含磷雙牙、三牙配子錳金屬羰基錯合物之合成及結構研究－[Mn2(CO)8(dppe)], [Mn2(CO)8(cis-vpp)],

Abstract

[Mn2(CO)10]與含磷雙牙配子dppm (dppm = Ph2PCH2PPh2)、dppe (dppe = Ph2P(CH2)2PPh2)、cis-vpp (cis-vpp = cis-Ph2PCHCHPPh2)、dppp (dppp = Ph2P(CH2)3PPh2)、dppb (dppb = Ph2P(CH2)4PPh2)及三牙配子tdppme (tdppme = MeC(CH2PPh2)3)反應，分別生成七個配位化合物[Mn2(CO)8(dppe)](1)、[Mn2(CO)8(cis-vpp)](2)、[Mn(CO)3(dppm)Cl](3)、[Mn(CO)3(cis-vpp)Cl](4)、[Mn(CO)3(dppp)Cl](5)、[Mn(CO)3(dppb)Cl](6)和[Mn(CO)3(η2-tdppme oxide)Cl](7)。其中以化學氧化法製得(1)、(2)、(4)、(5)、(6)和(7)，以熱裂法製得(3)、(4)、(5)和(6)。七個配位化合物皆以紅外線光譜初步鑑定，並以X射線單晶繞射的方法解析晶體結構。 黃色錯合物(1)之晶體屬單斜晶系，空間群C2/c，a = 23.0393(5)Å，b = 9.1227(2)Å，c = 18.1353(5)Å，β = 110.7326(8)°，最後Rf = 0.049(3343個繞射點)。以二個Mn金屬為八面體中心形成交錯型的雙八面體，其中Mn金屬各有一個羰基被dppe的磷所取代。 黃色錯合物(2)之晶體屬三斜晶系，空間群P¯1，a = 12.0256(3)Å，b = 12.1979(4) Å，c = 13.1346(4)Å，α = 90.011(1)°，β = 64.920(2)°，γ = 71.673(1)°，最後Rf = 0.053(5151個繞射點)。以二個Mn金屬為八面體中心形成交錯型的雙八面體，其中Mn金屬各有一個羰基被cis-vpp的磷所取代。 黃色錯合物(3)之晶體屬單斜晶系，空間群P21/n，a = 10.0391(1)Å，b = 22.4917(3)Å，c = 25.1645(4)Å，β = 98.7749(5)°，最後Rf = 0.055 (7261個繞射點)。起始物[Mn2(CO)10]之Mn-Mn鍵斷裂，並與氯反應形成八面體結構。其中二個末端羰基被dppm的二個磷所取代。 黃色錯合物(4)之晶體屬立方晶系，空間群Fdd2，a = 26.9295(6)Å，b = 43.166(1) Å，c = 9.2372(2)Å，最後Rf = 0.048(2633個繞射點)。起始物[Mn2(CO)10]之Mn-Mn鍵斷裂，並與氯反應形成八面體結構。其中二個末端羰基被cis-vpp的二個磷所取代。 黃橘色錯合物(5)之晶體屬單斜晶系，空間群P21/n，a = 10.107(3)Å，b = 20.780(3)Å，c = 13.909(4)Å，β = 105.84(2)°，最後Rf = 0.036 (4047個繞射點)。起始物[Mn2(CO)10]之Mn-Mn鍵斷裂，並與氯反應形成八面體結構。其中二個末端羰基被dppp的二個磷所取代。 橘色錯合物(6)之晶體屬單斜晶系，空間群P21/n，a = 11.924(3)Å，b = 15.149(5)Å，c = 16.531(6)Å，β = 105.52(2)°，最後Rf = 0.046 (2165個繞射點)。起始物[Mn2(CO)10]之Mn-Mn鍵斷裂，並與氯反應形成八面體結構。其中二個末端羰基被dppb的二個磷所取代。 橘色錯合物(7)之晶體屬單斜晶系，空間群P21/n，a = 9.893(2)Å，b = 23.271(4)Å，c = 17.853(4)Å，β = 106.22(2)°，最後Rf = 0.054 (4657個繞射點)。起始物[Mn2(CO)10]之Mn-Mn鍵斷裂，並與氯反應形成八面體結構。其中二個末端羰基被tdppme的二個磷所取代。而tdppme的第三個磷則是被氧化。

