210565-07-4Relevant academic research and scientific papers
Behavior of (ether-phosphine)ruthenium(II) complexes [(η6-C6Me6)RuH(PO)][BF4] containing reactive Ru-O and Ru-H bonds toward various small molecules and their application in ring-opening metathesis polymerization
Lindner, Ekkehard,Pautz, Stefan,Fawzi, Riad,Steimann, Manfred
, p. 3006 - 3014 (2008/10/08)
The ruthenium(II) complexes [(η6-C6Me6)RuH(PO)][BF4] (5a-c; PO = η2-(O,P)-chelated ether-phosphine; a, Ph2PCH2CH2OCH3; b, Ph2PCH2C4H7O2 (C4H7O2 = 1,3-dioxanyl); c, Ph2-PCH2C3H5O2 (C3H5O2 = 1,3-dioxolanyl)), each having a Ru-O and Ru-H functionality, were obtained by hydride abstraction from (n6-C6Me6)RuH2(P～O) (4a-c, P～O = η1-(P)-coordinated ligand) with Ph3CBF4. A facile Ru-O bond cleavage occurs when 5a-c are reacted with a variety of small molecules. Carbon monoxide, acetonitrile, tert-butyl isocyanide, and ethene were readily added to 5a-c, leading to the corresponding adducts [(η6-C6Me6)RuH(P～O)L]-[BF4] (6a-c, 7a-c, 8a-c, 10a-c; L = CO, CH3CN, t-BuNC, C2H4). π/σ rearrangements with incorporation of the Ru-H bonds in 10a-c were not observed. If 5a-c were treated with carbon disulfide, both functionalities were required. Rupture of the Ru-O contact resulted in a π-CS2-coordinated intermediate followed by an insertion of CS2 into the Ru-H bond to give the dithioformato complexes [(η6-C6Me6)RuH(P～O)(S 2CH)][BF4] (9a-c). All compounds were obtained in excellent yields under mild conditions. The structures of 5a, 7c, 8c, and 9a were determined by single-crystal X-ray diffraction methods. Ring-opening metathesis polymerization of norbornene was achieved using complexes 5a-c as the catalyst precursors.
