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Experimental and Computational Studies of Ruthenium Complexes Bearing Z-Acceptor Aluminum-Based Phosphine Pincer Ligands.

ABSTRACT: Reaction of [Ru(C₆H₄PPh₂)₂(Ph₂PC₆H₄AlMe(THF))H] with CO results in clean conversion to the Ru-Al heterobimetallic complex [Ru(AlMePhos)(CO)₃] (1), where AlMePhos is the novel P-Al(Me)-P pincer ligand (o-Ph₂PC₆H₄)₂AlMe. Under photolytic conditions, 1 reacts with H₂ to give [Ru(AlMePhos)(CO)₂(μ-H)H] (2) that is characterized by multinuclear NMR and IR spectroscopies. DFT calculations indicate that 2 features one terminal and one bridging hydride that are respectively anti and syn to the AlMe group. Calculations also define a mechanism for H₂ addition to 1 and predict facile hydride exchange in 2 that is also observed experimentally. Reaction of 1 with B(C₆F₅)₃ results in Me abstraction to form the ion pair [Ru(AlPhos)(CO)₃][MeB(C₆F₅)₃] (4) featuring a cationic [(o-Ph₂PC₆H₄)₂Al]⁺ ligand, [AlPhos]⁺. The Ru-Al distance in 4 (2.5334(16) Å) is significantly shorter than that in 1 (2.6578(6) Å), consistent with an enhanced Lewis acidity of the [AlPhos]⁺ ligand. This is corroborated by a blue shift in both the observed and computed ν_CO stretching frequencies upon Me abstraction. Electronic structure analyses (QTAIM and EDA-ETS) comparing 1, 4, and the previously reported [Ru(ZnPhos)(CO)₃] analogue (ZnPhos = (o-Ph₂PC₆H₄)₂Zn) indicate that the Lewis acidity of these pincer ligands increases along the series ZnPhos < AlMePhos < [AlPhos]⁺.

SUBMITTER: Isaac CJ

PROVIDER: S-EPMC9768752 | biostudies-literature | 2022 Dec

REPOSITORIES: biostudies-literature

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Experimental and Computational Studies of Ruthenium Complexes Bearing Z-Acceptor Aluminum-Based Phosphine Pincer Ligands.

Isaac Connie J CJ Wilson Cameron I CI Burnage Arron L AL Miloserdov Fedor M FM Mahon Mary F MF Macgregor Stuart A SA Whittlesey Michael K MK

Inorganic chemistry 20221207 50

Reaction of [Ru(C6H4PPh2)2(Ph2PC6H4AlMe(THF))H] with CO results in clean conversion to the Ru-Al heterobimetallic complex [Ru(AlMePhos)(CO)3] (1), where AlMePhos is the novel P-Al(Me)-P pincer ligand (o-Ph2PC6H4)2AlMe. Under photolytic conditions, 1 reacts with H2 to give [Ru(AlMePhos)(CO)2(μ-H)H] (2) that is charact ...[more]

PMID: 36475641

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Project description:A new family of cyclometalated ruthenium(II) complexes [Ru(N^N)2(C^N)]+ derived from the π-extended benzo[h]imidazo[4,5-f]quinolone ligand appended with thienyl groups (n = 1-4, compounds 1-4) was prepared and its members were characterized for their chemical, photophysical, and photobiological properties. The lipophilicities of 1-4, determined as octanol-water partition coefficients (log Po/w), were positive and increased with the number of thienyl units. The absorption and emission bands of the C^N compounds were red-shifted by up to 200 nm relative to the analogous Ru(II) diimine systems. All of the complexes exhibited dual emission with the intraligand fluorescence (1IL, C^N-based) shifting to lower energies with increasing n and the metal-to-ligand charge transfer phosphorescence (3MLCT, N^N-based) remaining unchanged. Compounds 1-3 exhibited excited state absorption (ESA) profiles consistent with lowest-lying 3MLCT states when probed by nanosecond transient absorption (TA) spectroscopy with 532 nm excitation and had contributions from 1IL(C^N) states with 355 nm excitation. These assignments were supported by the lifetimes observed (<10 ns for the 1IL states and around 20 ns for the 3MLCT states) as well as a noticeable ESA for 3 with 355 nm excitation that did not occur with 532 nm excitation. Compound 4 was the only member of the family with two 3MLCT emissive lifetimes (15, 110 ns), and the TA spectra collected with both 355 and 532 nm excitation was assigned to the 3IL state, which was corroborated by its 4-6 μs lifetime. The ESA for 4 had a rise time of approximately 10 ns and an initial decay of 110 ns, which suggests a possible 3MLCT-3IL excited state equilibrium that results in delayed emission from the 3MLCT state. Compound 4 was nontoxic toward human skin melanoma cells (SKMEL28) in the dark (EC50 = >300 μM); 1-3 were cytotoxic and yielded EC50 values between 1 and 20 μM. The photocytotoxicites with visible light ranged from 87 nM with a phototherapeutic index (PI) of 13 for 1 to approximately 1 μM (PI = >267) for 4. With red light, EC50 values varied from 270 nM (PI = 21) for 3 to 12 μM for 4 (PI = >25). The larger PIs for 4, especially with visible light, were attributed to the much lower dark cytotoxicity for this compound. Because the dark cytotoxicity contributes substantially to the observed photocytotoxicity for 1-3, it was not possible to assess whether the 3IL state of 4 led to a much more potent phototoxic mechanism in the absence of dark toxicity. There was no stark contrast in cellular uptake and accumulation by laser scanning confocal and differential interference contrast microscopy to explain the large differences in dark toxicities between 1-3 and 4. Nevertheless, the study highlights a new family of Ru(II) C^N complexes where π-conjugation beyond a certain point results in low dark cytotoxicity with high photocytotoxicity, opposing the notion that cyclometalated Ru(II) systems are too toxic to be phototherapeutic agents.

Dataset Information

Experimental and Computational Studies of Ruthenium Complexes Bearing Z-Acceptor Aluminum-Based Phosphine Pincer Ligands.

Publications

Experimental and Computational Studies of Ruthenium Complexes Bearing <i>Z</i>-Acceptor Aluminum-Based Phosphine Pincer Ligands.

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