Liang-Fu Tang

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Name: 唐良富; LiangFu Tang

Organization: Nankai University , China

Department: Department of Chemistry

Title: Professor(PhD)

TOPICS

Organic Chemistry

Chemicals
References

A convenient synthesis of N-vinyl enamides via the lithiation and ring-opening reaction of 2-phenyl-2-oxazolines

Co-reporter:Yi Xu, Xiao-Yu Liu, Zi-Qi Wang, Liang-Fu Tang

Tetrahedron Letters 2017 Volume 58, Issue 18(Issue 18) pp:

Publication Date(Web):3 May 2017

DOI:10.1016/j.tetlet.2017.03.080

•The lithiation of 2-phenyl-2-oxazoline with lithium diisopropylamide.•Ring-opening reaction of 2-phenyl-2-oxazoline at room temperature.•Synthesis of multifunctional N-vinyl tertiary enamides.A simple and efficient synthesis of N-vinyl enamides via the lithiation and ring-opening reaction of 2-phenyl-2-oxazolines with lithium diisopropylamide at room temperature has been developed. This method is especially suitable for the synthesis of multifunctional enamides. Good yields have been obtained when the reactions were amplified to gram scale.Download high-res image (58KB)Download full-size image

Synthesis of 3-acyl, methylene and epoxy substituted isoindolinone derivatives via the ortho-lithiation/cyclization procedures of aromatic imines with carbon monoxide

Co-reporter:Yi Xu, Xiao-Yu Liu, Zhi-Hong Wang, Liang-Fu Tang

Tetrahedron 2017 Volume 73, Issue 52(Issue 52) pp:

Publication Date(Web):28 December 2017

DOI:10.1016/j.tet.2017.11.001

A simple and convenient one-pot synthesis of 3-acyl, methylene and epoxy isoindolinone derivatives via the reaction of o-lithiated aromatic imines with carbon monoxide followed with acyl chlorides or PhCO(CH2)nBr (n = 1 or 3) under mild reaction conditions has been developed. Preliminary in vitro tests for fungicidal activity of these isoindolinone derivatives indicated that most of them exhibit good fungicidal activity against Sclerotinia sclerotiorum.Download high-res image (96KB)Download full-size image

Formation of propanedithioamide and 1,2-dithiole derivatives from reaction of the lithio derivative of 1-phenylthiomethyl-3,5-dimethylpyrazole with PhNCS and coordination behavior of propanedithioamide on tungsten carbonyl

Co-reporter:Yun-Fu Xie, Da-Wei Zhao, Liang-Fu Tang

Journal of Organometallic Chemistry 2016 Volume 819() pp:53-60

Publication Date(Web):15 September 2016

DOI:10.1016/j.jorganchem.2016.06.021

•Reaction of lithio derivative of phenylthiomethyl-3,5-dimethylpyrazole with PhNCS.•Propanedithioamide and 1,2-dithiole derivatives were obtained.•The CS bond cleavage induced by alkyllithium was observed.•(3,5-Dimethylpyrazol-1-yl) carbene was captured.Treatment of 1-phenylthiomethyl-3,5-dimethylpyrazole with n-butyllithium, and subsequently with phenyl isothiocyanate yielded 2-(3,5-dimethylpyrazol-1-yl)-2-(phenylthio)thioacetanilide, 2-(3,5-dimethylpyrazol-1-yl)thioacetanilide, N,N′-diphenyl-2-(3,5-dimethylpyrazol-1-yl)propanedithioamide and 5-anilino-4-(3,5-dimethylpyrazol-1-yl)-3-phenylimino-1,2-dithia-4-cyclopentene, respectively. Reaction of the propanedithioamide derivative with W(CO)5THF has been investigated, which gave a bis(chelate) tungsten complex through two relatively soft sulfur atoms. All these newly synthesized compounds were characterized by NMR and HRMS spectroscopy (or elemental analysis), and their structures were unambiguously confirmed by X-ray crystallography. Two possible pathways, including a carbanion or a carbene intermediate formed via the CS bond cleavage, have been suggested to explain the formation of propanedithioamide and 1,2-dithiole derivatives.

Synthesis and reactivity of a triphenyltin-functionalized 1H-(3,5-dimethylpyrazol-1-ylmethyl)-1,2,3-benzotriazole

