Orian Laura, Bisello Annalisa, Santi Saverio, Ceccon Alberto, Saielli Giacomo
Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Via Marzolo 1, 35131 Padova, Italy.
Chemistry. 2004 Aug 20;10(16):4029-40. doi: 10.1002/chem.200305671.
Experimental 103Rh NMR chemical shifts of mono- and binuclear rhodium(I) complexes containing s- or as-hydroindacenide and indacenediide bridging ligands with different ancillary ligands (1,5-cyclooctadiene, ethylene, carbonyl) are presented. A protocol, based on density functional theory calculations, was established to determine 103Rh NMR shielding constants in order to rationalise the effects of electronic and structural variations on the spectroscopic signal, and to gain insight into the efficiency of this computational method when applied to organometallic systems. Scalar and spin-orbit relativistic effects based on the ZORA (zeroth order regular approximation) level have been taken into account and discussed. A good agreement was found for model compounds over a wide range of chemical shifts of rhodium (approximately 10,000 ppm). This allowed us to discuss the experimental and calculated delta(103Rh) in larger complexes and to relate it to their electronic structure.
本文给出了含有s-或as-氢化茚并二烯化物以及茚并二烯二化物桥连配体与不同辅助配体（1,5-环辛二烯、乙烯、羰基）的单核和双核铑(I)配合物的实验103Rh NMR化学位移。建立了基于密度泛函理论计算的方法来确定103Rh NMR屏蔽常数，以便合理化电子和结构变化对光谱信号的影响，并深入了解该计算方法应用于有机金属体系时的效率。基于ZORA（零阶正则近似）水平的标量和自旋-轨道相对论效应已被考虑并讨论。在铑的广泛化学位移范围内（约10,000 ppm），模型化合物取得了良好的一致性。这使我们能够讨论较大配合物中的实验和计算的δ(103Rh)，并将其与它们的电子结构联系起来。
