Zhang Lutao, Christie Francesca A, Tarcza Anna E, Lancaster Helena G, Taylor Laurence J, Bühl Michael, Malkina Olga L, Woollins J Derek, Carpenter-Warren Cameron L, Cordes David B, Slawin Alexandra M Z, Chalmers Brian A, Kilian Petr
EaStChem School of Chemistry, University of St. Andrews, St. Andrews KY16 9ST, Fife, U.K.
Institute of Wolfberry Science, Ningxia Academy of Agriculture and Forestry Sciences, Yinchuan 750002, China.
Inorg Chem. 2023 Oct 2;62(39):16084-16100. doi: 10.1021/acs.inorgchem.3c02255. Epub 2023 Sep 18.
A series of -substituted acenaphthene-based phosphine selenoether bidentate ligands Acenap(PrP)(SeAr) (-, Acenap = acenaphthene-5,6-diyl, Ar = Ph, mesityl, 2,4,6-trisopropylphenyl and supermesityl) were prepared. The rigid acenaphthene framework induces a forced overlap of the phosphine and selenoether lone pairs, resulting in a large magnitude of through-space coupling, ranging from 452 to 545 Hz. These rigid ligands - were used to prepare a series of selected late d-block metals, mercury, and borane complexes, which were characterized, including by multinuclear NMR and single-crystal X-ray diffraction. The Lewis acidic motifs (BH, Mo(CO), Ag, PdCl, PtCl, and HgCl) bridge the two donor atoms (P and Se) in all but one case in the solid-state structures. Where the bridging motif contained NMR-active nuclei (B, Ag, Ag, Pt, and Hg), and couplings are observed directly, in addition to the altered in the respective NMR spectra. The solution NMR data are correlated with single-crystal diffraction data, and in the case of mercury(II) complexes, they are also correlated with the solid-state NMR data and coupling deformation density calculations. The latter indicate that the through-space interaction dominates in free , while in the complex, the main coupling pathway is via the metal atom and not through the carbon framework of the acenaphthene ring system.
制备了一系列基于苊并[1,2-b]菲的膦硒醚双齿配体Acenap(PrP)(SeAr)（其中，Acenap = 苊并[1,2-b]菲-5,6-二基，Ar = 苯基、均三甲苯基、2,4,6-三异丙基苯基和超均三甲苯基）。刚性的苊并[1,2-b]菲骨架促使膦和硒醚孤对电子发生强制重叠，从而导致较大的空间耦合，耦合值范围为452至545 Hz。这些刚性配体用于制备一系列选定的晚期d族金属、汞和硼烷配合物，并通过多核NMR和单晶X射线衍射等方法对其进行了表征。在固态结构中，除了一种情况外，路易斯酸性基团（BH、Mo(CO)、Ag、PdCl、PtCl和HgCl）桥接两个供体原子（P和Se）。当桥接基团包含NMR活性核（B、Ag、Ag、Pt和Hg）时，除了各自NMR光谱中的化学位移发生变化外，还能直接观察到J耦合。溶液NMR数据与单晶衍射数据相关，对于汞(II)配合物，它们还与固态NMR数据以及耦合变形密度计算相关。后者表明，在游离配体中，空间相互作用占主导，而在配合物中，主要的耦合途径是通过金属原子，而非通过苊并[1,2-b]菲环系的碳骨架。