Co-reporter:Huan Yang;Song Li

Transition Metal Chemistry 2016 Volume 41( Issue 6) pp:655-661

Publication Date(Web):2016 September

DOI:10.1007/s11243-016-0065-0

Treatment of 1H-(3,5-dimethylpyrazol-1-ylmethyl)-1,2,3-benzotriazole [CH2(3,5-Me2Pz)(Bt)] with one equivalent of n-BuLi followed by Ph3SnCl gave a ditin derivative [(Ph3Sn)2C(3,5-Me2Pz)(Bt)]. Use of two equivalents of n-BuLi gave CH2(3,5-Me2Pz)(Bt-SnPh3) together with (Ph3Sn)2C(3,5-Me2Pz)(Bt). Reaction of (Ph3Sn)2C(3,5-Me2Pz)(Bt) with W(CO)5(THF) gave (Ph3Sn)2C(3,5-Me2Pz)(BtW(CO)5), while the reaction of CH2(3,5-Me2Pz)(Bt-SnPh3) with W(CO)5(THF) resulted in the formation of three complexes, namely CH2(3,5-Me2Pz)(Bt-SnPh3)W(CO)5, CH2(3,5-Me2Pz)(Bt-SnPh3)W(CO)4 and CH2(3,5-Me2Pz)(Bt)W(CO)4. All of these products have been characterized by physicochemical and spectroscopic methods. In addition, the structures of five of the compounds have been confirmed by X-ray structural analyses, revealing that the functionalized 1H-(3,5-dimethylpyrazol-1-ylmethyl)-1,2,3-benzotriazole has variable coordination modes.

Synthesis and catalytic activity of N-heterocyclic carbene metal carbonyl complexes based on 1-[2-(pyrazol-1-yl)phenyl]imidazole

Co-reporter:Cai-Hong Cheng;Ren-Yu Guo;Qi Cui;Hai-Bin Song

Transition Metal Chemistry 2015 Volume 40( Issue 3) pp:297-304

Publication Date(Web):2015 April

DOI:10.1007/s11243-015-9917-2

A series of N-heterocyclic carbene transition metal (molybdenum, tungsten and ruthenium) carbonyl complexes derived from 1-[2-(pyrazol-1-yl)phenyl]-imidazole have been synthesized and characterized by physico-chemical and spectroscopic methods, and the structures of five complexes have been confirmed by X-ray crystal structure analyses. The azaaryl-functionalized N-heterocyclic carbenes act as chelating N,C-bidentate ligands in these five complexes. Preliminary catalytic tests of these NHC-molybdenum (tungsten) carbonyl complexes in the oxidation of styrene have been carried out, showing that benzaldehyde was the main oxidation product when hydrogen peroxide was used as the oxidant, while 2,5-diphenyl-1,4-dioxane was obtained as the exclusive product in the oxidation by tert-butyl hydroperoxide.

A simple and efficient synthesis of isoindolinone derivatives based on reaction of ortho-lithiated aromatic imines with CO

Co-reporter:Hai-Jun Li, Yu-Qing Zhang, Liang-Fu Tang

Tetrahedron 2015 Volume 71(Issue 40) pp:7681-7686

Publication Date(Web):7 October 2015

DOI:10.1016/j.tet.2015.07.060

A simple and efficient one-pot synthesis of 2,3-disubstituted isoindolinones via the reaction of o-lithiated aromatic imines with carbon monoxide under one atmospheric pressure has been developed. Preliminary in vitro tests for fungicidal activity of these isoindolinone derivatives have been carried out, indicating that most of them exhibit good fungicidal activities.

Synthesis of acyl iron complexes based on bis(heteroaryl)methanes

Co-reporter:Da-Wei Zhao, Xia-Li Liu, Xiao-Yan Zhang, Liang-Fu Tang

Journal of Organometallic Chemistry 2015 780() pp: 56-62

Publication Date(Web):

DOI:10.1016/j.jorganchem.2014.12.039

Functionalized bis(1-methylimidazol-2-yl)methane and 1-(1-methylimidazol-2-yl)methyl-3,5-dimethylpyrazole and their reactions

Co-reporter:Hai-Jun Li, Xia-Li Liu, Ke Ding, Hai-Bin Song, Liang-Fu Tang

Journal of Organometallic Chemistry 2014 Volume 757() pp:8-13

Publication Date(Web):1 May 2014

DOI:10.1016/j.jorganchem.2014.01.021

•The modification of bis(1-methylimidazol-2-yl)methane at the methylene group.•Reactivity of functionalized bis(1-methylimidazol-2-yl)methane has been investigated.•The lithiation of 1-(1-methylimidazol-2-yl)methyl-3,5-dimethylpyrazole.•The functionalized pyrazole-based ligand shows different reaction pattern.Bis(1-methylimidazol-2-yl)methane and 1-(1-methylimidazol-2-yl)methyl-3,5-dimethylpyrazole [CH2(min)(pz)] could be deprotonated with n-BuLi at the bridging carbon atom. The corresponding anions were inactive in the reaction with Ph3SnCl but reacted with sulfur, followed by reaction with Ph2SnCl2 to give organotin derivatives Ph2ClSnSCH(min)2 (1) and Ph2ClSnSCH(min)(pz) (4) (min = 1-methylimidazol-2-yl and pz = 3,5-dimethylpyrazol-1-yl, respectively). The structure of 1 determined by X-ray structural analyses indicated that bis(1-methylimidazol-2-yl)methylthiolate acted as a bidentate monoanionic κ2-[N,S] chelating ligand. Reaction of 1 with W(CO)5THF yielded heterobimetallic complex Ph2ClSnSCH(min)2W(CO)5 (2), while similar reaction of 4 with W(CO)5THF resulted in the decomposition of 4 to give pyrazole derivative W(CO)5(pzH). The structure of 2 has been confirmed by X-ray structural analyses, showing that 1 coordinated to the tungsten atom through the free nitrogen atom. Reaction of CH2(min)(pz) with W(CO)5THF yielded bidentate chelating complex CH2(min)(pz)W(CO)4, which when treated with n-BuLi, followed by reaction with Ph3SnCl, gave the final product CH2(minSnPh3)(pz)W(CO)4.The modification of bis(1-methylimidazol-2-yl)methane and 1-(1-methylimidazol-2-yl)methyl-3,5-dimethylpyrazole at the methylene group has been successfully carried out. These functionalized ligands showed markedly different reaction patterns, compared to the analogs of bis(pyrazol-1-yl)methanes.

