E-H Bond Cleavage Processes in Reactions of Heterometallic Phosphinidene-Bridged MoRe and MoMn Complexes with Hydrogen and p-Block Element Hydrides
© 2023 The Authors. Published by American Chemical Society.
| Veröffentlicht in: | Organometallics. - 1998. - 42(2023), 19 vom: 09. Okt., Seite 2826-2838 |
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| Weitere Verfasser: | , , , |
| Format: | Online-Aufsatz |
| Sprache: | English |
| Veröffentlicht: |
2023
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| Zugriff auf das übergeordnete Werk: | Organometallics |
| Schlagworte: | Journal Article |
| Zusammenfassung: | © 2023 The Authors. Published by American Chemical Society. Reactions of complexes [MoMCp(μ-PMes*)(CO)6] with H2 and several p-block element (E) hydrides mostly resulted in the cleavage of E-H bonds under mild conditions [M = Re (1a) and Mn (1b); Mes* = 2,4,6-C6H2tBu3]. The reaction with H2 (ca. 4 atm) proceeded even at 295 K to give the hydrides [MoMCp(μ-H)(μ-PHMes*)(CO)6]. The same result was obtained in the reactions with H3SiPh and, for 1a, upon reduction with Na(Hg) followed by protonation of the resulting anion [MoReCp(μ-PHMes*)(CO)6]-. The latter reacted with [AuCl{P(p-tol)3}] to yield the related heterotrimetallic cluster [MoReAuCp(μ-PHMes*)(CO)6{P(p-tol)3}]. The reaction of 1a with thiophenol gave the thiolate-bridged complex [MoReCp(μ-PHMes*)(μ-SPh)(CO)6], which evolved readily to the pentacarbonyl derivative [MoReCp(μ-PHMes*)(μ-SPh)(CO)5]. In contrast, no P-H bond cleavage was observed in reactions of complexes 1a,b with PHCy2, which just yielded the substituted derivatives [MoMCp(μ-PMes*)(CO)5(PHCy2)]. Reactions with HSnPh3 again resulted in E-H bond cleavage, but now with the stannyl group terminally bound to M, while 1a reacted with BH3·PPh3 to give the hydride-bridged derivatives [MoReCp(μ-H)(μ-PHMes*)(CO)5(PPh3)] and [MoReCp(μ-H){μ-P(CH2CMe2)C6H2tBu2}(CO)5(PPh3)], which follow from hydrogenation, C-H cleavage, and CO/PPh3 substitution steps. Density functional theory calculations on the PPh-bridged analogue of 1a revealed that hydrogenation likely proceeds through the addition of H2 to the Mo=P double bond of the complex, followed by rearrangement of the Mo fragment to drive the resulting terminal hydride into a bridging position |
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| Beschreibung: | Date Revised 20.10.2023 published: Electronic-eCollection Citation Status PubMed-not-MEDLINE |
| ISSN: | 0276-7333 |
| DOI: | 10.1021/acs.organomet.3c00295 |