Versatile Reactivity of Half-Sandwich Rhodium(III) Iminophosphonamide Complexes

Nekrasov, R.I.; Peganova, T.A.; Fedyanin, I.V.; Gutsul, E.I.; Filippov, O.A.; Belkova, N.V.; Kalsin, A.M.

Авторы: Nekrasov Roman I., Peganova Tat’yana A., Fedyanin Ivan V., Gutsul Evgenii I., Filippov Oleg A., Belkova Natalia V., Kalsin Alexander M.
Журнал: Inorganic Chemistry
Том: 61
Номер: 40
Год издания: 2022
Издательство: American Chemical Society
Местоположение издательства: United States
Первая страница: 16081
Последняя страница: 16092
DOI: 10.1021/acs.inorgchem.2c02478
Аннотация: Novel 18e̅ and 16e̅ pentamethylcyclopentadienyl rhodium(III) complexes [(η5-C5Me5)RhX(NPN)] (1a,b, X = Cl; 2a−c, X = PF6, BAr4F) with chelating zwitterionic iminophosphonamide (NPN) ligands (Ph2P(NR)(NR′); a, R = R′ = p-Tol; b, R =p-Tol, R′ = Me; c, R = R′ = Me) were synthesized and characterized by single-crystal X-ray diffraction. In the 16e̅ complexes 2, the rhodium (Rh) atom is efficiently stabilized by π-donation of unshared N electrons, thus hampering coordination of the external ligands and rendering the 18e̅ complexes labile. Due to low coordination enthalpy, the cationic 18e̅ monocarbonyl and pyridine adducts 2a·L are stable only at low temperatures. At room temperature, 2·CO adducts readily give stable carbonyl−carbamoyl complexes [(η5-C5Me5)Rh(CO){(CO(NR′)Ph2P(NR)}]+ (4) formed as a result of CO insertion into the Rh−N bond, thus showing high nucleophilicity of the N atoms in 18e̅ complexes. High basicity of the Na+NPN− precursors caused side deprotonation of the η5-C5Me5 ligand during the synthesis of 1 that yields unstable fulvene Rh(I) complexes [(η4-C5Me4CH2)Rh{Ph2P(NR)-(NR′)2}] (3a,b). Complex 3a undergoes a facile reaction with isoprene to yield an unusual [(η5:η1-C5Me4(CH2)C(Me)=CHCH2)Rh(NPN)] complex - the first example of intermolecular 1,4-metallacycloaddition of diene to the Rh−fulvene complex.
Добавил в систему: Кальсин Александр Михайлович

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Versatile Reactivity of Half-Sandwich Rhodium(III) Iminophosphonamide Complexesстатья

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