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Updated: Dec 13, 2025
The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
N-Heterocyclic Carbene Analogues of Nucleophilic Phosphinidene Transition Metal Complexes
Adinarayana Doddi1, Dirk Bockfeld2, Thomas Bannenberg2
1Department of Chemical Sciences, Indian Institute of, Science Education and Research Berhampur, Transit Campus, Govt. ITI Building, Engineering School Road, Ganjam, Berhampur, 760010, Odisha, India.
Abstract:
Chloride abstraction from the complexes [(η6 -p-cymene){(IDipp)P}MCl] (2 a, M=Ru; 2 b, M=Os) and [(η5 -C5 Me5 ){(IDipp)P}IrCl] (3 b, IDipp=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) with sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (NaBArF ) in the presence of trimethylphosphine (PMe3 ), 1,3,4,5-tetramethylimidazolin-2-ylidene (Me IMe) or carbon monoxide (CO) afforded the complexes [(η6 -p-cymene){(IDipp)P}M(PMe3 )]BArF ] (4 a, M=Ru; 4 b, M=Os), [(η6 -p-cymene){(IDipp)P}Os(Me IMe)]BArF ] (5) and [(η5 -C5 Me5 ){(IDipp)P}IrL][BArF ] (6, L=PMe3 ; 7, L=Me IMe; 8, L=CO). These cationic N-heterocyclic carbene-phosphinidene complexes feature very similar structural and spectroscopic properties as prototypic nucleophilic arylphosphinidene complexes such as low-field 31 P NMR resonances and short metal-phosphorus double bonds. Density functional theory (DFT) calculations reveal that the metal-phosphorus bond can be described in terms of an interaction between a triplet [(IDipp)P]+ cation and a triplet metal complex fragment ligand with highly covalent σ- and π-contributions. Crystals of the C-H activated complex 9 were isolated from solutions containing the PMe3 complex, and its formation can be rationalized by PMe3 dissociation and formation of a putative 16-electron intermediate [(η5 -C5 Me5 )Ir{P(IDipp)}I][BArF ], which undergoes C-H activation at one of the Dipp isopropyl groups and addition along the iridium-phosphorus bond to afford an unusual η3 -benzyl coordination mode.
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