We conducted a joint synthetic, spectroscopic and computational study to explore the reactivity towards cyanide (from Bu4NCN) of a series of dinuclear complexes based on the M2Cp2(CO)3 scaffold (M = Fe, Ru; Cp = eta 5-C5H5), namely [M2Cp2(CO)2(mu -CO){mu,eta 1:eta 2-CH=C=CMe2}]BF4 (1Fe-Ru), [Ru2Cp2(CO)2(mu -CO){mu,eta 1:eta 2-C(Ph)=CHPh}]BF4 (2Ru) and [M2Cp2(CO)2(mu -CO){mu -CN(Me)(R)}]CF3SO3 (3Fe-Ru). While the reaction of 1Fe with Bu4NCN resulted in prevalent allenyl deprotonation, preliminary CO-NCMe substitution in 1Ru enabled cyanide addition to both the allenyl ligand (resulting in the formation of a h1:h2-allene derivative, 5A) and the two metal centers (affording 5B1 and 5B2). The mixture of 5B1-2 was rapidly converted into 5A in heptane solution at 100 degrees C, with 5A being isolated with a total yield of 60%. Following carbonyl-chloride substitution in 2Ru, CN- was incorporated as a terminal ligand upon Cl- displacement, to give the alkenyl complex 6 (84%). The reactivity of 3Fe and 3Ru is strongly influenced by both the metal element, M, and the aminocarbyne substituent, R. Thus, 7aRu was obtained with a 74% yield from cyanide attack on the carbyne in 3aRu (R = Cy, cyclohexyl), whereas the reaction involving the diiron counterpart 3aFe yielded an unclean mixture of the metastable 7aFe and the CO/CN- substitution product 8aFe. The cyano-alkylidene complexes 7aRu (R = Cy) and 7bFe (R = Me) underwent CO loss and carbene to carbyne conversion in isopropanol at 60-80 degrees C, giving 8aRu (48%) and 8bFe (71%), respectively. The novel compounds 5A, 5B1-2, 6 and 7aRu were characterized by IR and NMR spectroscopy, with the structure of 7aRu further elucidated by single crystal X-ray diffraction analysis. Additionally, the DFT-optimized structures of potential isomers of 5A, 5B1-2 and 6 were calculated.
Cinci, A., Ciancaleoni, G., Zacchini, S., Marchetti, F. (2024). Cyanide Addition to Diiron and Diruthenium Bis-Cyclopentadienyl Complexes with Bridging Hydrocarbyl Ligands. INORGANICS, 12(6), 1-21 [10.3390/inorganics12060147].
Cyanide Addition to Diiron and Diruthenium Bis-Cyclopentadienyl Complexes with Bridging Hydrocarbyl Ligands
Zacchini, Stefano
;
2024
Abstract
We conducted a joint synthetic, spectroscopic and computational study to explore the reactivity towards cyanide (from Bu4NCN) of a series of dinuclear complexes based on the M2Cp2(CO)3 scaffold (M = Fe, Ru; Cp = eta 5-C5H5), namely [M2Cp2(CO)2(mu -CO){mu,eta 1:eta 2-CH=C=CMe2}]BF4 (1Fe-Ru), [Ru2Cp2(CO)2(mu -CO){mu,eta 1:eta 2-C(Ph)=CHPh}]BF4 (2Ru) and [M2Cp2(CO)2(mu -CO){mu -CN(Me)(R)}]CF3SO3 (3Fe-Ru). While the reaction of 1Fe with Bu4NCN resulted in prevalent allenyl deprotonation, preliminary CO-NCMe substitution in 1Ru enabled cyanide addition to both the allenyl ligand (resulting in the formation of a h1:h2-allene derivative, 5A) and the two metal centers (affording 5B1 and 5B2). The mixture of 5B1-2 was rapidly converted into 5A in heptane solution at 100 degrees C, with 5A being isolated with a total yield of 60%. Following carbonyl-chloride substitution in 2Ru, CN- was incorporated as a terminal ligand upon Cl- displacement, to give the alkenyl complex 6 (84%). The reactivity of 3Fe and 3Ru is strongly influenced by both the metal element, M, and the aminocarbyne substituent, R. Thus, 7aRu was obtained with a 74% yield from cyanide attack on the carbyne in 3aRu (R = Cy, cyclohexyl), whereas the reaction involving the diiron counterpart 3aFe yielded an unclean mixture of the metastable 7aFe and the CO/CN- substitution product 8aFe. The cyano-alkylidene complexes 7aRu (R = Cy) and 7bFe (R = Me) underwent CO loss and carbene to carbyne conversion in isopropanol at 60-80 degrees C, giving 8aRu (48%) and 8bFe (71%), respectively. The novel compounds 5A, 5B1-2, 6 and 7aRu were characterized by IR and NMR spectroscopy, with the structure of 7aRu further elucidated by single crystal X-ray diffraction analysis. Additionally, the DFT-optimized structures of potential isomers of 5A, 5B1-2 and 6 were calculated.File | Dimensione | Formato | |
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