Zhang Q F, Zheng H, Wong W Y, Wong W T, Leung W H
Department of Chemistry, Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, People's Republic of China, China.
Inorg Chem. 2000 Nov 13;39(23):5255-64. doi: 10.1021/ic000291c.
Reactions of coordinatively unsaturated Ru[N(Ph2PQ)2]2(PPh3) (Q = S (1), Se (2)) with pyridine (py), SO2, and NH3 afford the corresponding 18e adducts Ru[N(Ph2PQ)2]2(PPh3)(L) (Q = S, L = NH3 (5); Q = Se, L = py (3), SO2 (4), NH3 (6)). The molecular structures of complexes 2 and 6 are determined. The geometry around Ru in 2 is pseudo square pyramidal with PPh3 occupying the apical position, while that in 6 is pseudooctahedral with PPh3 and NH3 mutually cis. The Ru-P distances in 2 and 6 are 2.2025(11) and 2.2778(11) A, respectively. The Ru-N bond length in 6 is 2.185(3) A. Treatment of 1 or 2 with substituted hydrazines L or NH2OH yields the respective adducts Ru[N(Ph2PQ)2]2(PPh3)(L) (Q = S, L = NH2NH2 (12), t-BuNHNH2 (14), l-aminopiperidine (C5H10NNH2) (15); Q = Se, L = PhCONHNH2 (7), PhNHNH2 (8), NH2OH (9), t-BuNHNH2 (10), C5H10NNH2 (11), NH2NH2 (13)), which are isolated as mixtures of their trans and cis isomers. The structures of cis-14 and cis-15 are characterized by X-ray crystallography. In both molecular structures, the ruthenium adopts a pseudooctahedral arrangement with PPh3 and hydrazine mutually cis. The Ru-N bond lengths in cis-14.CH2Cl2 and cis-15 are 2.152(3) and 2.101(3) A, respectively. The Ru-N-N bond angles in cis-14.CH2Cl2 and cis-15 are 120.5(4) and 129.0(2) degrees, respectively. Treatment of 1 with hydrazine monohydrate leads to the isolation of yellow 5 and red trans-Ru[N(Ph2PS)2]2(NH3)(H2O) (16), which are characterized by mass spectrometry, 1H NMR spectroscopy, and elemental analyses. The geometry around ruthenium in 16 is pseudooctahedral with the NH3 and H2O ligands mutually trans. The Ru-O and Ru-N bond distances are 2.118(4) and 2.142(6) A, respectively. Oxidation reactions of the above ruthenium hydrazine complexes are also studied.
配位不饱和的Ru[N(Ph₂PQ)₂]₂(PPh₃)（Q = S (1)，Se (2)）与吡啶（py）、SO₂和NH₃反应生成相应的18电子加合物Ru[N(Ph₂PQ)₂]₂(PPh₃)(L)（Q = S，L = NH₃ (5)；Q = Se，L = py (3)，SO₂ (4)，NH₃ (6)）。测定了配合物2和6的分子结构。2中Ru周围的几何构型为假四方锥，PPh₃占据顶端位置，而6中的为假八面体，PPh₃和NH₃相互呈顺式。2和6中Ru - P的距离分别为2.2025(11) Å和2.2778(11) Å。6中Ru - N键长为2.185(3) Å。用取代肼L或NH₂OH处理1或2得到各自的加合物Ru[N(Ph₂PQ)₂]₂(PPh₃)(L)（Q = S，L = NH₂NH₂ (12)，t - BuNHNH₂ (14)，1 - 氨基哌啶（C₅H₁₀NNH₂）(15)；Q = Se，L = PhCONHNH₂ (7)，PhNHNH₂ (8)，NH₂OH (9)，t - BuNHNH₂ (10)，C₅H₁₀NNH₂ (11)，NH₂NH₂ (13)），它们以反式和顺式异构体的混合物形式分离出来。顺式 - 14和顺式 - 15的结构通过X射线晶体学表征。在这两种分子结构中，钌采用假八面体排列，PPh₃和肼相互呈顺式。顺式 - 14·CH₂Cl₂和顺式 - 15中Ru - N键长分别为2.152(3) Å和2.101(3) Å。顺式 - 14·CH₂Cl₂和顺式 - 15中Ru - N - N键角分别为120.5(4)°和129.0(2)°。用一水合肼处理1导致分离出黄色的5和红色的反式 - Ru[N(Ph₂PS)₂]₂(NH₃)(H₂O) (16)，通过质谱、¹H NMR光谱和元素分析对其进行了表征。16中钌周围的几何构型为假八面体，NH₃和H₂O配体相互呈反式。Ru - O和Ru - N键距离分别为2.118(4) Å和2.142(6) Å。还研究了上述钌肼配合物的氧化反应。
