33635-52-8Relevant articles and documents
In Situ FTIR and NMR Spectroscopic Investigations on Ruthenium-Based Catalysts for Alkene Hydroformylation
Kubis, Christoph,Profir, Irina,Fleischer, Ivana,Baumann, Wolfgang,Selent, Detlef,Fischer, Christine,Spannenberg, Anke,Ludwig, Ralf,Hess, Dieter,Franke, Robert,B?rner, Armin
supporting information, p. 2746 - 2757 (2016/02/27)
Homogeneous ruthenium complexes modified by imidazole-substituted monophosphines as catalysts for various highly efficient hydroformylation reactions were characterized by in situ IR spectroscopy under reaction conditions and NMR spectroscopy. A proper protocol for the preformation reaction from [Ru3(CO)12] is decisive to prevent the formation of inactive ligand-modified polynuclear complexes. During catalysis, ligand-modified mononuclear ruthenium(0) carbonyls were detected as resting states. Changes in the ligand structure have a crucial impact on the coordination behavior of the ligand and consequently on the catalytic performance. The substitution of CO by a nitrogen atom of the imidazolyl moiety in the ligand is not a general feature, but it takes place when structural prerequisites of the ligand are fulfilled.
Heterobinuclear and heterotrinuclear metal μ-allenyl complexes containing platinum and one or both of iron and ruthenium. Synthesis of higher nuclearity metal complexes from mononuclear metal η1-propargyls and η1-allenyls and from binuclear metal μ-η1:η2α,β-allenyls
Willis, Richard R.,Shuchart, Chris E.,Wojcicki, Andrew,Rheingold, Arnold L.,Haggerty, Brian S.
, p. 3179 - 3191 (2008/10/08)
The reactions of Cp(CO)2MCH2C≡CPh with Pt(PPh3)4 or Pt(PPh3)2C2H4 in THF at reflux and of Cp(CO)2MCH=C=CH2 with Pt(PPh3)2C2H4 in THF or hexane at -78 °C to ambient temperature afforded the heterobinuclear metal μ-allenyl complexes (PPh3)2Pt(μ-η1:η2 α,β-C(Ph)=C=CH2)M(CO)Cp (M = Ru, R = Ph (1a); M = Fe, R = Ph (2a); M = Ru, R = H (1b); M = Fe, R = H (2b)). The products reacted with Ru3(CO)12 or Fe2(CO)9 (Ru, Fe = M′) in THF at room temperature to yield open heterotrinuclear metal μ-allenyl complexes (PPh3)-(CO)Pt(μ3-η1:η 2:η2-C(R)=C=CH2)M′(CO) 3M(CO)Cp (M′ = M = Ru, R = H (4); M′ - Ru, M = Fe, R = H (5); M′ = Fe, M = Ru, R = Ph (6a); M′ = Fe, M = Ru, R = H (6b); M′ = M = Fe, R = H (7)), as well as M′(CO)4PPh3. The reaction of 1a with Fe2(CO)9 also afforded the CO-for-PPh3 substitution product (PPh3)(CO)Pt(μ-η1:η2 α,β-C(Ph)=C=CH2)Ru(CO)Cp (3). Treatment of the μ-allenylcarbonyl (CO)3Fe(μ-η1:η3-η 2-C(O)C(Ph)=C=CH2)Ru(CO)Cp with Pt(PPh3)2C2H4 in THF at 0 °C with warming to ambient temperature gave three heterometallic products: 6a, the PPh3-for-CO substituted (PPh3)(CO)2Fe(μ-η3:η 2-C(O)C(Ph)=C=CH2)Ru(CO)Cp, and (PPh3)2Pt(μ3-η1:η 1:η3-C(Ph)CCH2)Ru(CO)Cp(μ 2-CO)Fe(CO)2 (8). All new products were characterized by a combination of IR and NMR (1H, 13C{1H}, and 31P{1H}) spectroscopy, FAB mass spectrometry, and elemental analysis; the structures of 1b, 3, 6a, and 8 were elucidated by X-ray diffraction analysis. Complexes 1b and 3 each contain a Pt-Ru bond and a μ-allenyl group that is η1 ligated to Pt and η2 ligated, through the internal C=C bond, to Ru. 6a contains an open Pt-Fe-Ru metal framework, with the μ-C(Ph)=C=CH2 ligand being attached η1 to Pt, η2 through the C(Ph)=C to Fe, and η2 through the C=CH2 to Ru. 8 is also an open, Pt-Fe-Ru bonded cluster; however, it contains an η3-allyl group ligated to Fe and metalated at CPh (Ru) and Cβ (Pt). Possible mechanisms of formation of the new μ-allenylmetal complexes are presented. Complexes 1 and 2 underwent fragmentation of the binuclear framework to yield Cp(CO)2MCH=C=CH2 (M = Ru, Fe), Cp(CO)2RuC(Ph)=C=CH2, or Cp-(CO)2FeCH2C≡CPh, as appropriate, in addition to Pt(PPh3)2(CO)2, upon treatment with CO at room temperature. The reverse of these processes can be effected by sweeping the product solutions with Ar for the three η1-allenyl complexes, but not for Cp(CO)2FeCH2C=CPh.
The photochemical generation of novel neutral mononuclear ruthenium complexes and their reactivity
Edwards, Andrew J.,Leadbeater, Nicholas E.,Lewis, Jack,Raithby, Paul R.
, p. 15 - 20 (2007/10/03)
The room-temperature photolysis of Ru3(CO)12 (1) in dichloromethane under a flow of ethylene affords the highly reactive complex Ru(CO)4(C2H4) (2) in a quantitative yield.The addition of MeCN to the reaction mixture, while the photolytic conditions and the ethylene flow are maintained, gives Ru(CO)3(C2H4)(NCMe) (3).If the irradiation is continued but the ethylene flow stopped, a different product, namely Ru(CO)3(NCMe)2 (4) is obtained.The addition of an excess of triphenylphosphine to a dichloromethane solution of 2 in the absence of ethylene and of light gives two phosphine-substituted products: Ru(CO)4(PPh3) (5) and Ru(CO)3(PPh3)2 (6).Under similar conditions, 3 affords 6 and the trinuclear cluster Ru3(CO)9(PPh3)3 (7) while, if MeCN is added instead of PPh3, the reactive cluster Ru3(CO)9(NCMe)3 (8) is obtained.If an excess of acrylonitrile is used instead of ethylene, the photolysis of 1 in dichloromethane yields Ru(CO)4(NCCH=CH2) (9) which reacts under photolytic conditions but in the absence of an excess of acrylonitrile with MeCN to give Ru(CO)3(NCCH=CH2)(MeCN) (10) and this product reacts with a second equivalent of acrylonitrile to afford Ru(CO)3(NCCH=CH2)2 (11).All the products have been characterized by IR spectroscopy and their structures established from symmetry considerations.Keywords: Ruthenium; Carbonyl; Nitrile; Photochemical synthesis
