Schwermetall-π-Komplexe. IX. Die Kettenpolymere [(1,2- (CH3)2C6H4BiCl3)2], [(1,3) (CH3)2C6H4BiCl3)2] und [(1,4- (CH3)2C6H4BiCl3)2]

Heavy Metal π-Complexes. IX. The Chain Polymers [(1,2- (CH₃)₂C₆H₄BiCl₃)₂], [(1,3- (CH₃)₂C₆H₄BiCl₃)₂] and [(1,4- (CH₃)₂C₆H₄BiCl₃)₂] In the crystal structures of the three solid state complexes (C₆H₄(CH₃)₂BiCl₃ (C₆H₄(CH₃)₂ = o-xylene: 1 , m-xylene: 2 , p-xylene: 3 ) quasi-dimeric units of almost undistorted, arene coordinated BiCl₃ fragments can be found that are further associated via additional Bi? Cl contacts to form one-dimensional polymeric chains. Whereas the chains of 2 and 3 are constituted by Bi₂Cl₂ four-membered rings only, further Cl-bridging in 1 leads to additional trigonal-bipyramidal arrangements with Bi atoms exhibiting coordination numbers of 3 + 3 + 1 and 3 + 2 + 1, respectively (prim. + sec. Cl contacts + arene). The arene-metal bonding is characterized by Bi-arene distances in the range from 297 – 306 pm, including ring slippages of 24 –41 pm and 73 pm with the Bi atoms being six and seven coordinated, respectively. The direction of this slipping with respect to the arene's methylation sites cannot be understood in terms of electronic influences but is shown to be caused by steric demands. The values IP₁ of the arenes prove to determine the colours of the complexes.     

Hydrothermal Synthesis and Crystal Structure of a New Phosphonate： {[Cu（1,10-phen）]2-（H2O3PCH2C6H4C6H4CH2PO3H）2-（HO3PCH2C6H4C6H4CH2PO3H） }n

1 INTRODUCTION Metal organophosphonates have attracted considerable attention for over three decades due to their potential or practical applications, include- ing ion exchanges[1, 2], molecular sensors[3] and optics[4, 5]. Recently, a number of porous m…     

Characterization of the sterically encumbered terphenyl-substituted species 2,6-Trip2H3C6Sn-Sn(Me)2C6H3-2,6-Trip2, an unsymmetric, group 14 element, methylmethylene, valence isomer of an alkene, its related lithium derivative 2,6-Trip2H3C6(Me)2Sn-Sn(Li)(Me)C6H3-2,6-Trip2, and the monomer Sn(t-Bu)C6H3-2,6-Trip2 (Trip = C6H2-2,4,6-i-Pr3)

The reaction of the recently reported sterically encumbered terphenyl tin(II) halide species Sn(Cl)C6H3-2,6-Trip2 (Trip = C6H2-2,4,6-i-Pr3), 1, with 1 equiv of MeLi or MeMgBr afforded 2,6-Trip2H3C6Sn-Sn(Me)2C6H3-2,6-Trip2, 2, which is the first stable group 14 element methylmethylene (i.e., CH3CH) analogue of ethylene (H2CCH2). Reaction of 1 with 1.5 equiv of MeLi yielded the stannylstannate species 2,6-Trip2H3C6(Me)2Sn-Sn(Li)(Me)-C6H3-2,6-Trip2, 3, whereas reaction of 1 with 1 equiv of t-BuLi gave the heteroleptic stannanediyl monomer Sn(t-Bu)C6H3-2,6-Trip2 (4). The compounds 2-4 were characterized by 1H, 13C (7Li, 3 only), and 119Sn NMR spectroscopy in solution and by UV-vis spectroscopy. The X-ray crystal structures of 2-4 were also determined. The formation of the stannylstannanediyl 2 instead of the expected symmetrical, valence isomer "distannene" form (Sn(Me)C6H3-2,6-Trip2)2, 6, is explained through the ready formation of LiSn(Me)2C6H3-2,6-Trip2, 5, which reacts rapidly with 1 to produce 2 which can then react with a further equivalent of MeLi to give 3. The stability of singly bonded 2 in relation to the formally doubly bonded 6 was rationalized on the basis of the difference in the strength of their tin-tin bonds. In contrast to the methyl derivatives, the reaction of 1 with t-BuLi proceeded smoothly to give the monomeric compound 4. Apparently, the formation of a t-Bu analogue of 5 was prevented by the more crowding t-Bu group. Compound 2 is also the first example of a stable molecule with bonding between a two-coordinate, bivalent tin and four-coordinate tetravalent tin. Both compounds 2 and 3 display large J 119Sn-119Sn couplings between their tin nuclei and the tin-tin bond lengths in 2 (2.8909(2) A) and 3 (2.8508(4) A) are relatively normal despite the presence of the sterically crowding terphenyl substituents.     

