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Intermolecular activation of carbon-hydrogen bonds has been accomplished by reduction with sodium amalgam of (sip 3 )(Me 3 P)RuCl 2 , 1, [“sip 3 ” = MeSi(CH 2 PMe) 2 ) 3 ] in aromatic hydrocarbons, such as benzene and substituted derivatives thereof. In these reactions, the 16e equivalent (sip 3 XMe 3 P)Ru(O) thus generated exhibits a preference for insertion across the unhindered metaand para-C-H bonds to produce complexes of composition (sip 3 )(Me 3 P)RuH(C 6 H 3 RR′) [R = R′ = H, 2; R = H, R′ = CH 3 , 3; R = R′ = CH 3  (3,4-xylyl), 4; R = R′ = CH 3  (3,5-xylyl), 5; R = H, R′ = CF 3 , 6], of which 3, 4, and 6 were isolated as mixtures of meta/para-isomers and Ru-aryl rotamers, respectively. Reaction of the phenyl hydride 2 with 4-MeC 6 H 4 NCE (E = O, S) leads to insertion of the heteroallenes into the Ru-Η bond to give (sip 3 )(Me 3 P)Ru[N(C 6 H 4 Me-4)C(O)H]C 6 H 5 , 8, and (sip 3 )(Me 3 P)Ru[SC(=NC 6 H 4 Me-4)H]C 6 H 5 , 10, as the primary products. While the latter forms (sip 3 ), 11, by loss of PMe 3 , the former reacts with another molecule of isocyanate to afford the acyl compound (sip 3 )9, as the ultimate product. Treatment of 2 with CO 2  results in the formation of a carbonato derivative, (sip 3 )(Me 3 P)Ru(O 2 CO), 7.

zeitschrift für naturforschung b

Oligophosphan-Liganden, XXXVIII / Oligophosphine Ligands, XXXVIII: Darstellung, Isomerie und Reaktivität von Arylhydridoruthenium(II)-Komplexen [MeSi(CH 2 PMe 2 ) 3 l(Me 3 P)RuH(Ar) / Preparation, Isomerism, and Reactivity of Arylhydridoruthenium(II) Complexes [MeSi(CH 2 PMe 2 ) 3 ](Me 3 P)RuH(Ar)