SYNTHESIS OF 1-SUBSTITUTED-BENZENESULFO-NYL-3-(4'''',6''''-DISUBSTITUTED-s-TRIAZIN.2''''-YL)-1,3,2-DIAZAPHOSPHOLIDINES AND THEIR STRUCTURAL ANALYSES

The reaction of N-substituted-benzenesulfonyl-N'-(4,6-disubstituted-s-triazin-2-yl)-ethylene diamines with tri(dialkylamine)phosphine has been studied and the cyclic products have been obtained by one-pot reaction. It was found from ~1H NMR and ~(13)C NMR analyses that the single bond rotation between the nitrogen atom 3 in the 1,3,2-diazaphospholidines and the carbon atom 2 in the s-triazine was hindered at room temperature, which was further confirmed by X-ray diffraction results. The most stable conformation of the phosphorous heterocycle is envelope-form. From the bond length and the hybridization of the nitrogen atom outside the ring, it was deduced that there was a certain contribution of dπ-pπ bond between P and N atoms.     

Syntheses and bioactivities of mixed butyl/cyclohexyl tin carboxylates

Eight novel compounds have been synthesized and they are two series of mixed tri(butyl/cyclohexyl) tin carboxylates:Bu_nCy_(3-n) SnO_2CR (n=1,2;R=n-C_3H_7,C_6H_5,4-ClC_6H_4,4-NO_2C_6H_4).Inaddition to the studies of their structures with IR,~(119)Sn and ~(13)C NMR,we tested their fungicidal,insec-ticidal and acaricidal activities.The percentage of inhibition to the aforementioned phytopathogen isabout 80—100% at 50 ppm in glasshouse and 100% for T.Uriticae at 500 ppm.Those findingsindicate that this kindof compounds have both fungicidal and acaricidal activities and mayhave a goodprospect for applications.     

PREPARATION AND CRYSTAL STRUCTURE OF TETRAMETHYLETHENE-BRIDGED DICYCLOPENTADIENYLSAMARIUM (Ⅲ) COMPLEX

(CH_3)_4C_2(C_5H_4)_2Sm(C_5H_5)OC_4H_, Mr=499.4, orthorhombic, Cc2a, a=11.696(6), b=12.539(5), c=29.432(15), V=4316(4)~, Z=8, Dc=1.54g. cm~(-3), μ (MoKα)=27.8cm~(-1), F(000)=2024, R=0.077 for 1833 observed reflections. In the molecule the samarium atom is bonded to three cyclopentadienyl rings and an oxygen of tetrahydrofuran(THF). The three centroids of the cyclopentadienyl rings and the oxygen form a tetrahedral configuration around the Sm(Ⅲ) atom, The average Sm-C(η~) bond distances for the three cyclopentadienyl groups are 2.72(3), 2.76(3), 2.78(8) respectively, and Sm-0 bond is 2.53(1).     

SYNTHESIS AND STRUCTURE OF DIAQUO-μ-TRIETHYLENETE-TRA AMINOHEX A ACETATODI ANTIMONY ( Ⅲ) , C(H_2O)Sb(ttha)Sb-(H_2O)]

<正> C_18H_28N_4O_14Sb_2, MT = 767. 94, monoclinic, space group P2_1/c, a = 13. 847(2),b=6.866(2),c=13. 846(2) A,β=116. 46(1)°,V=1180. 3A3,Z=2,Dc = 2. 161g/cm3, F(000) = 756,μ(MoKa) = 23. 83cm-1. R and Rw were 0.054 and 0. 060, respectively, for 1357 observed reflections at room temperature. Each binuclear complexes arranged so that the centre of the carbon-carbon bond in the ethylenediamine group lies on a crystallographic centre of inversion. The ethylenediamine group forms a bridge between the two halves of the title molecule. Each antimony atom is ψ-heptacoordi-nated by a lone electron pair,one O atom from a water molecucle,one O atom from an ac-etato group and two amino N atoms at the equatorial plane as well as two O atoms from the acetato groups at the axial positions forming a pentagonal bipyramid.     

