Synthesis and reactivity of N,N-dialkylcarbamato complexes of manganese(II). Crystal and molecular structure of [Mn6(O2CNEt2)12], a hexamer with four five-co-ordinated manganese(II) atoms
作者:Antonio Belforte、Fausto Calderazzo、Pier Francesco Zanazzi
DOI:10.1039/dt9880002921
日期:——
[Mn6(O2CNEt2)12], containing four five-co-ordinated Mn atoms, joined by bridging carbamato ligands. It was found to be unreactive towards nucleophiles, while by reaction with [Ti(cp)2Cl}2] the new complex [Ti(cp)2(O2CNEt2)] has been obtained. Organic electrophiles react regioselectively at the oxygen or at the nitrogen atom of the carbamato ligand of the manganese complexes, and in the former case
化合物[的Mn(O 2 CNR 2)2 } Ñ ](R =甲基,乙基,或Pr我)已经制备通过处理[锰(CP)2 ](CP =η 5 -C 5 H ^ 5)与有机溶剂中的CO 2 -NHR 2。这些反应可能涉及加成化合物[Mn(cp)2 ]·NHR 2。在R = Et的情况下,已对加合物进行了分离和表征,并建立了空间群,晶体数据和金属连接性。N,N-二乙基氨基甲酸酯配合物的结构已通过X解析射线衍射。晶体数据:单斜晶,C 2 / c空间群,a = 18.546(3),b = 19.287(3),c = 24.877(3)Å,β= 95.38(2)°,R = 0.078。它由六聚体单元[Mn 6(O 2 CNEt 2)12 ]组成,该单元包含四个通过五聚氰胺桥接的五配位Mn原子。通过与[Ti(cp)2 Cl} 2 ]反应,新络合物[Ti(cp)2(O 2 CNEt 2)与亲核试剂无反应。)]