Carbene complexes. Part 14. The synthesis and steric and electronic effects in electron-rich olefin-derived bis-, tris-, and tetrakis-(carbene)-ruthenium(II) and a tetrakis(carbene)osmium(II) complex; the crystal and molecular structure of trans-dichiorotetrakis(1,3-diethylimidazo-lidin-2-ylidene)ru
Carbene complexes. Part 14. The synthesis and steric and electronic effects in electron-rich olefin-derived bis-, tris-, and tetrakis-(carbene)-ruthenium(II) and a tetrakis(carbene)osmium(II) complex; the crystal and molecular structure of trans-dichiorotetrakis(1,3-diethylimidazo-lidin-2-ylidene)ru
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卡宾配合物。
DOI：
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发表时间：
1978
期刊：
影响因子：
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通讯作者：
P. Pye
中科院分区：
文献类型：
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作者：
P. Hitchcock;M. Lappert;P. Pye
[RuCl 2（PPh 3）3]与[[省略图示]R]2（LR 2; R = Me、Et或CH 2 Ph）反应得到tans-[RuCl 2（LR）4][R = Me（1）、Et（Z）或CH 2 Ph（3）]。这些配合物的不稳定性和反应活性按（3）<（1）<（2）的顺序增加。因此，在CH 2Cl中，络合物（2）容易失去LEt得到[RuCl 2（LEt）3]（13），但（1）需要长时间加热以获得类似的LMe损失，得到[RuCl 2（LMe）3]（12），并且（3）不反应。配合物（1）（i）在与NaI反应时失去LMe以形成[Rul 2（LMe）3]（4），（ii）与过量的P（OMe）3反应以得到[RuCl（LMe）2-{P（OMe）3}3]Cl（14）。和（iii）在CO存在下与C5 H5 N反应得到trans-[Ru（CO）Cl（LMe），（NC 5 H5）2]Cl（16）。一氧化碳从络合物（1）中置换Cl-，得到trans-[Ru（CO）Cl（LMe）4]Cl（9），但（2）优先消除LEt，形成trans-[Ru（CO）Cl 2（LEt）3]（7），其在CHCl 3或CH 2Cl 2中异构化为顺式异构体（8），苄基衍生物（3）不反应。配合物（1）与PF_3形成反式-[RuCl（LMe）_4-（PF_3）] Cl（10），它表现出严重的空间拥挤和卡宾配体的受限旋转，正如通过分析它们的~ 1H和~（13）C n.m.r.谱配合物mer-[OsCl_3（PBun 1 Ph）_3]与烯烃LMe_2反应生成反式-[OsCl_2（LMe）_4]。标题配合物的X射线晶体结构测定（以其0.50Bun 2溶剂化物形式）已精制至R 0.055（R′ 0.087）对2641个独立反射的MO-Kα辐射测量结果表明：该分子具有近D4对称性，在赤道面内金属、反式氯原子和四个卡宾配体以规则的八面体配位，呈螺旋桨式排列;每个几乎平面的咪唑烷环以α角排列。与RuC 4赤道平面成45 °。鲁卡布距离为2.105（5）A，Ru-Cl为2.459（4）A。晶体为单斜晶系，a= 19.076（2），B= 13.409（1），c= 14.952（2）A，β= 102.85（6）°，Z= 4，空间群P21/c（No.14）。
The reaction of [RuCl2(PPh3)3] with [[graphics omitted]R]2(LR2; R Me, Et, or CH2Ph) affords tans-[RuCl2(LR)4][R = Me (1), Et (Z), or CH2Ph (3)]. The instability and reactivity of these complexes increases in the order (3) < (1) < (2). Thus in CH2Cl, complex (2) readily loses LEt to give [RuCl2(LEt)3](13), but (1) requires pro-longed heating for similar LMe loss, affording [RuCl2(LMe)3](12), and (3) does not react. Complex (1)(i) loses LMe on reaction with NaI to form [Rul2(LMe)3](4), (ii) reacts with excess of P(OMe)3 to give [RuCl(LMe)2–{P(OMe)3}3]Cl (14). and (iii) reacts with C5H5N in the presence of CO to give trans-[Ru(CO)Cl(LMe),(NC5H5)2]Cl (16). Carbon monoxide displaces Cl– from complex (1) to give trans-[Ru(CO)Cl(LMe)4]Cl (9), but (2) preferentially eliminates LEt forming trans-[Ru(CO)Cl2(LEt)3](7) which isomerises in CHCl3 or CH2Cl2, to the, cis isomer (8), and the benzyl derivative (3) does not react. With PF3 complex (1) forms trans-[RuCl(LMe)4–(PF3)] Cl (10) which exhibits severe steric crowding and restricted rotation of the carbene ligands, as is also shown for the tris- or tetrakis-(carbene) ruthenium(II) complexes derived from LEt or LCH2Ph ligands, by analysis of their 1H and 13C n.m.r. spectra. The complex mer-[OsCl3(PBun1Ph)3] and the olefin LMe2 give trans-[OsCl2(LMe)4]. An X-ray crystal structure determination of the title complex (as its 0.50Bun2 solvate) has been refined to R 0.055 (R′ 0.087) for 2 641 independent reflections measured with MO-Kα radiation: the molecule has nearly D4 sym-metry, with regular octahedral co-ordination about the metal, trans-chlorine atoms, and the four carbene ligands in a propeller arrangement in the equatorial plane; each almost planar imidazolidine ring is arranged at an angle of ca. 45 ° to the RuC4 equatorial plane. The Ru–Ccarb. distance is 2.105(5)A and Ru-Cl is 2.459(4)A. Crystals are monoclinic with a= 19.076(2), b= 13.409(l), c= 14.952(2)A, β= 102.85(6)°, Z= 4, and space group P21/c(No. 14).