Theoretical study on tetrazole and its derivatives (3) MP2 and thermodynamic calculations of amino derivatives of tetrazole

Fully optimized geometries and electronic structures of amino derivatives of tetrazole are obtained at MP2/6-31G* level. The tetrazole rings are planar and aromatic for all the amino derivatives of tetrazole. The amino group is not co-planar with the ring and its conformation is mainly determined by the lone pair electronic repulsion between the substituent and the ring. N(4) atom is more negatively charged and is the most probable coordination site. The energy gaps between LUMOs and HOMOs of 2H-aminotetrazoles and C-aminotetrazole neutrals are smaller than those of the corresponding 1H-isomers and N-aminotetrazole neutrals respectively. The IR frequencies, thermodynamic properties and temperature-dependent functions for heat capacities in the form (a bT cT2) in the 300-1000K range are reported.     

A SCF-SOCI STUDY ON THE LOW-LYING STATES OF H_3~+

The ground state and three low-lying states of the H_3~+ are determined by SOCI(Second Order Configuration Interaction) calculations. The results indicate that the ~3Σ_u~+ state of H_3~+ 3 is a bound state, but ~1A_1 and ~3A_1 states are not stable, each of them will dissociate into H_2~+ and H atom. The SOCI energy -1.1144065au at an equidistant nuclear separation of 1.296A is in good agreement with the lowest value reported so far.     

Ab Initio Study of Mechanism of Forming a Si-heterocyclic Spiro-Sn-heterocyclic Ring Compound by Cycloaddition Reaction of Cl_2Si=Sn: and Ethylene

X_2Si=Sn:(X = H, Me, F, Cl, Br, Ph, Ar…) are new species of chemistry. The cycloaddition reaction of X_2Si=Sn: is a new study field of stannylene chemistry. To explore the rules of cycloaddition reaction between X_2Si=Sn: and the symmetric p-bonded compounds, the cycloaddition reactions of Cl_2Si=Sn: and ethylene were selected as model reactions in this paper.The mechanism of cycloaddition reaction between singlet Cl_2Si=Sn: and ethylene has been first investigated with the MP2/GENECP(C, H, Cl, Si in 6-311++G**; Sn in LanL2dz) method in this paper. From the potential energy profile, it could be predicted that the reaction has one dominant reaction channel. The reaction rule presented is that the 5p unoccupied orbital of Sn in Cl_2Si=Sn: and the π orbital of ethylene forming a p→p donor-acceptor bond, resulting in the formation of an intermediate. Instability of the intermediate makes it isomerize to a four-membered Si-heterocyclic ring stannylene. Because the 5p unoccupied orbital of Sn atom in the four-membered Si-heterocyclic ring stannylene and the π orbital of ethylene form a p→p donor-acceptor bond, the four-membered Si-heterocyclic ring stannylene further combines with ethene to form another intermediate. Because the Sn atom in the intermediate shows sp~3 hybridization after transition state, the intermediate isomerizes to a Si-heterocyclic spiro-Sn-heterocyclic ring compound. The research result indicates the laws of cycloaddition reaction between X_2Si=Sn: and the symmetric π-bonded compounds. The study opens up a new research field for stannylene chemistry.     

STRUCTURAL STUDIES OF CHLORO(QUINOLINE-8-OLATO)DIETHYLTIN(IV),[SnEt_2Cl(CsH_6NO)]

<正> INTRODUCTION. The coordination and stereochemistry of organotin derivatives of 8-hydroxyquinoline(Hoxin) have been of interest because of forming various coordination geometies and exhibiting different isomer forms in the same geometry. This paper reports the structure of compound [SnEt_2Cl(oxin)] and discusses the interactions between adjacent molecules which lead to a 5+1 coordination of the central tin atom.     

