Synthesis and characterization of metallodendritic palladium-biscarbene complexes derived from 1,1′-methylenebis(1,2,4-triazole)

Hornillos V.; Guerra J.; De Cózar A.; Prieto P.; Merino S.; Maestro M.A.; Díez-Barra E.; Tejeda J.

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Synthesis and characterization of metallodendritic palladium-biscarbene complexes derived from 1,1′-methylenebis(1,2,4-triazole)

机译：1,1'-亚甲基双（1,2,4-三唑）衍生的金属树枝状钯-双卡宾配合物的合成与表征

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The syntheses of first generation dendritic compounds bearing 1,1′-alkane-1,1-diylbis(4-butyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene) palladium(ii) dibromide on the periphery are described. The metallabiscarbene moieties have also been studied separately from the dendrimer. These compounds display a non-symmetric boat-to-boat conformational equilibrium that has axial and equatorial arrangements. The predominance of the axial conformer in the equilibrium is supported by DFT calculations. The X-ray solid state structures of axial conformers of 3-hydroxy- and 3-mesyloxy-1,1′-propane-1,1- diylbis(4-butyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene)palladium(ii) dibromide are reported. These complexes display modest catalytic activity in the Heck reaction with activated aryl bromides and the dendritic catalysts were more active than the corresponding non-dendritic mononuclear species, a finding indicative of a cooperative effect.

机译：带有1,1'-烷烃1,1,1-二基双（4-丁基-4,5-二氢-1H-1,2,4-三唑-5-亚烷基）二溴化钯（ii）的第一代树枝状化合物的合成在外围描述。还已经与树枝状聚合物分开研究了金属金卡宾烯部分。这些化合物显示出具有轴向和赤道排列的不对称船到船构象平衡。 DFT计算支持了轴向平衡器在平衡中的优势。 3-羟基-和3-甲氧基-1,1'-丙烷-1,1-二基双（4-丁基-4,5-二氢-1H-1,2,4）的轴向构象的X射线固态结构报道了-（三唑-5-亚烷基）二溴化钯（ii）。这些配合物在与活化的芳基溴化物进行的Heck反应中显示出适度的催化活性，并且树枝状催化剂比相应的非树枝状单核物种更具活性，这一发现表明有协同作用。

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《Dalton transactions: An international journal of inorganic chemistry》 |2011年第16期|共9页
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Hornillos V.; Guerra J.; De Cózar A.; Prieto P.; Merino S.; Maestro M.A.; Díez-Barra E.; Tejeda J.;
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1. Synthesis and characterization of metallodendritic palladium-biscarbene complexes derived from 1,1′-methylenebis(1,2,4-triazole) [J] . Hornillos V., Guerra J., De Cózar A., Dalton transactions: An international journal of inorganic chemistry . 2011,第16期

机译：1,1'-亚甲基双（1,2,4-三唑）衍生的金属树枝状钯-双卡宾配合物的合成与表征
2. Synthesis, Characterization and Dynamic Behavior of Mono- and Dinuclear Palladium(II) Carbene Complexes Derived From 1,1'-Methylenebis(4-alkyl-1,2,4-triazolium) Diiodides [J] . Guy Bertrand, Enrique Diez-Barra, Juan Fernandez-Baeza, European journal of inorganic chemistry . 1999,第11期

机译：1,1'-亚甲基双（4-烷基-1,2,4-三唑鎓）二碘化物衍生的单核和二核钯（II）碳配合物的合成，表征和动力学行为
3. A hexacarbene complex derived from 1,1 '-methylenebis(4-butyl-1H-1,2,4-triazolium) diiodide. Synthesis, characterization and catalytic activity [J] . Diez-Barra E., Guerra J., Rodriguez-Curiel RI., Journal of Organometallic Chemistry . 2002,第1期

机译：衍生自1,1'-亚甲基双（4-丁基-1H-1,2,4-三唑鎓）二碘化物的六碳烯配合物。合成，表征和催化活性
4. The Novelty High–Nitrogen Energetic Compounds Based on the 4-amino-1,2,4-triazole and 1,1'-azobis(1,3,4-triazole) (1,1'-ATZ) [C] . Bi-Dong Wu, Yu-Lu Li, Tong-Lai Zhang, International pyrotechnics seminar;IPSUSA Seminars, Inc.;International Pyrotechnics Society . 2013

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5. Et(2)C(2)B(4)H(4)-titanium-phosphine complexes: Synthesis, characterization, and ethylene polymerization activity, and, Preliminary studies in combinatorial catalysis: Synthesis and catalytic testing of a resin-tethered 1,1'-2-binapthol. [D] . Dodge, Tye J. 2001

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6. Metal-Based Biologically Active Compounds: Synthesis Spectral and Antimicrobial Studies of Cobalt Nickel Copper and Zinc Complexes of Triazole-Derived Schiff Bases [O] . Kiran Singh, Yogender Kumar, Parvesh Puri, 2011

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7. Synthesis of 1,1′-methylenebis(1,2,4-triazole) functionalized in the methylene bridge. A new approach to dendrons bearing heterocyclic rings on the periphery [O] . Enrique Díez-Barra, Javier Guerra, Valentín Hornillos, 2005

机译：在亚甲基桥中官能化的1,1'-亚甲基双（1,2,4-三唑）的合成。在外围带有杂环的树枝状新方法
8. Synthesis of 1,1'-Dinitro-3,3'-Azo-1,2,4-Triazole [R] . Lee, K. Y. 1985

机译：1,1'-二硝基-3,3'-偶氮-1,2,4-三唑的合成

Synthesis and characterization of metallodendritic palladium-biscarbene complexes derived from 1,1′-methylenebis(1,2,4-triazole)

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