Reactions of Pyridyl Side Chain Functionalized Indenes with Ru₃(CO)₁₂

Abstract

Reactions of the pyridyl side chain functionalized indenes 3‐R‐C9H7 [R = (C5H4N)CH2CMe2 (1), (MeC5H3N)CH2CMe2 (2), (C5H4N)CH2 (6)] with Ru3(CO)12 in refluxing xylene gave the facial coordinated indenyl cluster [μ3‐η5:η2:η2‐(C5H3N)CH2Me2C(C9H6)]Ru4(μ3‐CO)(CO)7 (8), the syn‐η5:η6‐coordinated indenyl cluster [μ‐η5:η6‐(MeC5H3N)CH2CMe2(C9H6)Ru2(CO)3]2 (10), and the η1:η2‐coordinated indenyl complex[η2‐(C5H3N)CH2(C9H7)][η1:η2‐(C5H4N)CH2(C9H6)]Ru2(CO)4(18), respectively, in addition to the normal diruthenium complexes [(η5‐RC9H6)Ru(CO)]2(μ‐CO)2 [R = (C5H4N)CH2CMe2 (7), (MeC5H3N)CH2CMe2 (9), (C5H4N)CH2 (17)]. When the pyridyl side chains were replaced by other bulky groups [R = tBu (3), PhCH2Me2C (4), (C9H6N)CH2Me2C (5)], the similar syn‐η5:η6‐coordinated indenyl clusters 12, 14, and 16 were also obtained. When 1 or 2 were treated with Ru3(CO)12 in refluxing heptane, the ionic clusters {[(C5H4N)CH2Me2C(C9H6)]Ru(CO)2}+[HRu6(CO)18]– (19), [(C5H4N)CH2Me2C(C9H8)]+[HRu6(CO)18]– (20), and complex 8 or ionic clusters {[(MeC5H3N)CH2Me2C(C9H6)]Ru(CO)2}+[HRu6(CO)18]– (21) and [(MeC5H3N)CH2Me2C(C9H8)]+[HRu6(CO)18]– (22) were obtained. Similar treatment of 5 or 6 with Ru3(CO)12 in refluxing heptane gave the ionic clusters [(C9H6N)CH2Me2C(C9H8)]+[HRu6(CO)18]– (23) or {[η3‐(C5H4N)CH(C9H7)][η2‐(C5H4N)CH2(C9H7)]Ru(CO)}+[HRu6(CO)18]– (24), respectively, in addition to complex 18 in the latter case. The molecular structures of 8, 9, 10, 14, 17, 18, 21, 22, and 24 were determined by X‐ray diffraction analysis.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

Calcium-Mediated C–H and C–F Bond Cleavage: Synthesis of Indenes and Perfluorodibenzopentalenes from 1,4-Dilithio-1,3-butadienes

“…3 was fully characterized by NMR spectroscopy and single-crystal X-ray analysis. 3 is a dimeric indenyl lithium structure with a syn -η 5 : η 6 -facial coordination mode to the coplanar Cp ring and phenyl ring, respectively (Scheme a and Figure ). No C–M bond could be found at the methylene position, which also supports the in situ protonation of an elusive intermediate in this reaction.…”

Reactivity of a trinuclear ruthenium complex involving C–H activation and insertion of alkene

“…The ligand precursor 1-(6-bromo-2-pyridyl)indene was synthesized according to the literature. 21 Equipment and analyses. 1 H NMR spectra were recorded on a Bruker AV 500 instrument, while IR spectra were recorded as KBr disks on a FT IR 8900 spectrometer.…”

Pyridyl-Substituted Indenyl Ruthenium Complexes: Synthesis, Structures, and Reactivities

“…The cyclopentadienyl or indenyl ligands including periphery donor substituents have usually been used to synthesize oligonuclear transition metal complexes possessing distinct structures and reactivities owing to the favorable intramolecular coordination of these donors to Lewis acidic metal centers . In our previous work we studied the reactions of pyridyl-substituted cyclopentadienes and indenes with Ru 3 (CO) 12 and synthesized a series of ruthenium carbonyl complexes involving intramolecular C−H activation and including different bonding modes of indenyl ligands . Herein we report the synthesis of the pyridyl-substituted indenyl ruthenium carbonyl complex {μ 2 -η 5 :η 1 -(C 5 H 4 N)(C 9 H 5 )}Ru 3 (CO) 9 ( 1 ) and its reactivities with other pyridine derivatives, PPh 3 , and a series of terminal and internal alkenes.…”