Novel dinuclear and trinuclear ruthenium clusters derived from 2‐aryl‐substituted indenylphosphines via C─H bond cleavage

• Published in: Applied organometallic chemistry Vol. 31; no. 8
• Main Authors: Meng, Tong, Yuan, Jia, Han, Zhi‐Jun, Luo, Xue, Wu, Qing‐Guo, Liu, Sheng‐Hua, Chen, Jian, Yu, Guang‐Ao
• Format: Journal Article
• Language: English
• Published: Chichester Wiley Subscription Services, Inc 01.08.2017
• Subjects: Aromatic compounds; Carbonyls; Chemistry; Cleavage; Clusters; Crystals; C─H activation; Diffraction; Heptanes; Hydrogen bonds; indenylphosphine; Infrared radiation; Infrared spectroscopy; Insertion; NMR spectroscopy; Refluxing; Ruthenium; Single crystals; Spectroscopic analysis; X-ray diffraction; X-rays
• ISSN: 0268-2605; 1099-0739
• DOI: 10.1002/aoc.3670

Treatment of Ru3(CO)12 with an equivalent of (2‐phenyl‐1H‐inden‐3‐yl)dicyclohexylphosphine (1) and (2‐pyridyl‐1H‐inden‐1‐yl)dicyclohexylphosphine (4) in refluxing heptane gave the novel trinuclear ruthenium clusters (μ3‐η1:η2:η5–2‐phenyl‐3‐Cy2PC9H4)Ru3(CO)8 (1c) and [μ2‐η1–2‐(pyridin‐2‐yl)‐3‐Cy2PC9H6]Ru3(CO)9 (4a), respectively, via C─H bond cleavage. (2‐Mesityl‐1H‐inden‐3‐yl)dicyclohexylphosphine (2) reacted with Ru3(CO)12 in refluxing heptane to give the trinuclear ruthenium cluster [μ‐2‐mesityl‐(3‐Cy2PC9H5)](μ2‐CO)Ru3(CO)9 (2c) via C─H bond cleavage and carbonyl insertion. 2‐(Anthracen‐9‐yl)‐1H–inden‐3‐yldicyclohexylphosphine (3) reacted with Ru3(CO)12 in refluxing heptane to give the dinuclear ruthenium cluster [μ2‐η3:η3–2‐(anthracen‐9‐yl)‐3‐Cy2PC9H6]Ru2(CO)5 (3a). The structures of 1c, 2c, 3a and 4a were fully characterized using IR and NMR spectroscopy, elemental analysis and single‐crystal X‐ray diffraction. These results suggest that the 2‐aryl substituent on the indenyl ring has a pronounced effect on the reaction and coordination modes of Ru3(CO)12. Treatment of Ru3(CO)12 with (2‐phenyl‐1H‐inden‐3‐yl)dicyclohexylphosphine and (2‐pyridyl‐1H‐inden‐1‐yl)dicyclohexylphosphine gave trinuclear ruthenium clusters (μ3‐η1:η2:η5–2‐phenyl‐3‐Cy2PC9H4)Ru3(CO)8 (1c) and [μ2‐η1–2‐(pyridin‐2‐yl)‐3‐Cy2PC9H6]Ru3(CO)9, respectively. (2‐Mesityl‐1H‐inden‐3‐yl)dicyclohexylphosphine reacted with Ru3(CO)12 to give trinuclear ruthenium cluster [μ‐2‐mesityl‐(3‐Cy2PC9H5)](μ2‐CO)Ru3(CO)9. 2‐(Anthracen‐9‐yl)‐1H–inden‐3‐yldicyclohexylphosphine reacted with Ru3(CO)12 to give dinuclear ruthenium cluster [μ2‐η3:η3–2‐(anthracen‐9‐yl)‐3‐Cy2PC9H6]Ru2(CO)5. They were fully characterized by spectroscopic and elemental analyses and single‐crystal X‐ray diffraction. Notably, 1c contains an unprecedented η1:η2:η5 coordination mode of the indenyl ligand.