摘要
過渡金屬的化學與其d 軌域中的價電子息息相關，d 軌域依方向分為d_(z^2)、d_(xy)、d_(yz)、d_(xz)、d_(x^2-y^2) 這五個軌域。1964 年Cotton 鑑定出第一個雙錸金屬肆鍵錯合物[Re_2Cl_8]^(2-)，兩個錸金屬使用d_z2 軌域形成σ鍵、使用d_(xz) 及d_(yz) 軌域形成兩個π鍵、d_(xy) 軌域形成δ鍵，四個d 軌域形成四個鍵結。2005 年Power 合成出雙鉻金屬錯合物{Cr[C_6H_3-2,6-(Dipp)_2]}_2，兩個鉻金屬除了使用d_(z^2)、d_(xy)、d_(yz)、d_(xz) 軌域，形成一個σ鍵、兩個π鍵及一個δ鍵外，還用了d_(x^2-y^2) 軌域形成第二個δ鍵結，五個d 軌域形五個鍵結。此外本論文也將介紹新型雙鉬金屬參鍵錯合物syn-1,2-Mo_2Cl_2[μ-η^2-Me_2Si(NDipp)_2]_2 的合成，其為順式相蝕 (eclipsed) 類乙烷 (ethanelike) 的結構，再將其以Na/Hg 還原時，可得新型四配位雙鉬金屬肆鍵錯合物Mo_2[μ-η^2-Me_2Si(NDipp)_2]_2，這與文獻上所有的雙金屬肆鍵錯合物使用d_(xy) 軌域形成δ鍵不相同，因其金屬中心使用d_(x^2-y^2) 軌域同時和配基形成σ鍵及另一個金屬形成δ鍵，起因於基雙牙且立體障礙大的配基{Me_2Si[NLi(Dipp)]_2}_2。
並列摘要
The chemistry of transition metals are depended on the valence electrons located in the d orbitals, d_(z^2)、d_(xy)、d_(yz)、d_(xz) and d_(x^2-y^2). Cotton recognized the first quadruple bonded dirhenium complex [Re _2Cl_8]^(2-) in 1964. Two rhenium metals use four d orbitals to form four bondings, the dz2 orbital for σ bonding, dxz and dyz orbital for two π bondings, and dxy orbital for δ bonding. Power’s group reported the first dichromium complex {Cr[C_6H_3-2,6-(Dipp)_2]}_2 in 2005, with a five-fold bond between two Cr atom. The four orbitals d_(z^2)、d_(xy)、d_(yz)、d_(xz) formed 1σ, 2π, 1δ bondings, and the d_(x^2-y^2) orbital formed the second δ bonding. We also introduce the synthesis of new type of triply bonded di-molybdenum complex syn-1,2-Mo_2Cl_2[μ-η^2-Me_2Si (NDipp)_2]_2, which were ethane-like eclipsed syn conformation. Reduction of syn-1,2-Mo_2Cl_2[μ-η^2-Me_2Si (NDipp)_2]_2 by Na/Hg afforded the new type of four coordinated di-molybdenum quadruply bonded complex Mo_2[μ-η^2-Me_2Si(NDipp)_2]_2. Differ from others, it use d_(x^2-y^2) orbital to form both M-L σ bonds and M-M δ bond, which due to the large hindered ligand {Me_2Si[NLi(Dipp)]_2}_2.