Peloquin Andrew J, Smith Madelyn B, O'Connell Bryce J, Ghiassi Kamran B, Balaich Gary J, Iacono Scott T
Department of Chemistry & Chemistry Research Center, United States Air Force Academy, Colorado Springs, CO 80840, USA.
Aerospace Systems Directorate, Air Force Research Laboratory, Edwards AFB, CA 93524, USA.
Acta Crystallogr E Crystallogr Commun. 2018 Aug 10;74(Pt 9):1190-1194. doi: 10.1107/S2056989018010794. eCollection 2018 Sep 1.
The synthesis and structural properties of a series of chromium tricarbonyl 'piano-stool' complexes bearing substituted penta-fulvene ligands were studied. The complexes, tricarbon-yl(1,3,6-tri-phenyl-fulvene)chromium(0) benz-ene hemisolvate, [Cr(CH)(CO)]·0.5CH (), tricarbon-yl[1,3-di-phen-yl-6-(3-vinyl-phen-yl)fulvene]chromium(0), [Cr(CH)(CO)] (), and tricarbon-yl[1,3-diphenyl-6-(pyren-1-yl)fulvene]chromium(0), [Cr(CH)(CO)] (), each have a distorted octa-hedral geometry, with the fulvene coordinated in a π-η:π-ηπ-η fashion. Significant deviation of the exocyclic fulvene double bond from the cyclo-penta-diene plane accompanies coordination. Evidence of non-covalent π-π inter-actions was observed in both () and (), with centroid-to-centroid distances ranging from 3.330 (8) to 3.494 (8) Å.
研究了一系列带有取代戊搭烯配体的三羰基铬“钢琴凳”配合物的合成及结构性质。这些配合物，三羰基(1,3,6-三苯基-戊搭烯)铬(0)苯半溶剂化物，[Cr(C₅H₃)(CO)₃]·0.5C₆H₆ (1)，三羰基[1,3-二苯基-6-(3-乙烯基苯基)戊搭烯]铬(0)，[Cr(C₁₈H₁₃)(CO)₃] (2)，以及三羰基[1,3-二苯基-6-(芘-1-基)戊搭烯]铬(0)，[Cr(C₂₆H₁₅)(CO)₃] (3)，均具有扭曲的八面体几何构型，其中戊搭烯以π-η¹:π-η²:π-η³的方式配位。配位过程中，环外戊搭烯双键与环戊二烯平面存在显著偏差。在(2)和(3)中均观察到非共价π-π相互作用的证据，质心到质心距离范围为3.330 (8)至3.494 (8) Å。
