Synthesis and reactivity of [OsH{C<inf>6</inf>H<inf>4</inf>(CH=CHH)}(CO)(PPr<sup>i</sup><inf>3</inf>) <inf>2</inf>] and the formato compounds [Os{(E)-CH=CHPh}(η<sup>2</sup>-O<inf>2</inf>CH)-(CO)(PPr<sup>i</sup><inf>3</inf>)<inf>2</inf>] and [OsH(η<sup>2</sup>-O<inf>2</inf>CH)(CO)(PPr<sup>i</sup><inf>3</inf>) <inf>2</inf>]

María J. Albéniz, Miguel A. Esteruelas, Agustí Lledós, Feliu Maseras, Enrique Oñate, Luis A. Oro, Eduardo Sola, Bernd Zeier

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Abstract

The complex [OsH{C6H4(CH=CHH)}(CO)(PPri3) 2] has been prepared by reaction of the five-co-ordinate [Os{(E)-CH=CHPh}Cl(CO)(PPri3)2] with LiBun in hexane. It reacts with P(OMe)3 and CO to give [OsH{(E)CH=CHPh}(CO){P(OMe)3}(PPri3) 2] and [OsH{(E)-CH=CHPh}(CO)2(PPri3)2], while under a CO2 atmosphere the formate derivative [Os{(E)-CH=CHPh}(η2-O2CH)(CO)(PPri3)2] is obtained. Carbonylation of the latter leads to the monodentate formato complex [Os{(E)-CH=CHPh} {η1-OC(O)H}(CO)2(PPri3) 2] and under a hydrogen atmosphere it affords styrene and [OsH(η2-O2CH)(CO)(PPri3) 2], which can be also prepared by reaction of [OsH2(η2-CH2=CHEt)(CO)(PPri3)2] with CO2. The complex [OsH(η2-O2CH)(CO)(PPri3) 2] reacts with CO, P(OMe)3 and MeO2CC≡CCO2Me to give [OsH{η1-OC(O)H}(CO)L(PPri3)2] [L = CO, P(OMe)3 or MeO2CC≡ CCO2Me]; the carbon atom of its formate ligand is attacked by NEt2H leading to the carbamato compound [OsH(η2-O2CNEt2)(CO)(PPri3)2] and molecular hydrogen. Similarly treatment of [Os{(E)-CH=CHPh}(η2-O2CH)(CO)(PPri3)2] with NEt2H afforded [Os{(E)-CH=CHPh}(η2-O2CNEt2)(CO)(PPr i3)2]. The former complex also reacts with HBF4·OEt2, giving two different derivatives depending upon the conditions: in diethyl ether as solvent and in the presence of acetonitrile the vinyl complex [Os{(E)-CH=CHPh}(CO)(MeCN)2(PPri3) 2]BF4 is formed, while the carbene derivative [Os(η2-O2CH)(=CHCH2Ph)(CO)(PPr i3)2]BF4 is obtained in chloroform. The products formed by reaction of [OsH(η2-O2CH)(CO)(PPri3) 2] with HBF4·OEt2 also depend upon the reaction conditions: in diethyl ether and in the presence of MeCN the hydrido compound [OsH(CO)(MeCN)2(PPri3)2]BF 4 is obtained; however a mixture of products, mainly dihydrogen derivatives, is formed in CDCl3. On the basis of theoretical calculations and T1 measurements, the nature and structure of these dihydrogen compounds are discussed.
Original languageEnglish
Pages (from-to)181-192
JournalJournal of the Chemical Society - Dalton Transactions
Issue number2
DOIs
Publication statusPublished - 21 Jan 1997

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