Synthesis, Structure, and Fungicidal Activity of Organotin Dithiocarbamates Derived from Pyridinamines and Aryl Diamines

Co-reporter:Yang Yu;Huan Yang;Zhang-Wen Wei

Heteroatom Chemistry 2014 Volume 25( Issue 4) pp:274-281

Publication Date(Web):

DOI:10.1002/hc.21187

ABSTRACT

A reaction of N-benzylpyridinamines with n-BuLi, followed by a reaction with CS₂ and R₃SnCl or R₂SnCl₂ (R = n-Bu, PhCH₂, or Ph) gave a series of mononuclear organotin dithiocarbamates. A similar reaction of N,N'-bis(benzyl)-1,3-benzenediamine and N,N'-bis(benzyl)-2,6-pyridinediamine afforded dinuclear and macrocyclic organotin dithiocarbamates. All of these complexes were characterized by elemental analysis, IR, and multinuclear NMR (¹H, ¹³C, and ¹¹⁹Sn). Their structures have been confirmed by the X-ray single crystal diffraction analysis, suggesting the dithiocarbamate groups acted as anisobidentate chelating ligands in these complexes. The primary fungicidal activity of these complexes was tested in vitro, showing that most complexes displayed good antifungal activity to Sclerotinia sclerotiorum.

(Pyrazol-1-yl)carbonyl and Ester-Functionalized Bis(pyrazol-1-yl)methide Carbonyl Tungsten Complexes

Co-reporter:Jian-Peng Sun, Da-Wei Zhao, Hai-Bin Song, and Liang-Fu Tang

Organometallics 2014 Volume 33(Issue 17) pp:4425-4432

Publication Date(Web):August 19, 2014

DOI:10.1021/om500639f

(3,5-Dimethylpyrazol-1-yl)carbonyl- and n-butoxycarbonyl-functionalized bis(3,5-dimethylpyrazol-1-yl)methide carbonyl tungsten derivatives were unexpectedly formed, together with a bis(3,5-dimethylpyrazol-1-yl)acyl carbonyl tungsten complex, upon sequential treatment of bis(3,5-dimethylpyrazol-1-yl)methane with n-BuLi, tungsten carbonyl, and iodine. The resulting complexes were fully characterized using IR and NMR spectroscopy, and their structures were unambiguously determined by X-ray crystallography.

Synthesis and catalytic activity of pyrazolyl-functionalized N-heterocyclic carbene palladium complexes

Co-reporter:Cai-Hong Cheng;Jia-Ru Xu;Hai-Bin Song

Transition Metal Chemistry 2014 Volume 39( Issue 2) pp:151-157

Publication Date(Web):2014 March

DOI:10.1007/s11243-013-9784-7

Three pyrazolyl-functionalized N-heterocyclic carbene (NHC) palladium complexes based on 1-[2-(pyrazol-1-yl)phenyl]imidazole have been synthesized and characterized by physico-chemical and spectroscopic methods, and the structures of two of the complexes have been confirmed by single-crystal X-ray diffraction. The pyrazolyl-functionalized NHCs act as chelating N,C-bidentate ligands in these three complexes. Catalytic tests have proved that these complexes exhibit highly effective catalytic activity for the Suzuki–Miyaura and Mizoroki–Heck coupling reactions in water or aqueous/organic media under air. The substituents on the pyrazolyl ring exert different influences on the catalytic activity of the complexes in these coupling reactions.

