Octacarbonyl-1κ4C,2κ4C-μ3-[cyclohexylphosphanido(2-)]-μ-hydrido-1:2κ2H-tricyclohexylphosphine-3κP-golddimanganese(Mn—Mn)

Flörke, Ülrich; Haupt, H.‐J.

doi:10.1107/s0108270194011522

Cited by 7 publications

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“…The presence of a bridging hydride in 7 was confirmed by a doublet at −16.76 ppm ( J P–H = 30 Hz) in the 1 H NMR, and the bridging phosphido group shows a downfield resonance at 190.5 ppm in the 31 P{ 1 H} NMR spectrum (Figures S22 and S23), consistent overall with the known analogues and 3 . , Additionally, the structure was confirmed using single-crystal XRD (Figure , top). Both Mn(I) centers are hexacoordinated with a Mn···Mn distance of 2.94 Å, which is comparable to the Mn···Mn distance reported for 3 (2.95 Å) and other dialkylphosphido-bridged analogues. , However, this short distance is not a M–M bond but a three-center–two-electron bond in the usual formalism for bridging hydride ligands.…”

Section: Resultssupporting

confidence: 64%

“…Both Mn(I) centers are hexacoordinated with a Mn•••Mn distance of 2.94 Å, which is comparable to the Mn•••Mn distance reported for 3 (2.95 Å) and other dialkylphosphido-bridged analogues. 19,27 However, this short distance is not a M−M bond but a three-center−two-electron bond in the usual formalism for bridging hydride ligands. Treatment of 7 with 1 equiv of (iPr) 2 PH at 80 °C leads to the near-quantitative formation of the new complex 6 (Scheme 5, top arrow) (Figures S17−S21).…”

Section: H} Nmr Experiments (Figures S31− S33)mentioning

confidence: 99%

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Activation of H₂ with Dinuclear Manganese(I)-Phosphido Complexes

2021

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There are few reports of activation of H2 across metal–phosphido linkages, and all of the first-row metal examples use N-heterocyclic phosphido donors. In this report, we highlight the discovery of H2 activation using first-row transition-metal phosphido complexes with alkyl and aryl substituents. The complex [Mn(CO)4(μ-PPh2)]2 (1) was treated with H2 (125 °C, 33 h), affording [{Mn(CO)4}(μ-H)(μ-PPh2){Mn(CO)3(Ph2PH)}] (2). Treating 2 with Mn2(CO)10 leads to PH bond activation and formation of [{Mn(CO)4}(μ-H)(μ-PPh2){Mn(CO)4}] (3). The interconversion of 1 to 3 is reversible, as indicated by the treatment of 3 with free Ph2PH, giving 2 at 80 °C or 1 and H2 at 120 °C. The isopropyl analogue of 1, [Mn(CO)4(μ-P(iPr)2)]2 (5), was synthesized by the oxidative addition of [(iPr)2PP(iPr)2] (4) with Mn2(CO)10. The reactivity of 5 is analogous to that of 1, forming [{Mn(CO)4}(μ-H)(μ-P(iPr)2){Mn(CO)3((iPr)2PH}] (6) on treatment with H2, which in turn reacts with Mn2(CO)10, quantitatively affording [{Mn(CO)4}(μ-H)(μ-P(iPr)2){Mn(CO)4}] (7). The chemistry diverges upon use of the tBu substituent. Treating Na[Mn(CO)5] with Cl(tBu)2P results in formation of the bis-(tBu2P) hexacarbonyl complex [Mn(CO)3(μ-PtBu2)]2 (8), a dark green compound with a formal M–M double bond (2.5983(5) Å). 8 reacts sluggishly with H2 to form free tBu2PH and [MnH(CO)4(HPtBu2)] (10). The activation of H2 with 1 is incomplete even at high temperatures. In contrast, facile activation of H2 occurs with [{Mn(CO)3(μ-PPh2)}2(μ-CO)] (1-CO) to yield 2 (84%, 70 °C, 10 h), implicating thermally demanding CO dissociation from 1 as the first step in the H2 activation. PCl bond activation under hydrogenative conditions was also examined. The reactions between Mn2(CO)10 and ClPh2P or Cl(iPr)2P under 1 atm of H2 gave 3 (R = Ph) or 7 (R = iPr) in 50–60% yield, indicating the intermediacy of bisphosphido compounds. When Cl(tBu)2P was used instead, the compounds cis-[Mn(CO)4(H)((tBu2)P)2H)] (10), [Mn(CO)3(H)((tBu2)P)2H] (11), and diaxial-[Mn(CO)4((tBu2)PH)]2 (12) were isolated, indicating PCl bond hydrogenation to phosphines using H2 and Mn2(CO)10.

