Terminal Molybdenum Phosphides with d Electrons: Radical Character Promotes Coupling Chemistry

Buss, Joshua A.; Oyala, Paul H.; Agapie, Theodor

doi:10.1002/ange.201707921

Cited by 14 publications

(2 citation statements)

References 75 publications

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“…[2] Exceptions to these elements include the recently reported rhenium(V) phosphide with an aliphatic PNP ligand, [3] the C 3 symmetric anionic phosphide salt of niobium(V) [4] and the partially characterized tantalum(V) [5] supported by a three‐fold symmetric and tetra‐dentate ligand (Figure 1). Recently, the groups of Agapie and Schneider have reported Mo [2i] and Re [3] phosphido complexes (Figure 1) to undergo oxidative coupling to form bimolecular or unimolecular systems containing the P−P linkage, respectively. Their reactivity contrasts Cummins reductive splitting of a butterfly‐like Nb 2 (μ 2 : η 2 ,η 2 ‐P 2 ) scaffold to form an anionic niobium phosphido ligand [4a] .…”

Section: Figurementioning

confidence: 99%

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Metal‐Ligand Cooperativity to Assemble a Neutral and Terminal Niobium Phosphorus Triple Bond (Nb≡P)

et al. 2022

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Decarbonylation along with P‐atom transfer from the phosphaethynolate anion, PCO−, to the NbIV complex [(PNP)NbCl2(NtBuAr)] (1) (PNP=N[2‐PiPr2‐4‐methylphenyl]2−; Ar=3,5‐Me2C6H3) results in its coupling with one of the phosphine arms of the pincer ligand to produce a phosphanylidene phosphorane complex [(PNPP)NbCl(NtBuAr)] (2). Reduction of 2 with CoCp*2 cleaves the P−P bond to form the first neutral and terminal phosphido complex of a group 5 transition metal, namely, [(PNP)Nb≡P(NtBuAr)] (3). Theoretical studies have been used to understand both the coupling of the P‐atom and the reductive cleavage of the P−P bond. Reaction of 3 with a two‐electron oxidant such as ethylene sulfide results in a diamagnetic sulfido complex having a P−P coupled ligand, namely [(PNPP)Nb=S(NtBuAr)] (4).

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Section: Figurementioning

confidence: 99%

“…Given the precedence for oxidative coupling of terminal phosphido complexes of Mo and Re, [2i, 3] we inquired if such reactivity could occur between the phosphine arm of PNP and a putative Nb phosphido radical cation. Accordingly, chemical oxidation of 3 with various one‐electron oxidants resulted in complicated mixtures.…”

Section: Figurementioning

confidence: 99%

Metal‐Ligand Cooperativity to Assemble a Neutral and Terminal Niobium Phosphorus Triple Bond (Nb≡P)

et al. 2022

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A Low‐Valent Molybdenum Nitride Complex: Reduction Promotes Carbonylation Chemistry

2018

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Toward nitrogen functionalization, reactive terminal transition metal nitrides with high d‐electron counts are of interest. A series of terminal MoIV nitride complexes were prepared within the context of exploring nitride/carbonyl coupling to cyanate. Reduction affords the first MoII nitrido complex, an early metal nitride with four valence d‐electrons. The binding mode of the para‐terphenyl diphosphine ancillary ligand changes to stabilize an electronic configuration with a high electron count and a formal M−N bond order of three. Even with an intact Mo≡N bond, this low‐valent nitrido complex proves to be highly reactive, readily undergoing N‐atom transfer upon addition of CO, releasing cyanate anion.

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Molecular Mimics of Heterogeneous Metal Phosphides: Thermochemistry, Hydride‐Proton Isomerism, and HER Reactivity

et al. 2018

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A new series of low‐valent dinuclear molybdenum complexes bearing phosphido or phosphinidene bridging ligands was synthesized as a structural model of heterogeneous metal phosphide catalysts. Addition of acid to a monocationic Mo2‐μ‐P complex results in phosphide protonation, affording a dicationic Mo2‐μ‐PH species. Alternatively, reaction of an isoelectronic Mo2‐μ‐P precursor with LiBEt3H gives a Mo2H‐μ‐P complex. Mixing these species, one bearing a Mo−H and the other a P−H bond, results in facile H2 production at room temperature.

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Terminal Molybdenum Phosphides with d Electrons: Radical Character Promotes Coupling Chemistry

Cited by 14 publications

References 75 publications

Metal‐Ligand Cooperativity to Assemble a Neutral and Terminal Niobium Phosphorus Triple Bond (Nb≡P)

Metal‐Ligand Cooperativity to Assemble a Neutral and Terminal Niobium Phosphorus Triple Bond (Nb≡P)

A Low‐Valent Molybdenum Nitride Complex: Reduction Promotes Carbonylation Chemistry

Molecular Mimics of Heterogeneous Metal Phosphides: Thermochemistry, Hydride‐Proton Isomerism, and HER Reactivity

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