Synthesis and Characterization of a Noncovalently Linked Porphyrin-[1,2-(1-acridin-10′-yl-2-aza-2-methylprop-1,3-ylene)-fullerene]Dyad

1,2-(1-Acridin-10'-y1-2-aza-2-methylprop-1,3-ylene)fullerene was synthesized firstly and characterized byUV-Vis,~1H NMR,~(13)C NMR and electrospray ionization mass spectroscopy,which is capable of forming a stablecomplex with zinc tetraphenylporphyrin via the axial ligafion.The steady state fluorescence studies show efficientquenching of the zinc tetraphenylporphyrin emission upon axial coordination of acridine attached to C_(60).     

Synthesis and Crystal Structure of Tetra（o-cyanobenzyl）tin

The tetra（o-cyanobenzyl）tin compound has been synthesized by the reaction of cyanobenzyl chloride with tin, and its molecular structure was characterized by elemental analysis, IR spectra, ^1H NMR and X-ray diffraction. Crystal data for this compound： monoclinic, space group C2/c, Mr = 583.24, a = 1.9629（2）, b = 1.05967（13）, c = 1.41249（18） nm, β= 118.180（2）^o, V = 2.5898（5） nm^3, Z = 4, Dc =1.496 g/cm^3, μ（MoKa） = 1.015 cm^-1, F（000） = 1176, R = 0.0189, wR = 0.0497 （observed reflections with I 〉 20（I）） and R = 0.0218, wR = 0.0513 （all reflections）. The molecular structure adopts a distorted tetrahedral geometry around the tin atom. The Sn＇＂N weak interaction between the Sn and N atoms of cyano forms an intermolecular H-bonding, and the bond length is 0.3570 nm; the interaction between hydrogen of methylene and benzene ring of benzyl forms C-H…C with its bond length of 0.2817 nm; and the interaction among hydrogen of benzene ring and carbon of cyano forms Ph-H…C bond （0.2897 nm） Of the σ…π interaction. A 3D chain structure is formed by the above weak intermolecular interactions.     

SYNTHESIS OF NOVEL THIOPHENEDIMETHYLENE BRIDGED HOMOBINUCLEAR METALLOCENES AND THEIR CATALYTIC PROPERTIES FOR ETHYLENE POLYMERIZATION

By treating disodium(thiophenedirnethylene)dicyclopentadienide C_4H_2S(CH_2C_5H_4Na)_2 with two equivalent of CpTiCl_3 or CpZrCl_3 DME at 0℃ in THF,two new thiophenedimethylene bridged binuclear metallocenes [Cl_2MC_5H_5][C_5H_4CH_2C_4H_2SCH_2C_5H_4][C_5H_5MCl_2](M=Ti 3,M=Zr 4)were synthesized in high yield and their structures were characterized by ~1H-NMR.These complexes were used as catalysts for ethylene polymerization in the presence of methylaluminoxane(MAO).The effects of polymerization temperature,time,concentration of catalyst,molar ratio of MAO/Cat on polymerization were studied in detail.The catalytic activities of thiophenedimethylene bridged binuclear metallocene catalysts(3,4)reached 2.44×10~5 g PE mol~(-1)·cat~(-1)·h~(-1),9.61×10~5 g PE mol~(-1)·cat~(-1)·h~(-1) respectively,which are higher than that of pheneyldimethylene bridged binuclear metallocene catalysts and much higher than that of corresponding mononuclear metallocenes(Cp_2TiCl_2 and Cp_2ZrCl_2).The molecular weight distribution curves of polyethylenes produced by binuclear metallocene catalysts(3,4)and by mononuclear metallocene catalyst have only single peak,but the former(MWD=3.5-4.7)is obviously broader than the latter(MWD=2.0-2.2).     

STUDIES ON THE PROPERTIES OF SCHIFF BASE TYPE ARYLMERCURY COMPOUNDS.II ~(199)Hg NMR SPECTRA OF MERCURATED DERIVATIVES OF SUBSTITUTED BENZYLIDENEANILINES

~(199)Hg NHR spectra of 18 Schiff base type arylmercury compounds have beenstudied.It was further confirmed that in the molecule of XC_6H_4CH=NC_6H_3-2-HgC1-4-CH_3there exists an intramolecular N→Hg coordination via a four-membered ring.For theseries of XC_6H_4CH=NC_6H_3-2-HgCl-4-CH_3(X is a para-or mera-substituent),there is agood linear correlation between δ~(199)Hg and Hammett's o constants.The influence ofsubstituents of C-pheny1 ring on the δ ~(199)Hg can be explained in terms of theintramolecular N→Hg coordination.     