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Section: Resultssupporting

confidence: 64%

Section: H} Nmr Experiments (Figures S31− S33)mentioning

confidence: 99%

Activation of H₂ with Dinuclear Manganese(I)-Phosphido Complexes

2021

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“…The P−Au−P bond angle (173.7(3)°) is slightly less than the ideal angle of 180°. A similar deviation from the ideal 180° P−Au−P bond angle was observed in the isoelectronic homometallic complex Mn 2 (CO) 8 [μ-P(Cy)(AuPCy 3 )](μ-H), which was reported to have a P−Au−P angle of 171.12(5)° …”

Section: Resultssupporting

confidence: 65%

Synthesis, Characterization, and Reactivity of the Heterometallic Dinuclear μ-PH₂and μ-PPhH Complexes FeMn(CO)₈(μ-PH₂) and FeMn(CO)₈(μ-PPhH)

Colson

Whitmire

2010

Organometallics

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Deprotonation of Fe(CO)4PRH2 and treatment with Mn(CO)5Br afforded the dinuclear complexes FeMn(CO)8(μ-PRH) (1a, R = H; 1b, R = Ph), which contain the relatively rare μ-PH2 and μ-PPhH functionalities. The heterometallic nature of these complexes was confirmed by mass spectrometry, and the molecular structures of 1a and 1b were determined by X-ray diffraction experiments. Deprotonation of 1b and subsequent addition of Mn(CO)5Br or AuPPh3Cl yielded the trinuclear complexes FeMn(CO)8[μ-PPh(Mn(CO)5)] (3a) and FeMn(CO)8[μ-PPh(AuPPh3)] (3b), both of which were characterized structurally and spectroscopically. Deprotonation of 1a at room temperature resulted in rapid coupling of the deprotonated product [2a] − with neutral 1a to form M+[FeMn(CO)8(μ3-PH)Mn(CO)4(μ-PH2)Fe(CO)4]− (M+ [4] − ) (M+ = Li+, Na+, K+), the formation of which was observed using in situ infrared spectroscopy. M+ [4] − was found to decompose upon solvent removal, and the structure of [4] − was elucidated by examination of spectroscopic data. The 1H NMR spectrum of [4] - was characterized by first-order [ABMX] and [AMX] spin systems, and ESI-MS data confirmed that [4] − was formed by direct coupling of [2a] − with 1a without concomitant fragmentation or loss of CO ligands. Deprotonation of 1a at lower temperatures slowed the coupling process, allowing for the metalation of the monomeric anion [2a] − by treatment with AuPPh3Cl, the product of which was found to decompose gradually in solution and rapidly upon concentration.

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“…19,21 Additionally, the structure was confirmed using single-crystal XRD (Figure 2). Both the Mn(I) centers are hexa-coordinated with a Mn•••Mn distance of 2.94 Å, which is comparable to the Mn•••Mn distance reported for 3 (2.95 Å) and other dialkyl-phosphido bridged analogues, 19,22 however, this short distance is not a M-M bond but a 3-centered 2-electron bond in the usual formalism for bridging hydride ligands. Reaction of 7 and one equivalent of (iPr)2PH at 80 °C leads to the near quantitative formation of the new complex 6 (Figures S11-S15).…”

Section: Scheme 2 Observed Reversibility Of Mn-p/h2 Activationsupporting

confidence: 64%

Activation of H2 with Manganese(I)-Phosphido Complexes

Abhyankar

MacMillan

Lacy

2021

Preprint

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Metal-ligand cooperativity (MLC) predominantly occurs across transition-metal amido moieties. In contrast, there are few reports of activation of H2 or substrate across metal-phosphido linkages, and all of the first-row metal examples use N-heterocyclic phosphido donors. In this report, we highlight a discovery of the first MLC dihydrogen activation with first-row transition metal M-PR2 (R = alkyl or aryl) complexes using dinuclear Mn(I)-bisphosphido complexes. In addition, we demonstrate that oxidative addition of P-Cl bond leads to the same Mn(I)-bisphosphido complexes at elevated temperatures, enabling a simple and versatile strategy for in-situ reduction of phosphine chlorides to phosphine using dihydrogen, a process that appears general having success with both diaryl-and dialkyl-phosphines.

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Octacarbonyl-1κ4C,2κ4C-μ3-[cyclohexylphosphanido(2-)]-μ-hydrido-1:2κ2H-tricyclohexylphosphine-3κP-golddimanganese(Mn—Mn)

Cited by 7 publications

References 1 publication

Activation of H₂ with Dinuclear Manganese(I)-Phosphido Complexes

Activation of H₂ with Dinuclear Manganese(I)-Phosphido Complexes

Synthesis, Characterization, and Reactivity of the Heterometallic Dinuclear μ-PH₂and μ-PPhH Complexes FeMn(CO)₈(μ-PH₂) and FeMn(CO)₈(μ-PPhH)

Activation of H2 with Manganese(I)-Phosphido Complexes

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Octacarbonyl-1κ4C,2κ4C-μ3-[cyclohexylphosphanido(2-)]-μ-hydrido-1:2κ2H-tricyclohexylphosphine-3κP-golddimanganese(Mn—Mn)

Cited by 7 publications

References 1 publication

Activation of H2 with Dinuclear Manganese(I)-Phosphido Complexes

Activation of H2 with Dinuclear Manganese(I)-Phosphido Complexes

Synthesis, Characterization, and Reactivity of the Heterometallic Dinuclear μ-PH2and μ-PPhH Complexes FeMn(CO)8(μ-PH2) and FeMn(CO)8(μ-PPhH)

Activation of H2 with Manganese(I)-Phosphido Complexes

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Activation of H₂ with Dinuclear Manganese(I)-Phosphido Complexes

Activation of H₂ with Dinuclear Manganese(I)-Phosphido Complexes

Synthesis, Characterization, and Reactivity of the Heterometallic Dinuclear μ-PH₂and μ-PPhH Complexes FeMn(CO)₈(μ-PH₂) and FeMn(CO)₈(μ-PPhH)