Englich Ulrich, Hassler Karl, Ruhlandt-Senge Karin, Uhlig Frank
Contribution from the Department of Chemistry, 1-014 Center for Science and Technology, Syracuse University, Syracuse, New York 13244-4100, Institut für Anorganische Chemie II, Universität Dortmund, Otto-Hahn-Strasse 6, D-44221 Dortmund, Germany, and Institut für Anorganische Chemie, Technische Universität Graz, Stremayrgasse 16, A-8010 Graz, Austria.
Inorg Chem. 1998 Jul 13;37(14):3532-3537. doi: 10.1021/ic9801950.
A series of highly reactive heavy alkali metal phosphides was prepared by treating trimethylsilyl-substituted phosphines with alkali metal tert-butyl alcoholates. The compounds are formed in excellent yield and purity, and the side product can be easily removed in a vacuum. The high synthetic potential of this reaction route was further shown by utilizing excess alkali metal tert-butyl alcoholates in reaction with silyl substituted phosphines. In all cases, only monometalated products were isolated. In the course of this work the crystal structures of the bis(trimethylsilyl)phosphides K(thf)P(SiMe(3))(2), 1a, Rb(thf)P(SiMe(3))(2), 1b, and Cs(thf)P(SiMe(3))(2), 1c, were obtained. The compounds display polymeric ladder-type structures. Compounds 1a,b are isomorphous, while compound 1c displays a slightly altered local geometry. Despite small differences in local geometry, the coordination spheres for the phosphorus atoms and the alkali metal are fairly similar. The five coordinate phosphorus atoms are connected to three alkali metal centers in addition to two trimethylsilyl groups. The alkali metals are four coordinate with ligations to three phosphorus centers in addition to one thf oxygen donor. Compounds 1a-c were characterized using elemental analysis, NMR spectroscopy, and X-ray crystallography. Crystal data with Mo Kalpha (lambda = 0.710 73 Å) at 150 K are as follows: 1a, a = 6.4261(2) Å, b = 12.4119(2) Å, c = 21.5447(4) Å, V = 1718.41(7) Å(3), Z = 4, orthorhombic, space group P2(1)2(1)2(1), 3427 independent reflections, R1 (all data) = 0.0351; 1b, a = 6.5338(2) Å, b = 12.5664(3) Å, c = 21.5537(5) Å, V = 1769.70(8) Å(3), Z = 4, orthorhombic, space group P2(1)2(1)2(1), 4195 independent reflections, R1 (all data) = 0.0776; 1c, a = 11.3515(1) Å, b = 22.3445(3) Å, c = 7.2501(1) Å, beta = 96.017(1) degrees, V = 1828.81(4) Å(3), Z = 4, monoclinic, space group P2(1)/c, 4343 independent reflections, R1 (all data) = 0.0811.
通过用碱金属叔丁醇盐处理三甲基硅基取代的膦，制备了一系列高反应活性的重碱金属磷化物。这些化合物的产率和纯度都很高，副产物在真空中很容易除去。通过在与硅基取代膦的反应中使用过量的碱金属叔丁醇盐，进一步展示了这条反应路线的高合成潜力。在所有情况下，只分离出单金属化产物。在这项工作过程中，获得了双（三甲基硅基）磷化物K(thf)P(SiMe(3))(2)，1a、Rb(thf)P(SiMe(3))(2)，1b和Cs(thf)P(SiMe(3))(2)，1c的晶体结构。这些化合物呈现出聚合物梯型结构。化合物1a、b是同构的，而化合物1c显示出局部几何结构略有改变。尽管局部几何结构存在微小差异，但磷原子和碱金属的配位球相当相似。五配位的磷原子除了与两个三甲基硅基相连外，还与三个碱金属中心相连。碱金属是四配位的，除了一个thf氧供体外，还与三个磷中心配位。使用元素分析、核磁共振光谱和X射线晶体学对化合物1a - c进行了表征。在150 K下用Mo Kalpha（λ = 0.710 73 Å）的晶体数据如下：1a，a = 6.4261(2) Å，b = 12.4119(2) Å，c = 21.5447(4) Å，V = 1718.41(7) Å(3)，Z = 4，正交晶系，空间群P2(1)2(1)2(1)，3427个独立反射，R1（所有数据）= 0.0351；1b，a = 6.5338(2) Å，b = 12.5664(3) Å，c = 21.5537(5) Å，V = 1769.70(8) Å(3)，Z = 4，正交晶系，空间群P2(1)2(1)2(1)，4195个独立反射，R1（所有数据）= 0.0776；1c，a = 11.3515(1) Å，b = 22.3445(3) Å，c = 7.2501(1) Å，β = 96.017(1)°，V = 1828.81(4) Å(3)，Z = 4，单斜晶系，空间群P2(1)/c，4343个独立反射，R1（所有数据）= 0.0811。
