Mono‐ and Hetero‐Dinuclear Complexes of Janus‐Head NHC Ligands Possessing Backbone Phosphinoyl Groups: the Case of Soft and Hard Metal Centers
Mono‐ and Hetero‐Dinuclear Complexes of Janus‐Head NHC Ligands Possessing Backbone Phosphinoyl Groups: the Case of Soft and Hard Metal Centers
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具有主链膦酰基的 Janus 头 NHC 配体的单核和杂双核配合物：软金属和硬金属中心的情况
DOI：
10.1002/ejic.201402440
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发表时间：
2014
影响因子：
2.3
通讯作者：
R. Streubel
中科院分区：
文献类型：
--
作者：
P. K. Majhi;Spencer C. Serin;G. Schnakenburg;D. Gates;R. Streubel
报道了含4-膦酰-和4,5-二（膦酰）咪唑-2-酰基配体（NHCP）的RhI和IrI配合物的合成和结构。在[M(cod)Cl]2的存在下，KOtBu使相应的咪唑硫酸氢盐脱质子，得到式[M(cod)Cl(NHCP)] [5a/5b: NHCP = 4-Ph2P(O)- iiprme, 5a: M = Rh, 5b: M = Ir和7a/7b: NHCP = 4,5-{Ph2P(O)}2- inbume]。RhI配合物5a和7a与一氧化碳反应生成[Rh(CO)2Cl(NHCP)] 8a和9a；平均CO伸展频率[8a: (CO)av = 2036 cm-1和9a: (CO)av = 2038.4 cm-1]表明单官能化和双官能化NHCPs的供体作用相对弱于主干未取代NHC。对配合物7a的双头配体性质的初步研究表明，与TiCl4反应可得到异核10a， A '作为单齿磷酰钛（IV）异构体加合物的混合物。通过元素分析、光谱学和光谱分析等方法对产物进行了表征，并对配合物7a和7b进行了单晶x射线结构分析。
The synthesis and structures of RhI and IrI complexes bearing 4-phosphinoyl- and 4,5-bis(phosphinoyl)imidazol-2-ylidene ligands (NHCP) is reported. Deprotonation of the corresponding imidazolium hydrogen sulfate salts by KOtBu in the presence of [M(cod)Cl]2 afforded complexes of the formula [M(cod)Cl(NHCP)] [5a/5b: NHCP = 4-Ph2P(O)-IiPrMe, 5a: M = Rh, 5b: M = Ir and 7a/7b: NHCP = 4,5-{Ph2P(O)}2-InBuMe]. The RhI complexes 5a and 7a were then converted into [Rh(CO)2Cl(NHCP)] 8a and 9a via reaction with carbon monoxide; the average CO stretching frequencies [8a: (CO)av = 2036 cm–1 and 9a: (CO)av = 2038.4 cm–1] led to the conclusion that mono- and bis-functionalized NHCPs act as relatively weaker donors than backbone unsubstituted NHC. A first examination of Janus-head ligand properties of complex 7a revealed that reaction with TiCl4 afforded hetero-dinuclear 10a,a′ as a mixture of isomeric monodentate phosphinoyl titanium(IV) adducts. All products were characterized by elemental analyses, spectroscopic and spectrometric methods and, in addition, complexes 7a and 7b by single-crystal X-ray structure analysis.
使用 4-膦基取代的 NHC 配体轻松制备同二金属和异二金属配合物。
DOI：
10.1002/asia.201000856
发表时间：
2011
期刊：
Chemistry, an Asian journal
影响因子：
--
作者：
Mendoza-Espinosa,Daniel;Donnadieu,Bruno;Bertrand,Guy
通讯作者：
Bertrand,Guy