Syntheses, solid structures, and behavior in solution of [MI₂(CO)₃(pyrazole)₂] complexes (M = Mo, W)

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• 作者：Paloma Paredes^a ; Fernando Lorenzo^a ; Sonia Bajo^a ; Elena Cué ; llar^a ; Carsten Strohmann^b ; Jose M. Martí ; n-Alvarez^a ; Daniel Miguel^a ; Fernando Villafañ ; e^a ; ^{fervilla@qi.uva.es}
• 关键词：Pyrazole ; Molybdenum ; Tungsten ; Fluxionality ; Isomers
• 刊名：Inorganica Chimica Acta
• 出版年：2017
• 出版时间：24 February 2017
• 年：2017
• 卷：456
• 期：Complete
• 页码：9-17
• 全文大小：1425 K
• 卷排序：456

文摘

[MI2(CO)3(pz*H)2] complexes (M = Mo, W; pz*H = pzH, dmpzH, indzH) have been synthesized and characterized in solid state and in solution. These heptacoordinated complexes present a capped octahedron geometry in the solid state where the azole ligands are always coordinated pseudo-cis, and the iodido ligands are coordinated either pseudo-trans (pzH complexes and molybdenum complex with indzH) or pseudo-cis (tungsten complex with dmpzH). Both isomers are found in the crystal structure of [WI2(CO)3(indzH)2]. The difference in energies between both isomers have been theoretically calculated and range between −2.9 and +1.0 kcal/mol. The complexes where the iodido ligands are coordinated pseudo-trans show unequivalent azoles in the NMR at low temperature while they undergo a dynamic process in solution which makes both heterocycles equivalent at room temperature. The other complexes display a dynamic behavior in solution where both heterocycles are equivalent both at room and at low temperatures.