TY - JOUR

T1 - Synthesis, oxidation and unusual coordination chemistry of the diphosphete complex [(Cp′′′Co)2(μ,η4:4-(CH3CP)2)]

AU - Rummel, Eva-Maria

AU - Elsayed Moussa, Mehdi

AU - Parzefall, M

AU - Peresypkina, Eugenia V.

AU - Riesinger, Christoph

AU - Тимошкин, Алексей Юрьевич

AU - Balazs, Gabor

AU - Mastrorilli, Piero

AU - Todisco, Stefano

AU - Scheer, Manfred

PY - 2024/12/10

Y1 - 2024/12/10

N2 - Notwithstanding four decades of active research, very rare examples of diphosphabutadiene complexes arising from dimerisation of the phosphaalkyne CH3–C[triple bond, length as m-dash]P have been reported. Herein, we show that methyl phosphaalkyne dimerises in the coordination sphere of Cp′′′Co fragments to yield the unprecedented diphosphete complex [Cp′′′Co(η4-P2C2Me2)] (1) and the triple-decker complex [{Cp′′′Co}2(μ,η4:η4-P2C2Me2)] (2). Compound 2 can be oxidised with Ag[Al{OC(CF3)3}4] (Ag[TEF]) to give [{Cp′′′Co}2(μ,η4:η4-P2C2Me2)][TEF] (3). Additionally, it shows an unusual coordination behaviour towards copper halides and [W(CO)4(nbd)] (nbd = norbornadiene). Its reaction with CuCl leads to the formation of the 1D polymer [{Cp′′′Co}2(μ,η4:η2:η1:η1-P2C2Me2){Cu(μ-Cl)}2]n (6) while its reaction with CuBr, CuI and [W(CO)4(nbd)] results in the metallacyclic compounds [(Cp′′′Co){μ3,η4:η1:η1-P2C2Me2}(CH3CN){Cu(μ-X)}2]2 (X = Br (7a), I (7b)) and [Cp′′′Co{μ3,η4:η1:η1-P2C2Me2}{W(CO)4}]3 (8). In 6, an isomerisation of the diphosphete ring to a diphosphacyclopentadienyl ring occurs. In 7 and 8, the loss of Cp′′′Co moieties from the former compound 2 is observed. The formation of 1,3-diphosphete rings in 1 and 2 instead of the more thermodynamically favoured 1,2-diphosphete rings are explained by DFT computations.

AB - Notwithstanding four decades of active research, very rare examples of diphosphabutadiene complexes arising from dimerisation of the phosphaalkyne CH3–C[triple bond, length as m-dash]P have been reported. Herein, we show that methyl phosphaalkyne dimerises in the coordination sphere of Cp′′′Co fragments to yield the unprecedented diphosphete complex [Cp′′′Co(η4-P2C2Me2)] (1) and the triple-decker complex [{Cp′′′Co}2(μ,η4:η4-P2C2Me2)] (2). Compound 2 can be oxidised with Ag[Al{OC(CF3)3}4] (Ag[TEF]) to give [{Cp′′′Co}2(μ,η4:η4-P2C2Me2)][TEF] (3). Additionally, it shows an unusual coordination behaviour towards copper halides and [W(CO)4(nbd)] (nbd = norbornadiene). Its reaction with CuCl leads to the formation of the 1D polymer [{Cp′′′Co}2(μ,η4:η2:η1:η1-P2C2Me2){Cu(μ-Cl)}2]n (6) while its reaction with CuBr, CuI and [W(CO)4(nbd)] results in the metallacyclic compounds [(Cp′′′Co){μ3,η4:η1:η1-P2C2Me2}(CH3CN){Cu(μ-X)}2]2 (X = Br (7a), I (7b)) and [Cp′′′Co{μ3,η4:η1:η1-P2C2Me2}{W(CO)4}]3 (8). In 6, an isomerisation of the diphosphete ring to a diphosphacyclopentadienyl ring occurs. In 7 and 8, the loss of Cp′′′Co moieties from the former compound 2 is observed. The formation of 1,3-diphosphete rings in 1 and 2 instead of the more thermodynamically favoured 1,2-diphosphete rings are explained by DFT computations.

UR - https://pubs.rsc.org/en/content/articlelanding/2025/qi/d4qi02643h

U2 - 10.1039/D4QI02643H

DO - 10.1039/D4QI02643H

M3 - Article

JO - Inorganic Chemistry Frontiers

JF - Inorganic Chemistry Frontiers

SN - 2052-1545

ER -