Reactions between RuClH(CO)(PPh3)3 and primary or secondary allylamines give olefin-insertion products: Ru(CH2CH2CH2NHR)Cl(CO)(PPh3)2(R=H(1),CH3(4), and CH2CH=CH2 (5)). Analytical and spectroscopic studies on these products show they have an octahedral six-coordinate structure in which two triphenylphosphines are located mutually cis, and a phosphine-trans isomer is obtained only in the case of R=H. The insertion of the primary allylamine occurs after the initial ligand exchange of the allylamine with one PPh3 of the starting complex. The variable-temperature NMR analyses reveal that the complexes derived from the secondary allylamines liberate one of the two PPh3 ligands at high temperatures. When R = CH3, an isolable dichloro-bridged dinuclear complex [Ru(mu-Cl)(CH2CH2CH2NHCH3)(CO)(PPh3)-]2 (6) is formed by the liberation of PPh3. A carbon-nitrogen bond of some tertiary allylic amines is cleaved in the reaction with RuClH(CO) (PPh3)3 to give the (pi-allyl)ruthenium(II) complex Ru(eta3-C3H5)CI(CO)(PPh3)2 (7) and its analog. The direct interaction between the Ru-H bond and the allylic amine leads to the formation of the (pi-allyl)ruthenium(II) complex, and the corresponding secondary amine without an increase of the oxidation state. Catalytic isomerization of some allylic amines to the enamines is also recognized during the insertion and the carbon-nitrogen bond cleavage.
The coupling of methylene and vinyl ligands at a ruthenium(II) centre
作者:Anthony F. Hill、Chean T. Ho、James D. E. T. Wilton-Ely
DOI:10.1039/a704157h
日期:——
The reaction of [Ru(CHCH2)Cl(CO)(PPh3)2] with diazomethane provides the allyl complex [Ru(η3-CH2CHCH2)Cl(CO)(PPh3)2] which is also the product of the reactions of [RuHCl(CO)(PPh3)3] with either allene or propyne and which reacts subsequently with NaS2CNMe2 to provide [RuH(S2CNMe2)(CO)(PPh3)2] and allene.