Synthesis of organotin bis(pyrazol-1-yl)methane-tetracarboxylates and tris(pyrazol-1-yl)methane-hexacarboxylates

Co-reporter:Fang-Lin Li, Qi Chen, Hai-Bin Song, Bin Dai, Liang-Fu Tang

Polyhedron 2014 Volume 83() pp:102-107

Publication Date(Web):24 November 2014

DOI:10.1016/j.poly.2014.04.058

Bis(pyrazol-1-yl)methane-tetracarboxylic acid and tris(pyrazol-1-yl)methane-hexacarboxylic acid, namely bis(3,5-dicarboxypyrazol-1-yl)methane (CH2[3,5-Pz(CO2H)2]2) and tris(3,5-dicarboxypyrazol-1-yl)methane (CH[3,5-Pz(CO2H)2]3), have been synthesized by the oxidation reaction of bis(3,5-dimethylpyrazol-1-yl)methane and tris(3,5-dimethylpyrazol-1-yl)methane with an excess of KMnO4. Reaction of CH2[3,5-Pz(CO2H)2]2 with (R3Sn)2O yielded the corresponding organotin polycarboxylates (CH2[3,5-Pz(CO2SnR3)2]2, R = Et (1) and n-Bu (2), respectively). The structures of these two complexes have been confirmed by X-ray structural analyses. Complex 1 formed a coordination polymer containing fused 22- and 24-membered macrocyclic units. While complex 2 created a double-layer macrocyclic structure by the bridging coordination of carboxylate groups to the tin atoms as well as the hydrogen bonds in coordinated waters. Reaction of CH[3,5-Pz(CO2H)2]3 with (Ph3Sn)2O yielded hexanuclear triphenyltin polycarboxylate CH[3,5-Pz(CO2SnPh3)2]3, which did not assemble into a supramolecular architecture like those in complex 1 or 2, possibly owing to the relatively large steric hindrance of the phenyl groups as well as the relatively large size of the hexabasic carboxylic acid.Graphical abstractBis(pyrazol-1-yl)methane-tetracarboxylic acid and tris(pyrazol-1-yl)methane-hexacarboxylic acid as well as their organotin derivatives have been synthesized. These organotin complexes exhibited remarkably different supramolecular aggregates.

Synthesis and structural characterization of N-heterocyclic carbene silver complexes derived from N-ferrocenylmethyl-N′-(pyridylmethyl)imidazolium iodides

Co-reporter:Qiang Li, Xin Li, Jun Yang, Hai-Bin Song, Liang-Fu Tang

Polyhedron 2013 59() pp: 29-37

Publication Date(Web):

DOI:10.1016/j.poly.2013.04.032

Synthesis of N-heterocyclic carbene silver and palladium complexes bearing bis(pyrazol-1-yl)methyl moieties

Co-reporter:Qiang Li, Yun-Fu Xie, Bao-Chuan Sun, Jun Yang, Hai-Bin Song, Liang-Fu Tang

Journal of Organometallic Chemistry 2013 s 745–746() pp: 106-114

Publication Date(Web):

DOI:10.1016/j.jorganchem.2013.07.055

Synthesis and catalytic activity of N-heterocyclic carbene silver complexes derived from 1-[2-(pyrazol-1-yl)phenyl]imidazole

Co-reporter:Cai-Hong Cheng, Dan-Feng Chen, Hai-Bin Song, Liang-Fu Tang

Journal of Organometallic Chemistry 2013 726() pp: 1-8

Publication Date(Web):

DOI:10.1016/j.jorganchem.2012.12.008

Synthesis and reactivity of bis(3,5-dimethylpyrazol-1-yl)methanes functionalized by 2-halophenyl groups on the methine carbon

Co-reporter:Da-Wei Zhao, Yun-Fu Xie, Hai-Bin Song, Liang-Fu Tang

Journal of Organometallic Chemistry 2012 718() pp: 89-95

Publication Date(Web):

DOI:10.1016/j.jorganchem.2012.08.004

Reactivity of Bis(3,5-dimethylpyrazol-1-yl)methyllithium with S or CS2, Followed by Reaction with Fe3(CO)12 and Ar3SnCl or RX: Unexpected Formation of (3,5-Dimethylpyrazol-1-yl)dithioformate Derivatives

Co-reporter:Xia-Li Liu, Xiao-Yan Zhang, Hai-Bin Song, and Liang-Fu Tang

Organometallics 2012 Volume 31(Issue 14) pp:5108-5113

Publication Date(Web):July 9, 2012

DOI:10.1021/om300448a

Reaction of bis(3,5-dimethylpyrazol-1-yl)methyllithium with sulfur at −70 °C, followed by reaction with Fe3(CO)12 and triaryltin chlorides, yielded trinuclear butterfly cluster complexes. When the triaryltin chlorides were replaced by organic halides, unexpected (3,5-dimethylpyrazol-1-yl)dithioformate derivatives were obtained. In addition, treatment of bis(3,5-dimethylpyrazol-1-yl)methane with n-BuLi at 0 °C resulted in partial decomposition to yield a carbene intermediate and a 3,5-dimethylpyrazolate anion. The carbene intermediate readily dimerized, and reaction of the anion with carbon disulfide, and subsequently with Fe3(CO)12 and organic halides, also gave the dithioformate derivatives.

