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POP-pincer ruthenium complexes: d6 counterparts of osmium d4 species

AutorAlós, Joaquín ; Bolaño, Tamara ; Esteruelas, Miguel A. ; Oliván, Montserrat ; Oñate, Enrique ; Valencia, Marta
Fecha de publicación2014
EditorAmerican Chemical Society
CitaciónInorganic Chemistry 53(2): 1195-1209 (2014)
ResumenA wide range of ruthenium complexes stabilized by the POP-pincer ligand xant(PiPr2)2 (9,9-dimethyl-4,5- bis(diisopropylphosphino)xanthene) were prepared starting from cis-RuCl 2{κ-S-(DMSO)4} (1; DMSO = dimethyl sulfoxide). Treatment of toluene solutions of this adduct with the diphosphine under reflux leads to RuCl2{xant(PiPr2)2} (κ-S-DMSO) (2), which reacts with H2 in the presence of a Brønsted base. The reaction in the presence of Et3N affords RuHCl{xant(PiPr2)2}(κ-S-DMSO) (3), whereas NaH removes both chloride ligands to give RuH2{xant(P iPr2)2}(κ-S-DMSO) (4). The stirring of 3 in 2-propanol under 3 atm of H2 for a long time produces the elimination of DMSO and the coordination of H2 to yield the dihydrogen derivative, RuHCl(η2-H2){xant(P iPr2)2} (5). In contrast to H2, PPh3 easily displaces DMSO from the metal center of 3 to afford RuHCl{xant(PiPr2)2}(PPh3) (6), which can be also obtained starting from RuHCl(PPh3)3 (7) and xant(PiPr2)2. In contrast to 3, complex 4 does not undergo DMSO elimination to give RuH2(η2-H 2){xant(PiPr2)2} (8) under a H 2 atmosphere. However, the latter can be prepared by hydrogenation of Ru(COD)(COT) (9; COD = 1,5-cyclooctadiene and COT = 1,3,5-cyclooctatriene) in the presence of xant(PiPr2)2. A more efficient procedure to obtain 8 involves the sequential hydrogenation with ammonia borane of the allenylidene derivative RuCl2(i=Ci=Ci=CPh2) {xant(PiPr2)2} (10), which is formed from the reaction of 2 with 1,1-diphenyl-2-propyn-1-ol. The hydrogenation initially gives RuCl2(i=Ci=CHCHPh2){xant(PiPr 2)2} (11), which undergoes the subsequent reduction of the Ru-C double bond to yield the hydride-tetrahydroborate complex, RuH(η2-H2BH2){xant(PiPr 2)2} (12). The osmium complex, OsCl 2{xant(PiPr2)2}(κ-S-DMSO) (13), reacts with 1,1-diphenyl-2-propyn-1-ol in a similar manner to its ruthenium counterpart 2 to yield the allenylidene derivative, OsCl 2(i=Ci=Ci=CPh2){xant(PiPr2) 2} (14). Ammonia borane also reduces the Cβ-C γ double bond of the allenylidene of 14. However, the resulting vinylidene species, OsCl2(i=Ci=CHCHPh2){xant(P iPr2)2} (15), is inert. Complex 12 is an efficient catalyst precursor for the hydrogen transfer from 2-propanol to ketones, the α-alkylations of phenylacetonitrile and acetophenone with alcohols, and the regio- and stereoselective head-to-head (Z) dimerization of terminal alkynes. © 2014 American Chemical Society.
Identificadoresdoi: 10.1021/ic402795g
issn: 0020-1669
e-issn: 1520-510X
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