Trans-C versus Cis-C thermally induced isomerisation of a terpyridine adduct of cytotoxic cycloruthenated compound

Ali, Moussa; Hamada, Adel; Habbita, Houda; Weckbach, Jennifer; Orvain, Christophe; Gaiddon, Christian; Pfeffer, Michel

doi:10.1016/j.jorganchem.2017.05.022

Cited by 5 publications

(5 citation statements)

References 29 publications

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“…We have shown recently that the terpyridine adducts of cycloruthenated units, 2 and 3 , can interconvert into each other when they are submitted to an external stimulus such as an increased temperature as depicted in eqs and . …”

Section: Resultsmentioning

confidence: 99%

Follow-Up Study of Trans-C to Cis-C Thermally or Photochemically Induced Isomerization of Terpyridine Adducts of Cycloruthenated 2-Aryl-2′-pyridine Compounds

Ali,

Cornaton,

Djukic

et al. 2024

Inorg. Chem.

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The mechanism of isomerization of the known 2-phenyl,pyridine (phpy) derivatives [Ru(phpy-κC,N) (MeCN-trans-N)(terpy)]PF 6 , 2, to [Ru-(phpy-κC,N)(MeCN-trans-C)(terpy)]PF 6 (terpy = 2,2′;6′,2″-terpyridine), 3, at temperatures >50 °C has been investigated both by 1 H NMR spectroscopy and by DFT calculations. The photoisomerization of 2 to 3 by UV light occurred also quantitatively in MeCN after 20 h at room temperature. A similar behavior to that of 2 could be established for the related compound [Ru(3-acridine-2′-C 5 H 4 N-κC,N)(MeCN-trans-N)(2,2′;6′,2″-terpyridine)]PF 6 , 6 (acridine = dibenzo[b,e]pyridine or 2,3-benzoquinoline), that was obtained from the reaction between [Ru(3-acridine-2′-C 5 H 4 N-κC,N) (MeCN) 4 ]PF 6 , 4, and terpy in MeOH/MeCN at 60 °C for 24 h. Similar to 2, the isomerization of 6 to [Ru(3-acridine-2′-C 5 H 4 N-κC,N)(MeCN-trans-C) (terpy)]PF 6 , 7, could be induced thermally (48 h at 60 °C in pure MeOH) or photochemically under UV radiation in MeCN at room temperature. A compound closely related to 7 but in which MeCN was replaced by H 2 O was described earlier (Tanaka et al. Inorg. Chem. 2012, 51, 5386−539). The presence of water on this compound had a dramatic effect as far as the coordination of terpy was concerned as its isomerization to a compound related to 6 (in which H 2 O instead of MeCN is coordinated to Ru) occurred indeed photochemically via irradiation with visible light.

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Section: Resultsmentioning

confidence: 99%

Follow-Up Study of Trans-C to Cis-C Thermally or Photochemically Induced Isomerization of Terpyridine Adducts of Cycloruthenated 2-Aryl-2′-pyridine Compounds

Ali,

Cornaton,

Djukic

et al. 2024

Inorg. Chem.

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“…Finally, the broad singlet at δ C 184.1 is for the acetate CO and the doublet of doublets at δ C 182.4 with 2 J(C,P) = 16.1, and 8.8 Hz is for the cyclometalated Ru-C3 ′ atom. Also, in this case, the resonance of C4 ′ is significantly downfield shifted compared to that of the free ligand (∆δ = 15.9) [62]. According to the procedure described for 4, the reaction of 3 with tpy affords the acetate [Ru(η 2 -OAc)(NC-tpy)((S,S)-Skewphos)] (5) isolated in 70% yield (Scheme 2).…”

Section: Synthesis Of Nc-and Nnn-terpyridine Ruthenium Complexes With...mentioning

confidence: 95%

“…tpy protons are at δH 8.61 and 8.48, and the latter upfield shifted compared to the free ligand (δ 8.69) [62] (Figure 1). In the 13 C{ 1 H} NMR spectrum, the cyclometalated carbon C3′ appears at δ 182.7 ( 2 J(C,P) = 18.0 and 8.4 Hz), whereas the signal at δ 184.5 is attributed to the carboxylate CO group.…”

