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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Proton induced P-H and Mo-H bond activation at the phosphide bridged dimolybdenum complexes [Mo_2Cp_2(mu-H)(mu-PHR)(CO)_4] (R = Cy,2,4,6-C_6H_2R'_3;R' = H,Me,~tRu)
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Proton induced P-H and Mo-H bond activation at the phosphide bridged dimolybdenum complexes [Mo_2Cp_2(mu-H)(mu-PHR)(CO)_4] (R = Cy,2,4,6-C_6H_2R'_3;R' = H,Me,~tRu)

机译：质子诱导的磷桥接的二钼配合物[Mo_2Cp_2（mu-H）（mu-PHR）（CO）_4]引起的PH和Mo-H键活化（R = Cy，2,4,6-C_6H_2R'_3; R'= H，Me，〜tRu）

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摘要

The new hydride complexes [Mo_2Cp_2(mu-H)(mu-PHR)(CO)_4] having bulky substituents (R = 2,4,6-C_6H_2~tBu_3 = Mes~*,R = 2,4,6-C_6H_2Me_3 = Mes) have been prepared in good yield by addition of Li[PHR] to the triply bonded [Mo_2Cp_2(CO)_4] and further protonation of the resulting anionic phosphide complex [Mo_2Cp_2(mu-PHR)(CO)_4]~-.Protonation of the Mes~* compound with either [H(OEt_2)_2][B{3,5-C_6H_3(CF_3)_2}.4] or HBF_4-OEt_2 gives the cationic phosphinidene complex [Mo_2Cp_2(mu-H)(mu-PMes~*)(CO)_4]~- in high yield.In contrast,protonation of the analogous hydride compounds with Mes or Cy substituents on phosphorus give the corresponding unsaturated tetracarbonyls [Mo_2Cp_2(mu-PHR)(CO)_4]~+,which are unstable at room temperature and display a cis geometry.Decomposition of the latter give the electron-precise pentacarbonyls [Mo_2Cp_2(mu-PHR)(mu-CO)(CO)_4]~+,also displaying a cis arrangement of the metal fragments.In the presence of BF_4~- as external anion,fluoride abstraction competes with carbonylation to yield the neutral fluorophosphide hydrides [Mo_2Cp_2(mu-H)(mu-PFR)(CO)_4].Similar results were obtained in the protonation reactions of the hydride compounds having a Ph substituent on phosphorus.In that case,using HC1 as protonation reagent gave the chloro-complex [Mo_2ClCp_2(mu-PHPh)(CO)_4] in good yield.The structures and dynamic behaviour of the new compounds are analyzed on the basis of solution IR and ~1H,~(3I)P,~(19)F and ~(13)C NMR data as well as the X-ray studies carried out on [Mo_2Cp_2(mu-H)(mu-PHMes)(CO)_4] (cis isomer),[Mo_2Cp_2(mu-H)(mu-PFMes)(CO)_4] (trans isomer),[Mo_2Cp_2(mu-PHCy)(mu-CO)(CO)_4](BF_4) and [Mo_2ClCp_2(mu-PHPh)(CO)_4].
机译：具有庞大取代基的新氢化物配合物[Mo_2Cp_2（mu-H）（mu-PHR）（CO）_4（R = 2,4,6-C_6H_2〜tBu_3 = Mes〜*，R = 2,4,6-C_6H_2Me_3通过向三键结合的[Mo_2Cp_2（CO）_4]中添加Li [PHR]并进一步质子化生成的阴离子磷化物络合物[Mo_2Cp_2（mu-PHR）（CO）_4]〜-，可以高收率制备Mes）。用[H（OEt_2）_2] [B {3,5-C_6H_3（CF_3）_2} .4]或HBF_4-OEt_2对Mes〜*化合物进行质子化，得到阳离子次膦化合物[Mo_2Cp_2（mu-H）（ mu-PMes〜*）（CO）_4]-。相比之下，磷上带有Mes或Cy取代基的类似氢化物的质子化得到相应的不饱和四羰基[Mo_2Cp_2（mu-PHR）（CO）_4] 〜+，其在室温下不稳定并显示出顺式几何形状。后者的分解产生了电子精确的五羰基[Mo_2Cp_2（mu-PHR）（mu-CO）（CO）_4]〜+，也显示出顺式排列在作为外部阴离子的BF_4〜-存在下，氟化物的抽象与通过羰基化反应可制得中性氟化物氢化物[Mo_2Cp_2（mu-H）（mu-PFR）（CO）_4]。在磷上具有Ph取代基的氢化物化合物的质子化反应中也获得了相似的结果。 HCl为质子化剂，氯代[Mo_2ClCp_2（mu-PHPh）（CO）_4]收率良好。在IR和〜1H，〜（3I）溶液的基础上分析了新化合物的结构和动力学行为。 P，〜（19）F和〜（13）C NMR数据以及对[Mo_2Cp_2（mu-H）（mu-PHMes）（CO）_4]（顺式异构体），[Mo_2Cp_2 （mu-H）（mu-PFMes）（CO）_4]（反式异构体），[Mo_2Cp_2（mu-PHCy）（mu-CO）（CO）_4]（BF_4）和[Mo_2ClCp_2（mu-PHPh）（CO ）_4]。

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