A Ketimide-Stabilized Palladium Nanocluster with a Hexagonal Aromatic Pd7 Core

被引:20
作者
Cook, Andrew W. [1 ]
Hrobarik, Peter [2 ]
Damon, Peter L. [1 ]
Wu, Guang [1 ]
Hayton, Trevor W. [1 ]
机构
[1] Univ Calif Santa Barbara, Dept Chem & Biochem, Santa Barbara, CA 93106 USA
[2] Comenius Univ, Fac Nat Sci, Dept Inorgan Chem, SK-84215 Bratislava, Slovakia
基金
美国国家科学基金会; 欧盟地平线“2020”;
关键词
CAPPED 3-SHELL PD-145; RAY CRYSTAL-STRUCTURE; SPECTROSCOPIC CHARACTERIZATION; STRUCTURAL-CHARACTERIZATION; ETHYLENE POLYMERIZATION; ELECTRONIC-STRUCTURE; CARBONYL CLUSTERS; CURRENT DENSITIES; COMPLEXES; TITANIUM;
D O I
10.1021/acs.inorgchem.9b03276
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Herein, we report the synthesis and characterization of the mixed-valent, ketimide-stabilized Pd-7 nanosheet, [Pd-7(N=(CBu2)-Bu-t)(6)] (1), via reaction of PdCl2(PhCN)(2) and Li(N=(CBu2)-Bu-t). (BuCN)-Bu-t, isobutylene, and isobutane are also formed in the reaction. The presence of these products suggests that Li(N=(CBu2)-Bu-t) acts as a reducing agent in the transformation, converting the Pd(II) starting material into the mixed-valent Pd(I)/Pd(0) product. Complex 1 features a hexagonal planar [Pd-7](6+) core stabilized by six ketimide ligands, which surround the [Pd-7](6+) center in an alternating up/down fashion. In situ NMR spectroscopic studies, as well as density functional theory (DFT) calculations, suggest that 1 is formed via the intermediacy of the bimetallic Pd(II) ketimide complex, [((Bu2C)-Bu-t=N)Pd(mu-N,C-N=C(Bu-t)C(Me)(CH2)-C-2)Pd(N=(CBu2)-Bu-t)] (2). DFT calculations also reveal that 1 is a rare example of an all-metal aromatic nanocluster with hexagonal symmetry, sustaining a net diatropic ring-current of 10.6 nA/T, which is similar to that of benzene (11.8 nA/T) or other well-established transition-metal aromatic systems. Finally, we have found that 1 reacts with Ph3P, cleanly forming the tris-ligated 16-electron Pd(0) phosphine complex, Pd(PPh3)(3) (3), suggesting that 1 could be a useful precatalyst for a variety of cross-coupling reactions.
引用
收藏
页码:1471 / 1480
页数:10
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