CRYSTAL STRUCTURE OF [Ce~(Ⅲ)Cl_2(THF)_5][Ce~ⅣC15(THF)]

<正> INTRODUCTION. The attempt to prepare C_9H_7CeCl_2. nTHF(C_9H_7=indenyl) by the reaction of CeCl_4 3THF with C_9H_7Na in THF(tetrahydrofuran) has failed, but an unexpected orange crystal was obtained and determined by single cryntal X-ray diffraction to be a new complex [Ce~ⅢCl_2 (THF)_5]~+[Ce~ⅣCl_5 THF]~-. The valence state of the cerium atom in the cation is different from that in the anion, the former being trivalent while the latter quadrivalent. In this paper the crystal structure of the new complex is reported.     

Theoretical Investigations on the Structures and Properties of the Side-on Complexes B_2(N_2)_2 and Monocyclic B_n(N_2)_n~m (n=3～6,m=-1～+2)

The structures and energies of the side-on complexes B2(N2)2 and monocyclic Bn(N2)nm (n = 3～6,m = -1～+2) between N2 (1∑+g) and B (2P) have been investigated by the DFT-B3LYP and MP2 methods at the 6-311+G(2d) and aug-cc-pVTZ levels. The analyses of NICS (Nucleus Independent Chemical Shifts),NBO (nature bond orbital),AIM (atoms in molecules) and frontal orbitals have been used to reveal the origin of coordination bond between the π-electron donor N2 group and B atom,accompanied by the comparison with the end-on complexes. The results have indicated that the side-on coordination complexes can be formed due to the relative strong fluidity of the π-electrons,and the nature of the coordination bond has been exposed to be that the N2 group offers 1πu electron to the 2p orbital of boron. The coordinate energies of the side-on complexes are less than those of the end-on complexes. Furthermore,the aromaticity of side-on coordination complex is weaker than that of the corresponding end-on coordination complex.     

A highly stable and luminescent mononuclear Cu(Ⅰ) bis-{5-tert-butyl-3-(6-methyl-2-pyridyl)-1H-1,2,4-triazole} complex

A new emissive mononuclear homoleptic Cu(Ⅰ) complex of 5-rert-butyl-3-(6-methyl-2-pyridyl)-1H-1,2,4-triazole(bmptzH),[Cu(bmptzH)_2](ClO_4)(1),has been synthesized by treatment of[Cu(PPh_3)_2(CH_3CN)_2](ClO_4) or [Cu(CH_3CN)_4](ClO_4) with the bmptzH ligand.It is revealed that complex 1 displays a distorted N_4 tetrahedral arrangement formed by two bmptzH chelates,in which bmptzH adopts a neutral bidentate chelating coordination mode using the N atom of the pyridyl ring and the 4-N not 2-N atom of the 1,2,4-triazolyl ring.It is shown that complex 1 is highly stable and exhibits good luminescence properties in solution and solid states at room temperature due to the introduction of a methyl group at the ortho-position of the pyridyl ring.     

Synthesis, Reaction and Structures of Functionally Substituted η~5-Cyclopentadienyl Compounds With Cr≡S Triple Bond [η~5-RC_5H_4Cr(CO)_2]_2S (R=CH_3C(O),CH_3O_2C,C-2H_5O_2C,CH_3CH(OH),CO_2H)

