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Five-coordinate complex [RuHCl(CO)(PPri 3)2] as a precursor for the preparation of new cyclopentadienylruthenium compounds containing unsaturated η1-carbon ligands

AuthorsEsteruelas, Miguel A. ; Gómez, Angel V.; Lahoz, Fernando J. ; López, Ana M. ; Oñate, Enrique ; Oro, Luis A.
Issue Date1996
PublisherAmerican Chemical Society
CitationOrganometallics 15(15): 3423-3435 (1996)
AbstractThe five-coordinate complex [RuHCl(CO)(PPri 3)2] (1) reacts with cyclopentadiene in methanol under reflux to give [RuH(η5-C5H5)(CO)(PPri 3)] (2) and [HPPri 3]Cl. The protonation of 2 in dichloromethane-d2 leads to the dihydrogen complex [Ru(η5-C5H5)(η5-H 2)(CO)(PPri 3)]-BF4 (3) in equilibrium with traces of the dihydrido tautomer [RuH2(η5-C5H5)(CO)(PPr i 3)]-BF4 (4). The reaction of 2 with HBF4·Et2O in acetone affords the solvated complex [Ru(η5-C5H5)(CO){η 1-OC(CH3)2}(PPri 3)]BF4 (5), which reacts with CO, dimethyl acetylenedicarboxylate, and NaCl to give [Ru(η5-C5H5)(CO)2(PPr i 3)]BF4 (6), [Ru(η5-C5H5){η2-C 2(CO2CH3)2}(CO)(PPri 3)]-BF4 (7), and [Ru(η5-C5H5)Cl(CO)(PPri 3)] (8), respectively. Complex 5 also reacts with alkyn-1-ols. The reaction with 1,1-diphenyl-2-propyn-1-ol leads to the allenylidene complex [Ru(η5-C5H5)(C=C=CPh 2)(CO)(PPri 3)]BF4 (9), which affords [Ru(η5-C5H5){C(OH)CH=CPh 2}-(CO)(PPri 3)]BF4 (10) by reaction with water. 10 is converted into the acyl derivative [Ru-(η5-C5H5){C(O)CH=CPh 2}(CO)(PPri 3)] (11), when a CH2Cl2 solution of 10 is passed through an Al2O3 column. The structure of 11 was determined by an X-ray investigation. The reaction of 5 with 2-propyn-1-ol leads to the α,β-unsaturated hydroxycarbene complex [Ru-(η5-C5H5){C(OH)CH=CH 2}(CO)(PPri 3)]BF4 (12). Similarly to 10, 12 is converted into [Ru-(η5-C5H5){C(O)CH=CH 2}(CO)(PPri 3)] (13), when the solutions of 12 are passed through an Al2O3 column. Treatment of 5 with 1-ethynyl-1-cyclohexanol leads to a mixture of organometallic compounds including [Ru(η5-C5H5){C(OH)CH=C(CH2) 4CH2}(CO)(PPri 3)]BF4 (14). Chromatography of the mixture affords [Ru(η5-C5H5){C(O)CH=C(CH2) 4CH2}(CO)-(PPri 3)] (15) and [Ru(η5-C5H5){C≡CC=CH(CH 2)3CH2}(CO)(PPri 3)] (16). 9 reacts with alcohols and thiols to give [Ru(η5-C5H5){C(ER)CH=CPh 2}(CO)(PPri 3)]BF4 (ER = OMe (17), OEt (18), SPrn (21)), which by treatment with NaOMe afford [Ru(η5-C5H5){C(ER)=C=CPh 2}(CO)-(PPri 3)] (ER = OMe (19), OEt (20), SPrn (22)). Similarly, the reaction of 9 with benzophenone imine leads to [Ru(η5-C5H5){C(CH=CPh 2)=N=CPh2}(CO)(PPri 3)]BF4 (23), which by reaction with NaOMe gives [Ru(η5-C5H5){C(N=CPh 2)=C=CPh2}(CO)(PPri 3)] (24). The structure of 23 was also determined by an X-ray investigation. The C=N bond lengths are 1.283(9) and 1.252(9) Å, while the C-N-C angle is 149.9(6)°.
Identifiersdoi: 10.1021/om960124d
issn: 0276-7333
e-issn: 1520-6041
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