四氯合锌酸十四烷铵-四氯合锌酸十六烷铵二元体系相图

合成了四氯合锌酸十四烷铵(C4H29NH3)2ZnCl4(简记为C14ZnCl)和四氯合锌酸十六烷铵(C16H33NH3)2ZnCl4(简记为C16ZnC1),并配制了一系列不同组成的C14ZnCl-C16ZnCl二元体系,通过DSC测试,变温红外光谱法及X-ray粉末衍射法来绘制该二元体系相图。该相图是生成稳定中问化合物的固相部分互溶体系相图。     

2-(3-ethyl-2,2-dimethylcyclobutyl-methyl)-4(3H)-quinazolinones

Anthranilic acid and its 5-bromo and 4-chloro derivatives react with pinanoic and pinonoic acid chlorides to give the corresponding N-acyl derivatives. The pinanoyl derivatives give the corresponding 2-(3-ethyl-2,2-dimethyl-cyclobutylmethyl)-4-(3H)-quinazolinones when refluxed in formamide. Pinanoylanthranilic acid reacts with dicyclohexylcarbodiimide to give 2-(3-ethyl-2,2-dimethylcyclobutylmethyl)benz-3,1-oxazin-4(H)-one and subsequently with hydrazine hydrate to give 3-amino-2-(3-ethyl-2,2-dimethylcyclobutylmethyl)-4(3H)-quinazolinone. Refluxing of the pinanoyl- and pinonoylanthranilic acids with acetic anhydride gives acetylanthranilic acid, and pinonoylanthranilic acid gives 4(3H)-quinazolinone with formamide.Riga Technical University, Riga LV-1658, Latvia; e-mail: marina@osi.lanet.lv. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 811–817, June, 1999.     

Visible-Light-Induced Photocatalytic C3-Trifluoroethylation of Quinoxalin-2-(1H)-ones

A visible-light-induced Rose bengal catalyzed C3-trifluoroethylation of quinoxalin-2-(1H)-ones is reported. A wide range of quinoxalin-2-(1H)-ones was compatible, which led to the corresponding products in moderate to good yields. A gram-scale reaction proceeded well and afforded an efficient route to prepare C3-trifluoroethylated quinoxalin-2-(1H)-ones.     

Synthesis and characterization of cyano-substituted carborane-based compounds. Molecular structure of [1-(4-C7H7)-12-(C5H3-3-(CN)-3,4-(CH3)2)-C2B10H10

The reaction of cyanogen chloride with [1-(4-C(7)H(7))-12-(C(5)H(3)-3,4-(CH(3))(2))-C(2)B(10)H(10)] (7) was found to yield two new C(5)-substituted carborane cluster-based compounds, [1-(4-C(7)H(7))-12-(C(5)H(2)-3-(CN)-3,4-(CH(3))(2))-C(2)B(10)H(10)] (8) and [1-(4-C(7)H(7))-12-(C(5)H-2,4-(CN)(2)-3,4-(CH(3))(2))-C(2)B(10)H(10)] (9). This cyano-substitution pattern is in contrast to the known substitution for the analogous organic quinarene[5.6.7] system. The observed unique cluster-based products may be understood by a combination of steric and electronic effects. Compounds 8 and 9 were characterized by complete multinuclear NMR, (1)H-(1)H COSY NMR, (1)H-(13)C HMQC NMR, FTIR, UV-Vis, IR, MS data and a single crystal analysis for 8 [X-ray data for 8: C(17)H(25)B(10)N, monoclinic, space group P2(1)/n with cell constants a = 8.6794(17) ?, b = 11.021(2) ?, c = 43.175(9) ?, β = 91.00(3)°, V = 4129.2(14) ?(3), Z = 8, R(1) = 0.0729, wR(2) = 0.1464].