Synthesis of mono- and trinuclear palladium(II) complexes via oxidative addition of a bulky hexathioether containing a disulfide bond to palladium(0)

Shimizu, Daisuke; Takeda, Nobuhiro; Tokitoh, Norihiro

doi:10.1016/j.jorganchem.2006.10.056

Cited by 15 publications

(13 citation statements)

References 72 publications

(25 reference statements)

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“…In this case, such steric hindrance should monitored by UV during the reaction process. All the reactions of aryl palladium complexes with 1-naphthylisocyanate (NCO) and 1-naphthylisothiocyanate (NCS) were investigated, and some of these results were consistent with the results reported recently [62][63][64]68]. The band assignable to ν(aryl), ν(bpy), ν(dmbpy) and ν(phen) in the IR spectra of the palladacycles are observed within the range 1515-1731 cm -1 and two bands at 1716 and 1615 cm -1 ; one of them may be due to the (C=C), and the other remaining band may be assignable to the ν(C=N) mode, corresponding to the ligands coordinated to the palladium atom.…”

Section: Reaction With Bulky 1-naphthyl Isocyanate and Isothiocyanatesupporting

confidence: 84%

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Synthesis of Novel Palladacycles Inhibitors of the Cathepsin B Activity and Antitumoral Agents

Elgazwy

Shehata²,

Zaki³

et al. 2013

Med chem (Los Angeles)

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The reaction of 2-bromo-3,4,5-trimethoxybenzaldehyde 1 with Pd(dba) 2 ; dba=dibenzylideneacetone) in the presence of a stoichiometric amount of nitrogen donor ligands, such as N,N,N',, 2,2'-bipyridine (bpy) 4,4'-dimethyl-2,2'-bipyridine (dmbpy) and an 1,10-phenanthroline (Phen), should be added to with equimolar ratio in degassed acetone under nitrogen to give mononuclear σ-aryl palladium (II) complexes cis-[2-Pd{C 6 H(CHO)-6-(OMe) 3 -3,4,5}BrL 2 ] 3a-d, where L 2 =TMEDA (3a); L 2 =bpy (3b); L 2 =dmbpy (3c); L 2 =Phen (3d) in good yields 48-65%. The reaction of the synthesized five-membered C,N-palladacycle cis-[2-Pd{C 6 H(CHO)-6-(OMe) 3 -3,4,5} BrL 2 ] 3a-d, where L 2 =TMEDA (3a); L=bpy (3b); L 2 =dmbpy (3c); L 2 =Phen (3d), with an1-naphthylisocyanates (C 10 H 7 -NCO) and an 1-naphthylisothiocyanates (C 10 H 7 -NCS), leads to the formation of novel palladacycle 4a-d and 5a-d, which was characterized in solution by 1 H NMR spectroscopy. The solid products were characterized by satisfactory elemental analysis and spectra studies. All the resulting complexes 3a-d, 4a-d and 5a-d were tested in vitro against a number of cell lines. For example, it inhibited K562 leukaemia cells with an IC 50 value in the range of (3.00 -4.3) µM (1 h exposure) and displayed cathepsin B inhibitory action with an IC 50 value in the range of (0.045-0.055 µM). .

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Section: Reaction With Bulky 1-naphthyl Isocyanate and Isothiocyanatesupporting

confidence: 84%

“…Substitution around the periphery of the aromatic ligands also resulted in increased activity. One complex, derived from 1-(2'-pyridyl)indole, was tested in vivo and showed no significant antitumour inhibition against P388 leukaemia at doses below toxic levels [52][53][54][55][56][57][58][59][60][61][62][63][64][65][66][67][68].…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Novel Palladacycles Inhibitors of the Cathepsin B Activity and Antitumoral Agents

Elgazwy

Shehata²,

Zaki³

et al. 2013

Med chem (Los Angeles)

