Interplay of Electronic and Steric Effects of R2PH (R = tBu, o-tolyl) in Reactions with Triruthenium Dodecacarbonyl

Boettcher, Hans-Christian; Graf, Marion und Mayer, Peter (2018): Interplay of Electronic and Steric Effects of R2PH (R = tBu, o-tolyl) in Reactions with Triruthenium Dodecacarbonyl. In: Zeitschrift für Anorganische und Allgemeine Chemie, Bd. 644, Nr. 19: S. 1149-1152

Abstract

The reaction of [Ru-3(CO)(12)] with P(o-tolyl)(2)H (molar ratio of 1 to 2) in refluxing THF afforded the electron-precise metal cluster [Ru-3(-H)(2)(-P{o-tolyl}(2))(2)(CO)(8)] (3). This reaction behavior is comparable to that using the secondary phosphane PtBu2H operating with the same molar ratio. As shown in earlier work, the ruthenium carbonyl reacted with an excess of PtBu2H under similar conditions with cluster degradation affording the coordinatively unsaturated complex [Ru-2(-H)(-PtBu2)(PtBu2H)(2)(CO)(4)]. We found that the reaction using similar reaction conditions with P(o-tolyl)(2)H in excess did not result in such a reactive dinuclear species. Here compound 3 was formed in a first step, which reacted with excess of the phosphane affording the new cluster [Ru-3(-H)(2)(-P{o-tolyl}(2))(2)(P{o-tolyl}(2)H)(2)(CO)(6)] (2). The molecular structures of 2 and 3 in the solid were confirmed by single-crystal X-ray analysis. Moreover, the P-31 NMR spectra of the new compounds showed coalescence phenomena on the NMR time scale caused by a restricted rotation about the P-C bonds, and, presumably, about Ru-P bonds, within the phosphane and phosphanido ligands.

• Dokumententyp: Zeitschriftenartikel
• Fakultät: Chemie und Pharmazie > Department Chemie
• Themengebiete: 500 Naturwissenschaften und Mathematik > 540 Chemie
• ISSN: 0044-2313
• Sprache: Englisch