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|a 10.1021/acs.organomet.3c00295
|2 doi
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|a pubmed24n1211.xml
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|a (DE-627)NLM363349944
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|a (NLM)37842181
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|a DE-627
|b ger
|c DE-627
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|a eng
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|a Alvarez, M Angeles
|e verfasserin
|4 aut
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|a E-H Bond Cleavage Processes in Reactions of Heterometallic Phosphinidene-Bridged MoRe and MoMn Complexes with Hydrogen and p-Block Element Hydrides
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|c 2023
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|a Text
|b txt
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|a ƒaComputermedien
|b c
|2 rdamedia
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|a ƒa Online-Ressource
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|2 rdacarrier
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|a Date Revised 20.10.2023
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|a published: Electronic-eCollection
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|a Citation Status PubMed-not-MEDLINE
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|a © 2023 The Authors. Published by American Chemical Society.
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|a 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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|a Journal Article
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|a García, M Esther
|e verfasserin
|4 aut
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|a García-Vivó, Daniel
|e verfasserin
|4 aut
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| 700 |
1 |
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|a Ruiz, Miguel A
|e verfasserin
|4 aut
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| 700 |
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|a Vega, Patricia
|e verfasserin
|4 aut
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| 773 |
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|i Enthalten in
|t Organometallics
|d 1998
|g 42(2023), 19 vom: 09. Okt., Seite 2826-2838
|w (DE-627)NLM098167103
|x 0276-7333
|7 nnns
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|g volume:42
|g year:2023
|g number:19
|g day:09
|g month:10
|g pages:2826-2838
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|u http://dx.doi.org/10.1021/acs.organomet.3c00295
|3 Volltext
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