Protonenaustausch in Re(CO)4(μ‐H)(μ‐PPh2)Mo(η5‐C5H5)(CO)2 gegen Triphenylphosphan‐IB‐Metallkationen

Haupt, H.‐J.; Flörke, Ülrich; Disse, G.; Heinekamp, C.

doi:10.1002/cber.19911241008

Cited by 12 publications

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References 22 publications

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“…These parameters are comparable to those of the hydride complex 2a (δ P = 1.4 ppm, 1 J PH = 343 Hz). We note that similar anionic complexes [MoMCp(μ-PPh 2 )(CO) 6 ] − have been reported as being formed through deprotonation of the corresponding neutral hydrides [MoMCp(μ-H)(μ-PPh 2 )(CO) 6 ] (M = Re and Mn) . As expected, anion 3 reacted with NH 4 PF 6 to give the corresponding hydride-bridged derivative 2a in good yield.…”

Section: Resultssupporting

confidence: 79%

E–H Bond Cleavage Processes in Reactions of Heterometallic Phosphinidene-Bridged MoRe and MoMn Complexes with Hydrogen and p-Block Element Hydrides

Alvarez,

García,

García-Vivó

et al. 2023

Organometallics

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Reactions of complexes [MoMCp(μ-PMes*)(CO) 6 ] with H 2 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-C 6 H 2 t Bu 3 ]. The reaction with H 2 (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 H 3 SiPh 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 PHCy 2 , which just yielded the substituted derivatives [MoMCp(μ-PMes*)(CO) 5 (PHCy 2 )]. Reactions with HSnPh 3 again resulted in E−H bond cleavage, but now with the stannyl group terminally bound to M, while 1a reacted with BH 3 •PPh 3 to give the hydride-bridged derivatives [MoReCp(μ-H)(μ-PHMes*)(CO) 5 (PPh 3 )] and [MoReCp(μ-H){μ-P(CH 2 CMe 2 )C 6 H 2t Bu 2 }(CO) 5 (PPh 3 )], which follow from hydrogenation, C−H cleavage, and CO/PPh 3 substitution steps. Density functional theory calculations on the PPhbridged analogue of 1a revealed that hydrogenation likely proceeds through the addition of H 2 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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Section: Resultssupporting

confidence: 79%

E–H Bond Cleavage Processes in Reactions of Heterometallic Phosphinidene-Bridged MoRe and MoMn Complexes with Hydrogen and p-Block Element Hydrides

Alvarez,

García,

García-Vivó

et al. 2023

Organometallics

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Erste Cluster mit im Festkörper Y‐förmig dreifach koordinierten Rh^I‐Atomen: [M¹M²{μ‐P(C₆H₁₁)₂}(CO)₈Rh(PPh₃)] (M¹, M² = Mn, Re)

1995

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hochsten negativen von -0.07 C-2 sowie C-5 auf (Abb. 2). Niedrigere Partialladungen treten an C-8 (0.03) und C-I 0 (-0.02) auf. Alle anderen C-Atome des Fullerengeriistes tragen Partialladungen von 0.00 ?C 0.01. Das am starksten negativ polarisierte StickstofPatom des Azids (AM 1) ist das R-substituierte (Abb. 2). Ein kinetisch kontrollierter Angriff des Azids an 1 a fiihrt daher stark bevorzugt zu 6a. Bereits bei Raumtemperatur lagert sich 6a langsam in 4 a und 5 a im Verhaltnis 6:l um.

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The First Clusters with a Y‐Shaped Arrangement of Ligands at Three‐Coordinate Rh^I Atoms in the Solid State: [M¹M²{μ‐P(C₆H₁₁)₂}(CO)₈Rh(PPh₃)] (M¹, M² = Mn, Re)

Beckers

Flörke

Haupt

1995

Angew. Chem. Int. Ed. Engl.

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Protonenaustausch in Re(CO)₄(μ‐H)(μ‐PPh₂)Mo(η⁵‐C₅H₅)(CO)₂ gegen Triphenylphosphan‐IB‐Metallkationen

Cited by 12 publications

References 22 publications

E–H Bond Cleavage Processes in Reactions of Heterometallic Phosphinidene-Bridged MoRe and MoMn Complexes with Hydrogen and p-Block Element Hydrides

E–H Bond Cleavage Processes in Reactions of Heterometallic Phosphinidene-Bridged MoRe and MoMn Complexes with Hydrogen and p-Block Element Hydrides

Erste Cluster mit im Festkörper Y‐förmig dreifach koordinierten Rh^I‐Atomen: [M¹M²{μ‐P(C₆H₁₁)₂}(CO)₈Rh(PPh₃)] (M¹, M² = Mn, Re)

The First Clusters with a Y‐Shaped Arrangement of Ligands at Three‐Coordinate Rh^I Atoms in the Solid State: [M¹M²{μ‐P(C₆H₁₁)₂}(CO)₈Rh(PPh₃)] (M¹, M² = Mn, Re)

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Protonenaustausch in Re(CO)4(μ‐H)(μ‐PPh2)Mo(η5‐C5H5)(CO)2 gegen Triphenylphosphan‐IB‐Metallkationen

Cited by 12 publications

References 22 publications

E–H Bond Cleavage Processes in Reactions of Heterometallic Phosphinidene-Bridged MoRe and MoMn Complexes with Hydrogen and p-Block Element Hydrides

E–H Bond Cleavage Processes in Reactions of Heterometallic Phosphinidene-Bridged MoRe and MoMn Complexes with Hydrogen and p-Block Element Hydrides

Erste Cluster mit im Festkörper Y‐förmig dreifach koordinierten RhI‐Atomen: [M1M2{μ‐P(C6H11)2}(CO)8Rh(PPh3)] (M1, M2 = Mn, Re)

The First Clusters with a Y‐Shaped Arrangement of Ligands at Three‐Coordinate RhI Atoms in the Solid State: [M1M2{μ‐P(C6H11)2}(CO)8Rh(PPh3)] (M1, M2 = Mn, Re)

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Protonenaustausch in Re(CO)₄(μ‐H)(μ‐PPh₂)Mo(η⁵‐C₅H₅)(CO)₂ gegen Triphenylphosphan‐IB‐Metallkationen

Erste Cluster mit im Festkörper Y‐förmig dreifach koordinierten Rh^I‐Atomen: [M¹M²{μ‐P(C₆H₁₁)₂}(CO)₈Rh(PPh₃)] (M¹, M² = Mn, Re)

The First Clusters with a Y‐Shaped Arrangement of Ligands at Three‐Coordinate Rh^I Atoms in the Solid State: [M¹M²{μ‐P(C₆H₁₁)₂}(CO)₈Rh(PPh₃)] (M¹, M² = Mn, Re)