[η_5-OH_3C(O)C_5H_4Cr(CO)_2]_2S 1, [η~5-CH_3O_2CC_5H_4Cr(CO)_2]_2S 2 and [η~5-C_2H_5O_2CC_5H_4Cr(CO)_2]_2S 3 were prepared by the reactions of corresponding sodium salts of functional η~5-cyclopentadienyl-tricarbonylchromium anions with SOCl_2. Reduction of 1 with NaBH_4 prdouced [η~5-CH_3CH(OH)C_5H_4Cr(CO)_2]_2S 4, while saponification of 2 followed by acidification and recrystallization from acetone afforded [η~5-HO_2CC_5H_4Cr(CO)_2]_2S·nCH_3C·(O)CH_3 5. 1—5 are a new class of Cr≡S triple bond compounds containing functional organic group on the cyclopentadienyl ring. A single-crystal X-ray diffraction analysis of 1 revealed that it consists of two identical organometallic fragments η~5-CH_3C(O)C_5H_4Cr(CO)_2 joined together by a sulfur atom via triple bonds. The geometry of structural unit Cr≡S≡Cr belongs to linearity and the average triple bond length of Cr≡S is 2.072(?).     

Studies on Tricyclohexyltin ( Ⅳ ) Diaryldithiophosphates

Fourteen new tricyclohexyltin (Ⅳ)-O,O-diaryldithiophosphates were synthesized and determined by IR, 1H NMR, 13C NMR, 119Sn NMR MS, and elemental analysis. The structures of all the compounds consist of discrete molecule containing a four-coordinated tin atom. Results from the preliminary biological test show that these compounds have a high miticidal activity.     

Features of Mechanism of Cycloaddition Reaction between Me_2Ge=Sn: and Ethylene

X_2Ge=Sn:(X = H, Me, F, Cl, Br, Ph, Ar···) are new species of chemistry. The cycloaddition reaction of X_2Ge=Sn: is a new study field of stannylene chemistry. To explore the rules of cycloaddition reaction between X_2Ge=Sn: and the symmetric p-bonded compounds, the cycloaddition reactions of Me_2Ge=Sn: and ethylene were selected as model reactions in this paper, and the mechanism was investigated for the first time here using the MP2 theory together with the 6-311++G** basis set for C, H and Ge atoms and the LanL2dzbasis set for Sn atoms. From the potential energy profile, it could be predicted that the reaction has one dominant reaction channel. The reaction rule present is that the 5p unoccupied orbital of Sn in Me_2Ge=Sn: and the π orbital of ethylene form a p → p donor–acceptor bond, resulting in an intermediate which, due to its instability, makes itself isomerize into a four-membered Ge-heterocyclic ring stannylene. Because the 5p unoccupied orbital of Sn atom in the four-membered Ge-heterocyclic ring stannylene and the π orbital of ethylene form a p → p donor-acceptor bond, the four-membered Ge-heterocyclic ring stannylene further combines with ethylene to get another intermediate. Because the Sn atom in this intermediate exhibits sp3 hybridization after transition state, the intermediate isomerizes to a Ge-heterocyclic spiro-Sn-heterocyclic ring compound. The research result indicates the laws of cycloaddition reaction between X_2Ge=Sn: and the symmetric π-bonded compounds. This study opens up a new research field for stannylene chemistry.     

丙酮酸异烟酰腙四核有机锡配合物的合成、表征及{[nBu2Sn(C9H8N3O3)O]SnBu3n}2的晶体结构

The tetranuclear alkyltin(Ⅳ) compounds {[R2Sn(C9H8N3O3)O]SnR3}2 [R=n-Bu (1), 4-CNC6H4CH2 (2),C6H5CH2 (3), 4-ClC6H4CH2 (4)] were prepared by the reaction of Schiff base ligand pyruvic acid isonicotinyl hydrazone with (R3Sn)2O in the corresponding molar ratio of 1:1. All compounds have been characterized by elemental analysis, IR and ^1H NMR spectra. The crystal structure of compound 1 was determined by X-ray single crystal diffractional analysis. This compound exhibits a dimeric structure containing distannoxane units with two types of the tin atoms. For the first tin atom, it appears to be seven-coordinated with a distorted pentagonal bipyramid geometry, and the other is five-coordinated with a distorted trigonal bipyramidal geometry. The molecules are packed in the unit cell in two-dimensional network structure through an interaction between the N atoms of the pyridine and the tin atoms of an adjacent molecule.