The first trimetallic Pd/Tl/Co carbonyl cluster, trigonal [Pd9{mu3-TlCo(CO)3L}(mu2-CO)6(mu3-CO)3L6]: ligand-stabilization of the trigonal-bipyramidal [TlCo(CO)3L] entity.
The first trimetallic Pd/Tl/Co carbonyl cluster, trigonal [Pd9{mu3-TlCo(CO)3L}(mu2-CO)6(mu3-CO)3L6]: ligand-stabilization of the trigonal-bipyramidal [TlCo(CO)3L] entity.
复制标题
第一个三金属 Pd/Tl/Co 羰基簇，三角 [Pd9{mu3-TlCo(CO)3L}(mu2-CO)6(mu3-CO)3L6]：三角双锥体 [TlCo(CO) 的配体稳定性
DOI：
10.1002/anie.200461124
复制
发表时间：
2005
期刊：
影响因子：
--
通讯作者：
Dahl,LawrenceF
中科院分区：
文献类型：
--
作者：
Mednikov,EvgueniG;Fry,CharlesG;Dahl,LawrenceF
在我们探索钯的羰基/膦簇与铊 (i) 配合物的反应性的过程中，[1] 我们分离出了大约 40% 的产率），并通过晶体学和光谱表征了一个显着的 11 金属原子伪 C3v 簇，[Pd9 {μ3-TlCo-(CO) 3L}(μ2-CO) 6 (μ3-CO) 3L6],(L= PEt3)(1)，由[Pd4 (CO) 5L4](2) 和/或[Pd10 (CO) 12L6](3) 与[TlCo (CO) 4] 反应得到。其不寻常的固态分子几何形状是通过低温 X 射线衍射研究确定的。簇 1 提供了铊 (i) 的三角双锥体 [TlCo (CO) 3L] 实体的第一个晶体学实例，其在 1 中通过三钯配位作为配体稳定；否则会不稳定。 [TlCo (CO) 4] 唯一的其他分离的非亚磷酸酯 L 衍生物是 [TlCo (CO) 3P-Ph3],[2a]，但即使是这种分子铊 (i) 产品也很容易歧化成铊 (iii)[Tl {Co-(CO) 3PPh3} 3] 和铊金属。 [2]光谱测量包括多核 NMR（205,203 Tl、31P、13C、1H）研究以及固态/溶液红外和紫外/可见光谱，提供了有关溶液中整个 [TlCo (CO) 3PEt3] 配体 1 的动态行为的深入见解。四羰基钴酸铊 (i) 最初于 1942 年 [3a] 和 30 年制备后来 Robinson 及其同事 [3b, c] 将其可靠地引入合成有机金属化学中，作为“四羰基钴酸根阴离子的一种方便且通用的来源”。他们还通过 X 射线衍射表明
In the course of our exploration of reactivities of carbonyl/phosphine clusters of palladium with thallium (i) complexes,[1] we have isolated approximately 40% yield) and crystallographically and spectroscopically characterized a remarkable 11-metal-atom pseudo-C3v cluster,[Pd9 {μ3-TlCo-(CO) 3L}(μ2-CO) 6 (μ3-CO) 3L6],(L= PEt3)(1), from reactions of [Pd4 (CO) 5L4](2) and/or [Pd10 (CO) 12L6](3) with [TlCo (CO) 4]. Its unusual solid-state molecular geometry was ascertained from a low-temperature X-ray diffractometry study. Cluster 1 furnishes the first crystallographic example of a trigonal-bipyramidal [TlCo (CO) 3L] entity of thallium (i) which in 1 is stabilized as a ligand by tripalladium coordination; otherwise it would be unstable. The only other isolated non-phosphite L derivative of [TlCo (CO) 4] is [TlCo (CO) 3P-Ph3],[2a] but even this molecular thallium (i) product was found to readily disproportionate into thallium (iii)[Tl {Co-(CO) 3PPh3} 3] and thallium metal.[2] Spectroscopic measurements including a multinuclear NMR (205,203 Tl, 31P, 13C, 1H) investigation coupled with solid-state/solution IR and UV/Vis spectra have provided considerable insight concerning the indicated dynamic behavior of the entire [TlCo (CO) 3PEt3] ligand of 1 in solution.Thallium (i) tetracarbonylcobaltate was initially prepared in 1942 [3a] and 30 years later reliably introduced in synthetic organometallic chemistry by Robinson and co-workers [3b, c] as “a convenient and versatile source of the tetracarbonylcobaltate anion.” They also showed from an X-ray diffraction