Group 8 and 10 hyponitrite and dinitrosyl complexes
Group 8 and 10 hyponitrite and dinitrosyl complexes
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DOI：
10.1016/j.poly.2007.05.009
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发表时间：
2007-10-10
期刊：
影响因子：
2.6
通讯作者：
Moore, Raecca C.
中科院分区：
文献类型：
--
作者：
Arulsamy, Navamoney;Bohle, D. Scott;Moore, Raecca C.
以前已经证明，通过用sodium-(Z)-1-{4-(2，6-di-tert-butyl-4-methoxycyclohexadienonyl)}diazen-1-ium-1，2-diolate.处理相应的LnMCl2衍生物，二价金属的顺式次亚硝酸盐配合物LnM(N2O2)(M=Ni，Pt；L-n=PPh_3，PPh_2Me，dppe和dppt)很容易制备这些配合物采用抗磁性正方形平面构型，带有氧结合的平面螯合顺式次亚硝酸盐配体。它们在室温下很容易制备，但在90摄氏度以上会随着一氧化二氮的释放而热分解。亲电剂如碘、三氟化甲酯和盐酸也能迅速与顺式次硝酸盐络合物反应生成一氧化二氮。其中一种先前制备的络合物(PPh_3)(2)铂(N_2O_2)的结构已在-100℃下作为二氯甲烷溶剂重新测定，精密度提高。重新研究了相关的8-二亚硝基四面体配合物(PPh_3)(2)M(NO)(2)(M=Ru，Os；L-n=PPh_3，dppe和dppf)，并在相应的(PPh_3)(2)M(NO)(2)上进行了配体取代，合成了新的具有螯合膦的衍生物。测定了Ru(Dppf)(NO)(2)和Os(Dppe)(NO)(2)的结构。这两个类似的顺式次亚硝酸盐和二亚硝基配合物家族说明了金属d(N)电子计数和亚硝基氧化还原状态的平衡，其中一个家族的线性亚硝基与低价金属中心结合，而前者将N2O22-配体偶联到较高氧化态的金属中心。(C)2007爱思唯尔有限公司。保留所有权利。
cis-Hyponitrite complexes LnM(N2O2) (M = Ni, Pt; L-n = PPh3, PPh2Me, dppe, and dppt) of divalent group 10 metals have been previously shown to be readily prepared by treating the corresponding LnMCl2 derivatives with sodium-(Z)-1-{4-(2,6-di-tert-butyl-4-methoxycyclohexadienonyl)}diazen-1-ium-1,2-diolate. These complexes adopt a diamagnetic square planar geometry with oxygen bound chelating planar cis-hyponitrite ligands. They are readily prepared at room temperature but thermally decompose above 90 degrees C with release of nitrous oxide. Electrophiles such as iodine, methyltriflate, and hydrochloric acid also react rapidly with the cis-hyponitrite complexes to give nitrous oxide. The structure of one of these previously prepared complexes, (PPh3)(2)Pt(N2O2), has been redetermined at -100 degrees C as a dichloromethane solvate with improved precision. The related tetrahedral group 8 dinitrosyl complexes, (PPh3)(2)M(NO)(2) (M = Ru, Os; L-n = PPh3, dppe, and dppf) have been reexamined and new derivatives with chelating phosphines have been prepared by ligand substitution on the corresponding (PPh3)(2)M(NO)(2). The structures of Ru(dppf)(NO)(2) and Os(dppe)(NO)(2) have been determined. These two analogous families of cis-hyponitrite and dinitrosyl complexes illustrate the balance of metal d(n) electron count and nitrosyl redox state with one having linear nitrosyls bound to low valent metal centers, and the former having coupled N2O22- ligands bound to a higher oxidation state metal center. (c) 2007 Elsevier Ltd. All rights reserved.