157741-64-5Relevant academic research and scientific papers
Ru(CO)4(PMe2Ph) catalyzed carbonylation of Ru(CH3)I(CO)2(iPr-DAB) and Ru(CH3)I(CO)2(iPr-Pyca) complexes. X-ray structure of [Ru(CH3)(CO)2[(2-methoxyethyl)Pyca]][OTf]
De Klerk-Engels, Barbara,Groen, Johannes H.,Kraakman, Marco J. A.,Ernsting, Jan Meine,Vrieze, Kees,Goubitz, Kees,Fraanje, Jan
, p. 3279 - 3292 (2008/10/08)
The synthesis and characterization of complexes Ru(R)X(CO)2(R′-Pyca) (R = CH3 and X = I (2); R = C(O)CH3 and X = I (3); R = CH3 and X = OTf = SO3CF3 (4); R = C(O)CH3 and X = OTf (5); R1-Pyca = 2-R1-pyridinecarbaldimine; and R′ = isopropyl (b), methoxyethyl (c), or isopropoxypropyl (d)), respectively, will be presented. The X-ray structure determination of the yellow crystals of [Ru(CH3)(CO)2(CH3OCH2CH 2-PyCa)][OTf] (4c) has been carried out. Crystal data for 4c: monoclinic, space group P21/c with a = 8.5008(4) ?, b = 12.3281(8) ?, c = 18.412(1) ?, β = 101.118(6)°, V = 1893.4(2) ?3, Z = 4. The Ru(CO)4(PMe2Ph) (13) catalyzed CO insertion in the methyl-ruthenium bond of Ru(CH3)X(CO)2(iPr-DAB) (X = I (2a); X = OTf (4a); X = Cl (6a); DAB = 1,4-diaza-1,3-butadiene) and Ru(CH3)X(CO)2(iPr-Pyca) (X - I (2b); X = OTf (4b)) has been studied by use of labeled Ru(13CO)4(PMe2Ph) (13) and by reaction in the absence or presence of additional ligand PPh3 and CO. For the neutral complexes 2a, 6a, and 2b the key intermediate for the CO insertion catalyzed by 13 is most probably of the type [Ru(CH3)X(CO)(α-diimine)Ru(CO)3(PMe 2Ph)(μ-CO)2] (X1), which is, however, not observed during the reaction. By 13CO labeling experiments it has clearly been demonstrated that binuclear species are involved in this reaction. Complex Ru(CO)4(PMe2Ph) (13) decomposes in CDCl3 at 45°C under N2 and under a CO atmosphere (1 and 8 atm) within 3 h to form Ru2(CO)4(PMe2Ph)2(μ-Cl) 2 (15), which can further react with PPh3 to Ru2(CO)4(PMe2Ph)2(PPh 3)2(μ-Cl)2 (16). Suprisingly, 13 is stable under high CO pressure in the presence of 2a, 6a, and 2b in CDCl3 at 45°C for several hours, most probably as a result of a faster reaction of Ru(CO)4(PMe2Ph) (13) or most likely [Ru(CO)3(PMe2Ph)] with 2a, 6a, or 2b than with CDCl3, which prohibits decomposition.
Carbonylation of the Ru-Me bond of Ru(Me)(I)(CO)2(iPr-N=CHCH=N-iPr) catalyzed by Ru(CO)4(PR3), ZnCl2, and H+
Kraakman, Marco J. A.,De Klerk-Engels, Barbara,De Lange, Paul P. M.,Vrieze, Kees,Smeets, Wilberth J. J.,Spek, Anthony L.
, p. 3774 - 3784 (2008/10/08)
Reaction of the dimetallic compound Ru2(Me)(I)(CO)4(PR3)(iPr-DAB) (iPr-DAB = iPr-N=C(H)C-(H)=N-iPr; PR3 = P(nBu)3 (2a), PMe2Ph (2b), PMePh2 (2c), PPh3 (2d), P(OMe)3 (2e), P(OPh)3 (2f)) with carbon monoxide afforded a mixture of the monomeric complexes Ru(R)(I)(CO)2(iPr-DAB) (R = Me (3); R = C(O)Me (4)) and Ru(CO)4(PR3) (5a-f). It was found that with increasing basicity of the phosphine there is a stronger tendency to form the acetyl product 4, although 3 is formed initially for all phosphines used. Mechanistic studies showed that the conversion of 3 to 4 is catalyzed by Ru(CO)4(PR3), provided PR3 is sufficiently basic. The use of 13CO-enriched Ru(CO)4(PR3) led to the incorporation of 13CO into both the acetyl CO group and the terminal CO groups of 4, indicating the presence of a dimetallic intermediate, by which intermetallic CO exchange becomes possible. Further evidence for this was obtained from the observation that the conversion of 3 to 4 can also be effected in the absence of free CO, by reaction of 3 with Ru(CO)4(PMe2Ph) (5b) and L′ (L′ = PPh3, P(OPh)3). In addition to 4 the complex Ru(CO)3(PMe2Ph)(L′) is also formed under these conditions. Interestingly, reaction of 3 with 5b in the absence of both CO and L′ also gave carbonylation of the Ru-Me bond, which, however, was accompanied by transfer of a H-atom from an iPr-CH group to an imine C-atom, with formation of Ru(C(O)Me)(I)(CO)2(iPr-N= CH-CH2-N=C(Me)2) (7). Reaction of 3 with AgOTF yielded [Ru(Me)(CO)2(iPr-DAB)][OTF] (8), which in the presence of CO is rapidly converted to [Ru(C(O)Me)(CO)2(iPr-DAB)][OTF] (9), whereas 8 with tBu isocyanide and PMe2Ph gave [Ru(Me)(CO)2(L)(iPr-DAB)][OTF] (L = tBu-NC (10), PMe2Ph (11)). Attempts to carbonylate the Ru-Me bond in complexes 10 and 11 were not successful. Finally it was shown that the carbonylation of the Ru-Me bond of 3 could also be promoted by H+ and ZnCl2. Single-crystal X-ray structure determinations of complexes 4 and 8 have been carried out, and their molecular structures are discussed. Salient features are that 4 has a configuration similar to that of 3; i.e., the acetyl group is trans to I. The trifluorosulfonate anion in 8 is found to be η1-coordinated to the ruthenium center and trans to the methyl group. Crystals of 4 (C12H19N2O3RuI) are monoclinic, space group P21/n, with a = 8.556 (1) A?, b = 18.510 (2) A?, c = 10.500 (1) A?, β = 94.90 (1)°, V = 1656.7 (3) A?3, Z = 4, and final R = 0.0435 for 2565 reflections with I > 2.5σ(I) and 188 parameters. Crystals of 8 (C12H19F3N2O5RuS) are monoclinic, space group P21/c, with a = 8.288 (1) A?, b = 25.839 (2) A?, c = 17.994 (1) A?, β = 100.47 (1)°, V = 3789.1 (6) A?3, Z = 8, and final R = 0.0476 for 3917 reflections with I > 2.5σ(I) and 500 parameters.