The reactions of [Mn2(CO)10] with bidentate phosphines dppm (dppm = Ph2PCH2PPh2), dppe (dppe = Ph2P(CH2)2PPh2), cis-vpp (cis-vpp = cis-Ph2PCHCHPPh2), dppp (dppp = Ph2P(CH2)3PPh2), and dppb (dppb = Ph2P(CH2)4PPh2) and tridentate phosphine tdppme (tdppme = MeC(CH2PPh2)3), yield the following seven complexes: [Mn2(CO)8(dppe)](1), [Mn2(CO)8(cis-vpp)](2), [Mn(CO)3(dppm)Cl](3), [Mn(CO)3(cis-vpp)Cl](4), [Mn(CO)3(dppp)Cl](5), [Mn(CO)3(dppb)Cl](6) and [Mn(CO)3(η2-tdppme oxide)Cl](7), respectively complexes (1), (2), (4), (5), (6) and (7) were prepared by chemical oxidation method with TMNO as an initiator at 25℃. Complexes (3), (4), (5) and (6) were also synthesized by thermolytic method. These products have been characterized by infrared spectra, and their crystal structures have been determined by X-ray diffraction analyses. The yellow crystal of (1) crystallized in monoclinic lattice, space group C2/c, a = 23.0393(5)Å, b = 9.1227(2)Å, c = 18.1353(5)Å, β = 110.7326(8)°, final Rf = 0.049 for 3343 observed reflections. Complex (1) contains two Mn centers with staggered conformation, and two carbonyl ligands are substituted by two phosphorous atoms of the dppe ligand. The yellow crystal of (2) crystallized in triclinic lattice, space group P¯1, a = 12.0256(3)Å, b = 12.1979(4)Å, c = 13.1346(4)Å, α = 90.011(1)°, β = 64.920(2)°, γ = 71.673(1)°, final Rf = 0.053 for 5151 observedreflections. Complex (2) contains two Mn centers with staggered conformation, and two carbonyl ligands are substituted by two phosphorous atoms of the cis-vpp ligand. The yellow crystal of (3) crystallized in monoclinic lattice, space group P21/n, a = 10.0391(1)Å, b = 22.4917(3)Å, c = 25.1645(4)Å, β = 98.7749(5)°, final Rf = 0.055 for 7261 observed reflections. The Mn atom is octahedrally coordinated by three carbonyl ligands, two phosphorous of dppm, and a chloride. The yellow crystal of (4) crystallized in orthorhombic lattice, space group Fdd2, a = 26.9295(6)Å, b = 43.166(1)Å , c = 9.2372(2)Å, final Rf = 0.048 for 2633 observed reflections. The Mn atom is octahedrally coordinated by three carbonyl ligands, two phosphorous of cis-vpp, and a chloride. The yellow-orange crystal of (5) crystallized in monoclinic lattice, space group P21/n, a = 10.107(3)Å, b = 20.780(3)Å, c = 13.909(4)Å, and β = 105.84(2)°, final Rf = 0.036 for 4047 observed reflections. The Mn atom is octahedrally coordinated by three carbonyl ligands, two phosphorous of dppp, and a chloride. The orange crystal of (6) crystallized in monoclinic lattice, space group P21/n, a = 11.924(3)Å, b = 15.149(5)Å, c = 16.531(6)Å, and β = 105.52(2)°, final Rf = 0.046 for 2165 observed reflections. The Mn atom is octahedrally coordinated by three carbonyl ligands, two phosphorous of dppb, and a chloride. The orange crystal of (7) crystallized in monoclinic lattice, space group P21/n, a = 9.893(2)Å, b = 23.271(4)Å, c = 17.853(4)Å, β = 106.22(2)°, final Rf = 0.054 for 4657 observed reflections. The Mn atom is octahedrally coordinated by three carbonyl ligands, two phosphorous of tdppme, and a chloride.