20574-17-8Relevant articles and documents
METATHETICAL REACTIONS OF CARBONYLATE ANIONS WITH DICHLORORUTHENIUM COMPLEXES: PREPARATION AND CHARACTERIZATION OF RUTHENIUM-MOLYBDENUM AND RUTHENIUM-MANGANESE COMPLEXES
Sabo, Sylviane,Chaudret, Bruno,Gervais, Daniele
, p. 411 - 418 (1985)
The possibility of making metal-metal bonded heterobimetallic species by metathesis of ruthenium dichlorides with anionic carbonylates is demonstrated by the isolation of MoRu(μ-Cl)(CO)2(PPh3)2(η-C5H5) (1) and MnRuCl(μ-CO)2(CO)3(μ-dppm)2 (2), obtained by action of - on RuCl2(PPh3)3 and of Mn(CO)5- on RuCl2(dppm)2, respectively.In contrast, reaction of Mn(CO5)- with RuCl2(PMe3)4 yielded an ionic species 3 containing the diruthenium cation Ru2Cl3(PMe3)46+.More interestingly, the action of Mn(CO)5- on RuCl2(PPh3)3 resulted in formation of the unexpected complex MnRu(μ-PPh2)(CO)6(PPh3)2 (4) in which the phosphido group PPh2 bridges the two metals; this process is shown to involve a hydride intermediate, and elimination of a molecule of benzene, both identified in the reaction mixture.
Impact of the novel Z-acceptor ligand bis{(ortho-diphenylphosphino)phenyl}zinc (ZnPhos) on the formation and reactivity of low-coordinate Ru(0) centers
Beck, Madeleine L.,Burnage, Arron L.,Farmer, James C. B.,Isaac, Connie J.,Macgregor, Stuart A.,Mahon, Mary F.,Miloserdov, Fedor M.,Whittlesey, Michael K.
, p. 15606 - 15619 (2020)
The preparation and reactivity with H2 of two Ru complexes of the novel ZnPhos ligand (ZnPhos = Zn(o-C6H4PPh2)2) are described. Ru(ZnPhos)(CO)3 (2) and Ru(ZnPhos)(IMe4)2 (4; IMe4 = 1,3,4,5-tetramethylimidazol-2-ylidene) are formed directly from the reaction of Ru(PPh3)(C6H4PPh2)2(ZnMe)2 (1) or Ru(PPh3)3HCl/LiCH2TMS/ZnMe2 with CO and IMe4, respectively. Structural and electronic structure analyses characterize both 2 and 4 as Ru(0) species in which Ru donates to the Z-type Zn center of the ZnPhos ligand; in 2, Ru adopts an octahedral coordination, while 4 displays square-pyramidal coordination with Zn in the axial position. Under photolytic conditions, 2 loses CO to give Ru(ZnPhos)(CO)2 that then adds H2 over the Ru-Zn bond to form Ru(ZnPhos)(CO)2(μ-H)2 (3). In contrast, 4 reacts directly with H2 to set up an equilibrium with Ru(ZnPhos)(IMe4)2H2 (5), the product of oxidative addition at the Ru center. DFT calculations rationalize these different outcomes in terms of the energies of the square-pyramidal Ru(ZnPhos)L2 intermediates in which Zn sits in a basal site: for L = CO, this is readily accessed and allows H2 to add across the Ru-Zn bond, but for L = IMe4, this species is kinetically inaccessible and reaction can only occur at the Ru center. This difference is related to the strong π-acceptor ability of CO compared to IMe4. Steric effects associated with the larger IMe4 ligands are not significant. Species 4 can be considered as a Ru(0)L4 species that is stabilized by the Ru→Zn interaction. As such, it is a rare example of a stable Ru(0)L4 species devoid of strong π-acceptor ligands.
Bis(methimazolyl)silyl complexes of ruthenium
Hill, Anthony F.,Neumann, Horst,Wagler, Joerg
, p. 1026 - 1031 (2010/04/25)
The new bis(methimazolyl)silane PhSiH(mt)2 (mt = methimazolyl), obtained from methimazole (Hmt) and phenyldichlorosilane, reacts with [Ru(η4-C8H12)(η6-C 8H10)] in refiuxing tetra
Chemoselective hydrogenation of α,β-unsaturated ketones to allylic alcohols, catalyzed by a mononuclear ruthenium complex containing trans PnBu3 and PPh3 ligands
Micoli, Francesca,Oberhauser, Werner,Salvini, Antonella,Bianchini, Claudio
, p. 2334 - 2341 (2008/01/27)
The ruthenium(II) bis(acetate) complex Ru(CO)2(OAc)2(PnBu3) (PPh3) (OAc = acetate) containing two different trans phosphine ligands, has been employed as pre-catalyst for the chemoselective hydrogenation of α,β-unsaturated ketones to allylic alcohols. Analogous catalytic reactions with the homodiphosphine pre-catalysts Ru(CO)2(OAc)2(PnBu3) 2 and Ru(CO)2(OAc)2(PPh3)2 gave lower conversions and selectivities. Batch catalytic reactions and operando high-pressure NMR experiments have contributed to establish that the hydrogenation of the C{double bond, long}O group is performed by the heterodiphosphine monohydride RuH(CO)2(OAc)(PnBu3)(PPh3) generated in situ by hydrogenation of the bis(OAc) precursor. PPh3 unfastening from this monohydride complex is an essential condition for the occurrence of catalytic activity.
