北京大学-无机化学课件-有机金属化学（二）.pptVIP

第7章 有机金属化学（二） 一. 常见的有机配体和齿合度 二. 环戊二烯基(cyclopentadienyl)配合物 Common Types of Cp complexes: 若干茂金属的结构性质 (COT) Er(Cp*) (COT)ErCp* (COT)ErCp* SIM: (COT)ErCp* 有效原子数规则（Effective Atomic Number EAN规则） 配位电子+中心金属原子的价电子= 18/16 18-electron compounds Six sigma bonding interation are possible in an octahedral complex and, when pi-acceptor ligands are present, bonding combinations can be made with the three orbitals of the t2g set, leading to nine bonding MOs, and space for a total of 18 electrons. 16-electron square-planar compounds with strong-field ligands, a square-planar complex has only eight-bonding MOs, thus a 16-electron configuration is the most energetically favorable configuration. 价电子计数方法 Neutral-ligand method All ligands are treated as neutral and are categorized according to how many electrons they are considered to donate. L type: two-electron donor, CO, PMe3 X type: one-electron radical donor, Cl, H, CH3 Donor-pair method Ligands are considered to donate electrons in pairs, resulting in the need to treat some ligand as neutral and others as charged. CO, PMe3, two-electron donor, oxidation number 0 Cl-,H-,CH3-, two-electron donor, oxidation number -1 C5H5-(Cp), six-electron donor, oxidation number -1 The oxidation number of metal atom is the total charge of the complex minus the charge of any ligands. The number of electrons of metal provides is its group number minus its oxidation nummer. The total electron count is the sum of the number of electrons on the metal atom and the number of electrons provided by the ligands. 三. 卡宾(carbene)和卡拜(carbyne)化合物 四. 等瓣(isolobal) 相似 练 习 (?5–C5H5)2Mo2(?-CO)4 (?5–C5H5)2M2(CO)4 (?5–C5H5)2M2(CO)6 固体中trans 液体中trans, cis 通过非桥联羰基达到平衡 (P164-165) 讨论： 烯丙基配合物[PdC3H5Cl]2的结构和总价电子计数, 金属原子间是否存在M–M键 ? 对比 [Pt(CO)Cl2]2和[Mn(CO)4Cl]2 2. Fe2(CO)9 中Fe和 Fe之间的化学键 * In the presence of p-acceptors: D is large. t2g are bonding MOs, and prefer to be occupied. === eg* (strongly antibonding): 0 e t2g (bonding):