Reactivity of Cyclopentadienes Modified by Bis(3,5-dimethylpyrazol-1-yl)methyl Group to W(CO)5THF

Co-reporter:Xiaoyan Zhang;Xiali Liu;Haibin Song ;Liangfu Tang

Chinese Journal of Chemistry 2011 Volume 29( Issue 12) pp:2702-2706

Publication Date(Web):

DOI:10.1002/cjoc.201180443

Abstract

The reactions of the mixture of 1- and 2-[2,2-bis(3,5-dimethylpyrazol-1-yl)-1-phenylethyl]-1,3-cyclopentadiene (bpzpcpH) and mixture of 1- and 2-[2,2-bis(3,5-dimethylpyrazol-1-yl)-1,1-diphenylethyl]-1,3-cyclopentadiene (bpzdpcpH) with W(CO)₅THF have been carried out. The former yields complex (bpzpcpH)W(CO)₄, in which the bpzpcpH acts as a κ²-(N,N) bidentate ligand, and the cyclopentadiene moiety does not participate in the coordination to the tungsten atom. While the latter gives complex (bpzdpcpH)W(CO)₃, in which the cyclopentadiene moiety coordinates to the tungsten atom in η²-fashion instead of general η⁵-coordinated mode, causing bpzdpcpH to act as a tridentate κ³-(π,N,N) ligand.

Reactivity of bis(pyrazol-1-yl)methanes functionalized by 2-hydroxyphenyl and 2-methoxyphenyl on the methine carbon atom with W(CO)5THF

Co-reporter:Ke Ding, Cai-Hong Cheng, Yan-Xin Yang, Hai-Bin Song, Liang-Fu Tang

Journal of Organometallic Chemistry 2011 696(23) pp: 3662-3667

Publication Date(Web):

DOI:10.1016/j.jorganchem.2011.08.023

Synthesis, structure and biological activity of triorganotin 1H-tetrazolyl-1-acetates: cyclic hexamer and linkage coordination polymers

Co-reporter:Yun-Fu Xie;Yang Yu;Zhi-Jin Fan;Lin Ma;Na Mi

Applied Organometallic Chemistry 2010 Volume 24( Issue 1) pp:1-7

Publication Date(Web):

DOI:10.1002/aoc.1569

Abstract

Reaction of 1H-tetrazolyl-1-acetic acid (CHN₄CH₂CO₂H) with (R₃Sn)₂O or R₃SnOH yields triorganotin 1H-tetrazolyl-1-acetates [CHN₄CH₂CO₂SnR₃, R = Ph (1), p-tolyl (2), cyclohexyl (3), n-Bu (4) and Et (5)]. 1H-tetrazolyl-1-acetates in these triorganotin derivatives display remarkably different coordination modes, depending on the properties of the organic substituents bonded to the tin atoms. Complex 1 displays a rare cyclohexameric structure by the assembly of the SnN coordination bond, while complex 2 forms a linkage coordination polymer through the intermolecular Sn···N interactions. The structure of complex 3 is similar to that of complex 2, but the intermolecular Sn···N interactions are weaker in the former. However, in complex 4, the tetrazolyl nitrogen atoms do not coordinate to the tin atoms. This complex forms a polymeric chain by the unsymmetric bridging carboxylate group. All these complexes exhibit good antifungal activities in vitro against Alternaria solani, Cercospora arachidicola, Gibberella zeae, Physalospora piricola and Botrytis cinerea. The corresponding EC₅₀ values of these complexes were tested. Copyright © 2009 John Wiley & Sons, Ltd.

Synthesis, structure and biological activity of diorganotin derivatives with pyridyl functionalized bis(pyrazol-1-yl)methanes

Co-reporter:Fang-Lin Li;Hai-Bin Song;Bin Dai

Applied Organometallic Chemistry 2010 Volume 24( Issue 10) pp:669-674

Publication Date(Web):

DOI:10.1002/aoc.1664

Abstract

Three pyridyl functionalized bis(pyrazol-1-yl)methanes, namely 2-[(4-pyridyl)methoxyphenyl] bis(pyrazol-1-yl)methane (L¹), 2-[(4-pyridyl)methoxyphenyl]bis(3,5-dimethylpyrazol-1-yl)methane (L²) and 2-[(3-pyridyl)methoxyphenyl]bis(pyrazol-1-yl)methane (L³) have been synthesized by the reactions of (2-hydroxyphenyl)bis(pyrazol-1-yl)methanes with chloromethylpyridine. Treatment of these three ligands with R₂SnCl₂ (R = Et, n-Bu or Ph) yields a series of symmetric 2:1 adducts of (L)₂SnR₂Cl₂ (L = L¹, L² or L³), which have been confirmed by elemental analysis and NMR spectroscopy. The crystal structures of (L²)₂Sn(n-Bu)₂Cl₂·0.5C₆H₁₄ and (L³)₂SnEt₂Cl₂ determined by X-ray crystallography show that the functionalized bis(pyrazol-1-yl)methane acts as a monodentate ligand through the pyridyl nitrogen atom, and the pyrazolyl nitrogen atoms do not coordinate to the tin atom. The cytotoxic activity of these complexes for Hela cells in vitro was tested. Copyright © 2010 John Wiley & Sons, Ltd.