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“…[1][2][3][4][5] The remarkable reactivity of Ni 0 and Pd 0 complexes has been exploited in regio-and stereoselective E-E addition to CuC bonds in organic synthesis. 3,[6][7][8] The reaction also provides a convenient route for the synthesis of metal chalcogenolate complexes which find applications in organic synthesis 9 and materials science. 10 Oxidative addition reactions of RE-ER (E = S or Se) with platinum(0) precursors, [Pt(PPh 3 ) 4 ] or [Pt(PPh 3 ) 2 (olefin)], afford mononuclear platinum chalcogenolates, [Pt-(ER) 2 (PR 3 ) 2 ], [11][12][13][14][15][16] whereas similar reactions with palladium(0) complexes, in general, yield binuclear derivatives, [Pd 2 (μ-ER) 2 (ER) 2 (PR′ 3 ) 2 ] (E = S or Se).…”

Section: Introductionmentioning

confidence: 99%

Reactivity of 2-chalcogenopyridines with palladium–phosphine complexes: isolation of different complexes depending on the nature of chalcogen atom and phosphine ligand

et al. 2013

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Reactions of either Pd(0) phosphine complexes with dipyridyldichalcogenides or [PdCl2(P∩P)] (P∩P = dppe, dppp) with pyridylchalcogenolate ions have been examined and a variety of Pd(II) complexes have been isolated and characterized. Oxidative addition of {SeC5H3(3-R)N}2 (R = H or Me) to [Pd(P∩P)2] (P∩P = dppe, dppp) gave either a mononuclear complex, [Pd{2-Se-C5H3(3-R)N}2(P∩P)] (for P∩P/R: dppe/H or Me; dppp/H) or a cationic binuclear complex, [Pd2{μ-SeC5H3(3-Me)N}2(dppp)2]2+ (4b) (R = Me) whereas reactions involving the tellurium analogue exclusively afforded trinuclear complexes, [Pd3(μ-Te)2(P∩P)3]Cl2 (P∩P = dppe (2) or dppp (6)). The latter was also obtained in the substitution reaction between [PdCl2(P∩P)] and NaTeC5H3(3-R)N. The substitution reactions between [PdCl2(dppe)] and Pb{EC5H3(3-R)N}2 yielded mononuclear complexes, [Pd{2-E-C5H3(3-R)N}2(dppe)] (1a–1e) (E = S, Se or Te) while in the case of [PdCl2(dppp)], the reactions resulted in the formation of mono-, bi- and tri- nuclear complexes depending on the nature of the chalcogen atom (E = S, Se or Te) and the substituent on the pyridyl ring (R = H or Me). Treatment of dipyridyl ditellurides, {TeC5H3(3-R)N}2 (R = H or Me), with [Pd(PPh3)4] gave expected tellurolate complexes, [Pd{2-TeC5H3(3-R)N}2(PPh3)2] (7a, 7b) which on prolonged standing in CDCl3 solution gave green crystals of [PdCl{2-Te(Cl)2C5H3(3-Me)N}(PPh3)] (9). The molecular structures of {TeC5H3(3-Me)N}2, [Pd2{μ-TeC5H3(3-Me)N}2(dppp)2]Cl2·3H2O (5·3H2O), [Pd3(μ-Te)2(dppp)3]Cl2·3CHCl3 (6·3CHCl3) and [PdCl{2-Te(Cl)2C5H3(3-Me)N}(PPh3)] (9) were established by single crystal X-ray diffraction analyses.

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“…Labeled atoms with "A" are related to unlabeled ones by the crystallographic inversion symmetry. Selected bond lengths (Å) and angles (°): Pd1-P1 2.3185(4), Pd1-S1 2.3358(4), S1-C1 1.753(2); P1-Pd1-S1 93.46 (14), C1-S1-Pd1 108.47(5). Figure 3.…”

Section: -9mentioning

confidence: 99%

“…Labeled atoms with "A" are related to unlabeled ones by the crystallographic inversion symmetry. Selected bond lengths (Å) and angles (°): Pd1-P1 2.3175(7), Pd1-S1 2.3422(6), S1-C1 1.739(2), S2-C4 1.701(3), S2-C1 1.720(2); P1-Pd1-P1A 180.00(3), P1-Pd1-S1 87.06(3), P1-Pd1-S1A 92.94(3), C1-S1-Pd1 105.37(8), C4-S2-C1 92.38 (14).…”

Section: -9mentioning

confidence: 99%

Oxidative Addition of Aryl Disulfides to Pd(0) Complexes: Synthesis and Structures of Bis(thiolato) Pd(II) Complexes

