中级无机化学北大10年第7章有机金属化学2.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 若干茂金属的结构性质 Dy(COT)(Cp*) 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 ste, 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 ?接受体 卡宾(Fischer型) 配合物的成键 卡宾(Fischer)配合物（金属低氧化态） C亲电 卡宾(Schrock)配合物（金属高氧化态） C亲核 Ta的茂基, 甲基, 亚甲基化合物 TaCp*2(CH2)(CH3) Carbyne配合物 Alkylidyne （ ?CR ）次烷基配合物 3电子给体 卡宾化合物 卡拜化合物 Carbene 和 Carbyne的配合物 （等叶片相似） 分子片（molecular fragments) 的前线轨道和成键行为相似 CH3 Mn(CO)5 有机分子片 无机分子片 H—CH3 H—Mn(CO)5 H3C—CH3 (CO)5Mn—