Synthesis and Crystal Structure of (PzCH2CHOHCH2PzH)·(Ph2SnCl3) (Pz = 3,5-dimethylpyrazol-1-yl)

Co-reporter:Ji-Ting Lu;Miao Du

Journal of Chemical Crystallography 2010 Volume 40( Issue 8) pp:668-671

Publication Date(Web):2010 August

DOI:10.1007/s10870-010-9717-7

Reaction of Ph2SnCl2 with 1,3-bis(3,5-dimethylpyrazol-1-yl)-2-propanol (L) in a 1:1 ratio yields L(SnPh2Cl2)2 adduct, which partly hydrolyzes to the title complex (C25H31Cl3N4OSn, Mr = 628.58) during crystal growing in the air. The title complex is of monoclinic, space group P21/n with a = 9.0338(9), b = 17.890(1), c = 17.340(1) Å, β = 95.533(1)o, V = 2798.9(5) Å3, Z = 4, Dc = 1.492 Mg/m3, λ(MoKα) = 0.71073 Å, μ = 1.224 mm−1, F(000) = 1272, R = 0.023, wR = 0.054 for 4212 observed reflections with I ≥ 2σ(I). The crystal structure indicates that there is no direct interaction between the pyrazolyl ligand and the tin atom, but this complex forms a supramolecular structure through weak intermolecular C–H⋯Cl and O–H⋯Cl hydrogen bonds.

The modification of ArSCH2(3,5-Me2Pz) (Ar = phenyl or 2-pyridyl, Pz = pyrazol-1-yl) by organotin group and related reactions

Co-reporter:Yun-Fu Xie, Guang-Tong Zeng, Hai-Bin Song, Liang-Fu Tang

Journal of Organometallic Chemistry 2010 695(19–20) pp: 2172-2179

Publication Date(Web):

DOI:10.1016/j.jorganchem.2010.06.006

Synthesis and Reactivity of Group 6 Metal Carbonyl Complexes with Bis(pyrazol-1-yl)methanes Modified by the Vinyltin Groups

Co-reporter:Zhenkang WEN;Zhi YANG;Haibin SONG ;Liangfu TANG

Chinese Journal of Chemistry 2009 Volume 27( Issue 5) pp:993-998

Publication Date(Web):

DOI:10.1002/cjoc.200990169

Abstract

Diphenyl(vinyl)stannylbis(3,5-dimethylpyrazol-1-yl)methane and diphenyl(vinyl)stannylbis(3,4,5-trimethyl- pyrazol-1-yl)methane have been synthesized by the reaction of bis(3,5-dimethylpyrazol-1-yl)methyl or bis(3,4,5- trimethylpyrazol-1-yl)methyllithium with diphenyl(vinyl)tin iodide. Treatment of these bis(pyrazol-1-yl)methanes modified by the vinyltin groups with M(CO)₅THF (M=Mo and W) in refluxing THF resulted in new heterobimetallic complexes R₃SnCHPz₂M(CO)₃ (R₃Sn represents trivinyltin or diphenyl(vinyl)tin, and Pz represents substituted pyrazol-1-yl), in which a vinyl group bonds to the molybdenum or tungsten atom in η²-fashion to lead to bis(pyrazol-1-yl)methanes acting as a tridentate κ³-(π,N,N) ligand. Reaction of (CH₂=CH)₃SnCH(3,5-Me₂Pz)₂W(CO)₃ and Ph₂(CH₂=CH)SnCH(3,5-Me₂Pz)₂W(CO)₃ with I₂ has been investigated. The former gave a complex CH₂(3,5-Me₂Pz)₂W(CO)₄, while the latter yielded a four-membered heterometallocyclic complex CH(3,5-Me₂Pz)₂W(CO)₃I with the loss of the organotin group. Treatment of this four-membered heterometallocyclic complex with PhSNa led to the iodide anion replaced by the thiophenolate anion to give a complex CH(3,5-Me₂Pz)₂W(CO)₃SPh.

Synthesis, structure, and fungicidal activity of triorganotin (4H-1,2,4-triazol-4-yl)benzoates

Co-reporter:Fang-Lin Li;Bin Dai;Hai-Bin Song;Na Mi

Heteroatom Chemistry 2009 Volume 20( Issue 7) pp:411-417

Publication Date(Web):