Section: Synthesis Of Nc-and Nnn-terpyridine Ruthenium Complexes With...mentioning

confidence: 99%

“…The signals of the H6 and H6″ The 31 P{ 1 H} NMR spectrum of 1 in CD 2 Cl 2 displays two doublets at δ 56.7 and 52.0 with a 2 J(P,P) of 37.1 Hz, for the phosphorous trans to O and N atoms, respectively, as inferred from 2D 1 H-31 P HMBC NMR spectrum (Figure S7). The signals of the H6 and H6 ′′ tpy protons are at δ H 8.61 and 8.48, and the latter upfield shifted compared to the free ligand (δ 8.69) [62] (Figure 1).…”

Section: Synthesis Of Nc-and Nnn-terpyridine Ruthenium Complexes With...mentioning

confidence: 99%

“…Interestingly, the complexes [Ru(η 1 -OAc)(CO)(PP)(phen)]OAc [37,38] showed high cytotoxicity against cancer cell lines and reacted with NADH as a hydrogen donor, affording Ru-H species [39] that may play a role in disturbing the cellular redox homeostasis [40][41][42]. It is worth noting that ruthenium carboxylates are reactive species which can be employed for the synthesis of electron reach ruthenium cyclometalated complexes via a concerted carboxylate-assisted deprotonation process [43][44][45][46][47], which can find applications in catalysis [48][49][50][51][52][53][54][55][56][57], photochemistry [58][59][60], and medicine [61,62].…”

Section: Introductionmentioning

confidence: 99%

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Cyclometalated and NNN Terpyridine Ruthenium Photocatalysts and Their Cytotoxic Activity

Ballico,

Alessi,

Aneggi

et al. 2024

Molecules

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The cyclometalated terpyridine complexes [Ru(η2-OAc)(NC-tpy)(PP)] (PP = dppb 1, (R,R)-Skewphos 4, (S,S)-Skewphos 5) are easily obtained from the acetate derivatives [Ru(η2-OAc)2(PP)] (PP = dppb, (R,R)-Skewphos 2, (S,S)-Skewphos 3) and tpy in methanol by elimination of AcOH. The precursors 2, 3 are prepared from [Ru(η2-OAc)2(PPh3)2] and Skewphos in cyclohexane. Conversely, the NNN complexes [Ru(η1-OAc)(NNN-tpy)(PP)]OAc (PP = (R,R)-Skewphos 6, (S,S)-Skewphos 7) are synthesized in a one pot reaction from [Ru(η2-OAc)2(PPh3)2], PP and tpy in methanol. The neutral NC-tpy 1, 4, 5 and cationic NNN-tpy 6, 7 complexes catalyze the transfer hydrogenation of acetophenone (S/C = 1000) in 2-propanol with NaOiPr under light irradiation at 30 °C. Formation of (S)-1-phenylethanol has been observed with 4, 6 in a MeOH/iPrOH mixture, whereas the R-enantiomer is obtained with 5, 7 (50–52% ee). The tpy complexes show cytotoxic activity against the anaplastic thyroid cancer 8505C and SW1736 cell lines (ED50 = 0.31–8.53 µM), with the cationic 7 displaying an ED50 of 0.31 µM, four times lower compared to the enantiomer 6.

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Metal-Carbon Bonds of Heavier Group 7 and 8 Metals (Tc, Re, Ru, Os): Mononuclear Tc/Re/Ru/Os Complexes With Metal-Carbon Bonds

Wei

Jia

2021

Comprehensive Coordination Chemistry III

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Trans-C versus Cis-C thermally induced isomerisation of a terpyridine adduct of cytotoxic cycloruthenated compound

Cited by 5 publications

References 29 publications

Follow-Up Study of Trans-C to Cis-C Thermally or Photochemically Induced Isomerization of Terpyridine Adducts of Cycloruthenated 2-Aryl-2′-pyridine Compounds

Follow-Up Study of Trans-C to Cis-C Thermally or Photochemically Induced Isomerization of Terpyridine Adducts of Cycloruthenated 2-Aryl-2′-pyridine Compounds

Cyclometalated and NNN Terpyridine Ruthenium Photocatalysts and Their Cytotoxic Activity

Metal-Carbon Bonds of Heavier Group 7 and 8 Metals (Tc, Re, Ru, Os): Mononuclear Tc/Re/Ru/Os Complexes With Metal-Carbon Bonds

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