Kim¹,

Choi²,

Lee³

et al. 2014

Bulletin of the Korean Chemical Society

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The oxidative addition of dihalo-organic compounds to zerovalent transition-metal complexes is a well-known fundamental reaction, which affords self-assembled transitionmetal complexes or π-conjugated polymers in catalytic reactions.1 In particular, dinuclear group 10 metal complexes with bridging aryl groups act as catalytic intermediates or potential precursors in the preparation of π-conjugated conducting polymers or electronic and optical materials. These complexes are typically prepared by the double oxidative addition of dihalo-aryl derivatives to zerovalent metal complexes. 1-3We previously reported the double oxidative addition of dihalo-aryl or dihalo-thiophene compounds to zerovalent Pd or Ni complexes to afford linear dinuclear Pd(II) or Ni(II) compounds containing bridging aryl or thiophene ligands. 4,5However, to the best of our knowledge, studies on linear disulfido-aryl-bridged dinuclear Pd(II) complexes ([Pd]-ArS-SAr-[Pd]) have not been reported yet. Therefore, we attempted to prepare novel dinuclear Pd(II) complexes containing an aryl disulfide bridge (-Ar-S-S-Ar-) by the C-X (X = halogen) oxidative addition of haloaryl disulfide compounds to zerovalent Pd complexes. However, when pchlorophenyl disulfide (Cl-p-C 6 H 4 -S-S-C 6 H 4 -p-Cl) was treated with Pd(0)-bis(phosphine) complexes, we obtained the mononuclear bis(thiolato) Pd(II)-bis(phosphine) complex, trans-[Pd(S-C 6 H 4 -p-Cl) 2 (PR 3 ) 2 ], which is an S-S oxidative addition product instead of an initially expected C-X oxidative-addition product. Herein, we report the synthesis of such mononuclear bis(thiolato) complexes. These thiolato complexes are regarded as an intermediate or precursor related to the addition of organic disulfides to the organic unsaturated molecules or the adduct formation of organic disulfides and isocynides catalyzed by late transition-metal complexes. 6-9Many reactions, except for a few cases, 8a,c for the preparation of thiolato complexes typically use zerovalent group 10 metal complexes containing low basic PPh 3 ligand as a supporting ligand. In this study, we used Pd(0) complexes containing PMe 3 or PEt 3 ligands, which are more basic than PPh 3 . Reactions of [Pd(styrene)(PR 3 ) 2 ] (PR 3 = PMe 3 , PEt 3 ), 10 which was generated from trans-[PdEt 2 (PR 3 ) 2 ] and styrene, with p-chlorophenyl disulfide in a 2:1 or 1:1 molar ratio afforded the bis(arylthiolato) Pd(II) complexes, trans-(1), PEt 3 (2)) in moderateto-good yields (Eq. (1) in Scheme 1). A one-step reaction of trans-[PdEt 2 (PMe 3 ) 2 ] with p-chlorophenyl disulfide in 2:1 molar ratio also produced complex 1 in 69% yield.The peak-intensity ratios of the aromatic hydrogens to the PR 3 hydrogens in the 1 H NMR spectra of complexes 1 and 2 strongly support the proposed structures. Spectral data ( (1)) can be formed by the S-S bond cleavage, whereas the dinuclear Pd(II) complexes (in Eq. (2)) can be formed by the C-Cl bond cleavage of the aryl disulfide, followed by subsequent dimerization accomplished by the dissociation of phosphine. The above resu...

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Synthesis of mono- and trinuclear palladium(II) complexes via oxidative addition of a bulky hexathioether containing a disulfide bond to palladium(0)

Cited by 15 publications

References 72 publications

Synthesis of Novel Palladacycles Inhibitors of the Cathepsin B Activity and Antitumoral Agents

Synthesis of Novel Palladacycles Inhibitors of the Cathepsin B Activity and Antitumoral Agents

Reactivity of 2-chalcogenopyridines with palladium–phosphine complexes: isolation of different complexes depending on the nature of chalcogen atom and phosphine ligand

Oxidative Addition of Aryl Disulfides to Pd(0) Complexes: Synthesis and Structures of Bis(thiolato) Pd(II) Complexes

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