...
首页> 外文期刊>Journal of Organometallic Chemistry >New Ni-Rh carbonyl clusters with unprecedented structural and electronic features:synthesis and X-ray structure of [NEt_4]_3[Ni_(10)Rh(CO)_(19)] centre dot C_2H_5CN,[NMe_3CH_2Ph]_3[Ni_6Rh_3(CO)_(17)] and [NEt_4]_3[NiRh_3(CO)_(22)]
【24h】

New Ni-Rh carbonyl clusters with unprecedented structural and electronic features:synthesis and X-ray structure of [NEt_4]_3[Ni_(10)Rh(CO)_(19)] centre dot C_2H_5CN,[NMe_3CH_2Ph]_3[Ni_6Rh_3(CO)_(17)] and [NEt_4]_3[NiRh_3(CO)_(22)]

机译:具有前所未有的结构和电子特征的新型Ni-Rh羰基簇:[NEt_4] _3 [Ni_(10)Rh(CO)_(19)]中心点C_2H_5CN,[NMe_3CH_2Ph] _3 [Ni_6Rh_3(CO)的合成和X射线结构)_(17)]和[NEt_4] _3 [NiRh_3(CO)_(22)]

获取原文
获取原文并翻译 | 示例
           

摘要

The reaction of the rNi6(CO)1J2 dianion with [Rh(COD)Cl]2 (COD = cyclooctadiene) affords in sequence the [Ni10Rh(CO)19]3 — (1) and [Ni9Rh3(CO)2J3 — (2) trianionic clusters with good selectivity. The related [Ni6Rh3(CO)1713 —trianionic cluster has been initially isolated among the degradation products of [Ni9Rh3(CO)2J3 (2) under carbon monoxide has been more conveniently synthesized by condensation of [Rh(CO)4— with Ni(CO)4 in excess. All these new bimetallic Ni carbonyl clusters have been isolated in the solid state as tetrasubstituted animonium salts and were characterized by elem analysis, spectroscopy and X-ray diffraction studies. The structure of [Ni10Rh(CO)19]3 (1) consists of a distorted and incomp Rh-centered Ni9(p~-Rh) icosahedral moiety, capped by the tenth Ni atom on one of the interlayer triangular faces. [Ni10Rh(CO)19]3 — (1) trianion is moderately stable to oxidation and, as inferable from IR monitoring of the resulting reac mixture, is irreversibly degraded upon exposure to an atmosphere of carbon monoxide to a mixture of Ni(CO)4, [Rh(CO)4] -[Ni5(CO)1212 —. The [Ni9Rh3(CO)2j3 (2) trianion displays a three layer metal frame identical to that previously found in ti~ [H4 rNj9Pt3(CO)2i]~ — (x = 2—4) clusters. However, it features two less valence electrons. The structure of [Ni6Rh3(CO),7]3 —is closely related to that of [Ni9Rh3(CO)2j3 — (2) and may be formally derived from that of the latter by substitution of. Ni3(CO)3(p-CO)3 moiety with a face bridging carbonyl group. Notably, [Ni6Rh3(CO)17]3 — (3) is isoelectronic but not isostructu.rd with the known [Ni6Ir3(CO)1713 — congener. Both [Ni6Rh3(CO),4’ (3) and [Ni9Rh3(CO)2j3 — (2) are readily degraded by carb~ monoxide at atmospheric pressure to colourless solutions containing Ni(CO)4 and [Rh(CO)4] mixtures. Their reaction with [Rh(COD)Cl]2 leads to the previously reported [Ni6Rh5(CO)21]3 trianion and other yet uncharacterised Ni—Rh carbonyl clusters.. All above Ni—Rh clusters do not display protonation—deprotonation behaviour and chemically reversible redox propensity; electrochemical experiments failed in all cases to show the occurrence of electrochemically reversible redox changes.
机译:rNi6(CO)1J2二价阴离子与[Rh(COD)Cl] 2(COD =环辛二烯)的反应依次提供[Ni10Rh(CO)19] 3-(1)和[Ni9Rh3(CO)2J3-(2 )具有良好选择性的三阴离子簇。最初在[Ni9Rh3(CO)2J3(2)的降解产物中,分离出了相关的[Ni6Rh3(CO)1713-三价离子簇],通过[Rh(CO)4-与Ni( CO)4过量。所有这些新的双金属Ni羰基镍新金属簇均以四取代的imo盐形式被分离出来,并通过元素分析,光谱学和X射线衍射研究对其进行了表征。 [Ni10Rh(CO)19] 3(1)的结构由一个扭曲且不完整的Rh中心Ni9(p〜-Rh)二十面体部分组成,在一个层间三角形面上被第十个Ni原子封端。 [Ni10Rh(CO)19] 3-(1)三价阴离子对氧化具有中等稳定性,并且从红外监测所得反应混合物可推断出,三价阴离子在暴露于一氧化碳气氛中时会不可逆地降解为Ni(CO)混合物4,[Rh(CO)4]-[Ni 5(CO)1212-。 [Ni9Rh3(CO)2j3(2)三价阴离子显示三层金属框架,该框架与先前在[〜H4 rNj9Pt3(CO)2i]-(x = 2-4)簇中发现的金属框架相同。但是,它的特征是两个价电子少。 [Ni6Rh3(CO),7] 3-的结构与[Ni9Rh3(CO)2j3-(2)的结构密切相关,并且可以通过取代而从后者的形式上正式衍生出来。具有羰基面的Ni3(CO)3(p-CO)3部分。值得注意的是,[Ni6Rh3(CO)1713-]是等电的,但不是同构的。 [Ni6Rh3(CO),4'(3)和[Ni9Rh3(CO)2j3-(2)都容易在大气压下被一氧化碳降解为含有Ni(CO)4和[Rh(CO)4]的无色溶液。混合物。它们与[Rh(COD)Cl] 2的反应导致先前报道的[Ni6Rh5(CO)21] 3三阴离子和其他尚未表征的Ni-Rh羰基簇。所有以上的Ni-Rh簇均未显示质子化-去质子化行为,化学可逆的氧化还原倾向;电化学实验在所有情况下均失败,未能证明发生了电化学可逆的氧化还原变化。

著录项

相似文献

  • 外文文献
获取原文

客服邮箱:kefu@zhangqiaokeyan.com

京公网安备:11010802029741号 ICP备案号:京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有
  • 客服微信

  • 服务号