DOI:10.1002/hc.20566

Abstract

A series of triorganotin (4H-1,2,4-triazol-4-yl)benzoates have been synthesized by the reaction of 4-(4H-1,2,4-triazol-4-yl)benzoic acid and 3-(4H-1,2,4-triazol-4-yl)benzoic acid with (R₃Sn)₂O (R = Et, n-Bu and Ph) or R′₃SnOH (R′ = p-tolyl and cyclohexyl). The molecular structure of tri(p-tolyl)tin 3-(4H-1,2,4-triazol-4-yl)benzoate determined by X-ray crystallography displays that the tin atom adopts a five-coordinate distorted trigonal bipyramidal geometry with the carboxyl oxygen atom and the nitrogen atom on 1-position of triazole ring occupying the apical position. Moreover, this complex forms a polymeric chain by the intermolecular Sn–N interactions. All these complexes show good antifungal activities in vitro against Alternaria solani, Cercospora arachidicola, Gibberella zeae, Physalospora piricola, and Botrytis cinerea. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 20:411–417, 2009; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20566

Synthesis of group 6 metal carbonyl complexes containing oxygen- and sulfur-functionalized 1,2,4-triazoles

Co-reporter:Yang Yu;Xiao-Yan Zhang;Juan Hong;Hai-Bin Song

Transition Metal Chemistry 2009 Volume 34( Issue 7) pp:791-795

Publication Date(Web):2009 October

DOI:10.1007/s11243-009-9264-2

Reaction of RCOCH2Tz and PhCOCH(CH2SPh)Tz with M(CO)6 or M(CO)5THF results in RCOCH2TzM(CO)5 and PhCOCH(CH2SPh)TzM(CO)5 (R = phenyl or ferrocenyl, Tz = 1,2,4-triazol-1-yl and M = Mo or W). X-ray crystal structure analyses show that the triazolyl group acts as a monodentate ligand through the exodentate nitrogen atom in these complexes. The electrochemical behavior of these complexes has been investigated by cyclic voltammetry.

Bis(3,5-dimethylpyrazol-1-yl)acyl and Bis(3,5-dimethylpyrazol-1-yl)methide Carbonyl Tungsten Derivatives

Co-reporter:Yun-Fu Xie, Zhen-Kang Wen, Run-Yu Tan, Juan Hong, Shu-Bin Zhao and Liang-Fu Tang

Organometallics 2008 Volume 27(Issue 21) pp:5684-5690

Publication Date(Web):October 3, 2008

DOI:10.1021/om800603p

Reaction of (isopropyl)diphenylstannylbis(3,5-dimethylpyrazol-1-yl)methane [(i-Pr)Ph2SnCH(3,5-Me2Pz)2] and tricyclohexylstannylbis(3,5-dimethylpyrazol-1-yl)methane [Cy3SnCH(3,5-Me2Pz)2] with W(CO)5THF in refluxing THF yields heterobimetallic complexes (i-Pr)Ph2SnCH(3,5-Me2Pz)2W(CO)4 and Cy3SnCH(3,5-Me2Pz)2W(CO)4, respectively. Treatment of these heterobimetallic complexes, R3SnCH(3,5-Me2Pz)2W(CO)4 (R3 = (i-Pr)Ph2, Cy3, Et3), with I2 results in the formation of a novel η1-bis(pyrazol-1-yl)acyl complex CHC(O)(3,5-Me2Pz)2W(CO)3I, with the loss of the organotin group from the methine carbon. In addition, the reaction of R3SnCH(3,5-Me2Pz)2W(CO)4 with SnCl4 in a 1:1 molar ratio gives heterotrimetallic complexes R3SnCH(3,5-Me2Pz)2W(Cl)(CO)3SnCl3 (R = Cy, Et). It is unexpected that these heterotrimetallic complexes are also reactive in solution. They change to a novel four-membered heterometallacyclic complex CH(3,5-Me2Pz)2W(CO)3Cl in dichloromethane solution at room temperature. Furthermore, this complex can also be obtained by the selective cleavage of the W−Sn bond in complexes CH(3,5-Me2Pz)2W(CO)3SnAr3 with SnCl4.

Synthesis, characterization and biological activity of diorganotin dithioate derivatives

Co-reporter:Ji-Ting Lu;Shan-Shan Chen;Miao Du

Applied Organometallic Chemistry 2006 Volume 20(Issue 7) pp:

Publication Date(Web):15 JUN 2006

DOI:10.1002/aoc.1087

Reaction of dithioacid (ArCS₂CH₂CO₂H, Ar = phenyl, 2-furyl or 2-thienyl) with ⁿBu₂SnO gives monomeric (ArCS₂CH₂CO₂)₂Sn(Buⁿ)₂ in a 2:1 molar ratio, and dimeric {[(ArCS₂CH₂CO₂)Sn(Buⁿ)₂]₂O}₂ in a 1:1 molar ratio, respectively, which have been characterized by IR, NMR (¹H, ¹³C and ¹¹⁹Sn) spectra and elemental analyses. X-ray crystal structure analyses indicate that the compound [(C₄H₃S)CS₂CH₂CO₂]₂Sn(Buⁿ)₂ is monomeric with the tin atom occupying a skew-trapezoidal bipyramidal geometry. In addition, this compound forms a three-dimensional structure through the weak intermolecular S^…S and Sn^…O interactions. Compound {[((C₄H₃S)CS₂CH₂CO₂)Sn(Buⁿ)₂]₂O}₂ is a centrosymmetric dimer with a cyclic Sn₂O₂ unit, in which the coordination modes of the two crystallographically unique carboxylic ligands are different. One acts as monodentate ligand by the carboxylate oxygen atom, the other bridges two tin atoms via only one carboxylate oxygen atom. Furthermore, each tin atom in this compound locates a distorted trigonal bipyramidal geometry. Biological activities of these organotin compounds show that they have hardly acaricidal activity, but display certain activities on fungi. In mononuclear tin compounds, the inhibition percentage of [(C₄H₃S)CS₂CH₂CO₂]₂Sn(Buⁿ)₂in vitro for Alternaria solani and Physolospora piricola is 57.1% and 43.9%, respectively, while in dimers {[((C₄H₃O)CS₂CH₂CO₂)Sn(Buⁿ)₂]₂O}₂ shows high inhibition percentage for Gibbereila zeae (52.6%) and Physolospora piricola (50.0%), respectively. Copyright © 2006 John Wiley & Sons, Ltd.

Synthesis, structural characterization and bioassay screening of dimeric bis[dicarboxylatotetraorganodistannoxanes]

Co-reporter:Zhen-Kang Wen;Hai-Bin Song;Miao Du;Yu-Ping Zhai

Applied Organometallic Chemistry 2005 Volume 19(Issue 9) pp:

Publication Date(Web):24 AUG 2005

DOI:10.1002/aoc.960

Reaction of bis(pyrazol-1-yl)acetic acid with n-Bu₂SnO in a 1:1 molar ratio gives dimeric bis[dicarboxylatotetraorganodistannoxanes], {[(n-Bu)₂(Pz₂CHCO₂)Sn]₂O}₂ (Pz = pyrazol-1-yl or 3,5-dimethylpyrazol-1-yl), which are characterized by IR and NMR (¹H, ¹³C and ¹¹⁹Sn) spectra and elemental analyses. The X-ray crystal structure analyses indicate that {[(n-Bu)₂(Pz₂CHCO₂)Sn]₂O}₂ is a centrosymmetric dimer with a cyclic Sn₂O₂ unit, in which each tin atom is situated in a distorted trigonal bipyramidal geometry. In addition, bis(3,5-dimethylpyrazol-1-yl)acetic acid in the solid state forms a dimer through two intermolecular OH···N hydrogen bonds. These organotin derivatives display low fungicide, insecticide and miticide activities, but display certain cytotoxicities for Hela cells in vitro. Copyright © 2005 John Wiley & Sons, Ltd.

Crystallographic report: Tricarbonylacetylcyclopentadienylmolybdenumtin(IV) trichloride

Co-reporter:Xue-Mei Zhao;Ji-Tao Wang

Applied Organometallic Chemistry 2005 Volume 19(Issue 1) pp:

Publication Date(Web):6 JAN 2005

DOI:10.1002/aoc.783

Synthesis and crystal structures of cyclodiazastannoxides fused cyclopentadienyl M–Sn (M = Mo, W) bonded organometallic heterocycle

Co-reporter:Liang-Fu Tang, Xue-Mei Zhao, Zhi-Hong Zou, Hai-Bin Song, Yu-Ping Zhai

Journal of Organometallic Chemistry 2005 Volume 690(Issue 18) pp:4124-4131

Publication Date(Web):15 September 2005

DOI:10.1016/j.jorganchem.2005.06.027

The condensation reaction of CH3COC5H4M(CO)3SnCl3 (M = Mo or W) with PyCONHNH2 (Py = 2,3,4-pyridyl or 2-pyridylmethyl) in mild conditions yields cyclodiazastannoxides fused cyclopentadienyl M–Sn bonded organometallic heterocycle {μ-[C5H4(CH3)CN–NC(O)PyH]M(CO)3SnCl3}. The similar reaction of CH3COC5H4M(CO)3SnCl3 with ArCONHNH2 (Ar = 2-furanyl) gives complexes μ-[C5H4(CH3)CN–NC(O)Ar]M(CO)3SnCl2(H2O), in which the water molecule can be replaced by other N-donor ligands, such as pyridine or 4,4-bipyridine. Arene-bridged organometallic heterocyclic complexes μ-{[C5H4(CH3)CN–NC(O)]2C6H4}{M(CO)3SnCl2(Solvent)}2 have also been prepared by the reaction of CH3COC5H4M(CO)3SnCl3 with terephthaloyl hydrazine. In these new organometallic heterocyclic complexes, it seems that the tin atom prefers to be six-coordinate through absorbing the chloridion or solvent molecules.Reaction of CH3COC5H4M(CO)3SnCl3 (M = Mo or W) with heteroaroylhydrazine in mild conditions yields cyclodiazastannoxides fused cyclopentadienyl M–Sn bonded organometallic heterocycle.