethylenediamine (1c)) were synthesized by oxidative addition of 2-iodobenzyl alcohol to one equivalent of "[Pd(dba)2]" (dba = dibenzylideneacetone) in the presence of the N N ligands. By reaction of 1a with three equivalents of XyNC (Xy = 2,6-dimethylphenyl) the insertion complex trans-[PdI{C(-NXy)(C6H4CH2OH-2)}(CNXy)2] (2) was formed. The reaction of 1a with KOtBu resulted in the formation of the chelate complex [Pd(κ2-C,O-C6H4CH2O-2)(bpy)] (3), which crystallizes as pairs of molecules bridged by hydrogen bonds to water of crystallization. Complex 3 reacts with XyNC, forming the cyclic imidate N-(2,6-dimethylphenyl)-2-benzofuran-1(3H)-imine (4). By reaction of 3 with various primary alkyl halides RCH2X, the complexes [PdX(C6H4CH2OCH2R-2)(bpy)] (X = I, R = H (5a), X = Br, R = Ph (5b), p-C6H4CH2Br (5c), p-C6H4Br (5d), and p-C6H4I (5e)) were obtained. When the reaction of 3 with p-C6H4(CH2Br)2 was carried out in a 2:1 ratio, the dinuclear arylpalladium complex [{(bpy)BrPd(C6H4CH2OCH2-2)}2(C6H4-1,4)] (6) formed. An halide exchange reaction on 5e, using AgOTf and an excess of NaI, afforded [PdI{C6H4(CH2OCH2(C6H4I-4))-2}(bpy)] (5f), which by oxidative addition to [Pd(dba)2] in the presence of bpy formed another dinuclear arylpalladium complex, [(bpy)IPd(C6H4CH2-2)O(CH2C6H4-4)PdI(bpy)] (7). All the complexes have been extensively characterized by NMR spectroscopy. The crystal structures of 1a, 3·H2O, and 5e were determined by X-ray diffraction studies.
