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Expected and Unexpected Reactivities of Homoleptic LiNacNac and Heteroleptic NacNacMg(TMP) β-Diketiminates toward Various Small Unsaturated Organic Molecules.

ABSTRACT: Homoleptic LiNacNac forms simple donor-acceptor complexes with N,N'-dicyclohexylcarbodiimide (CyN═C═NCy), triphenylphosphine oxide (Ph₃P═O), and benzophenone (Ph₂CO). These crystallographically characterized compounds could be regarded as model intermediates en route to reducing the N═C, P═O, and C═O bonds of unsaturated substrates. Heteroleptic NacNacMg(TMP) intriguingly functions as a TMP nucleophile both with t-BuNCO and t-BuNCS, producing a urea or thiourea derivative respectively attached to Mg, though the NacNac ligand in the former reaction also engages noninnocently with a second t-BuNCO molecule via insertion at the reactive NacNac backbone γ-carbon site.

SUBMITTER: Gauld RM

PROVIDER: S-EPMC8154426 | biostudies-literature | 2021 Apr

REPOSITORIES: biostudies-literature

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Expected and Unexpected Reactivities of Homoleptic LiNacNac and Heteroleptic NacNacMg(TMP) β-Diketiminates toward Various Small Unsaturated Organic Molecules.

Gauld Richard M RM Lynch Jennifer R JR Kennedy Alan R AR Barker Jim J Reid Jacqueline J Mulvey Robert E RE

Inorganic chemistry 20210408 8

Homoleptic LiNacNac forms simple donor-acceptor complexes with N,N'-dicyclohexylcarbodiimide (CyN═C═NCy), triphenylphosphine oxide (Ph3P═O), and benzophenone (Ph2CO). These crystallographically characterized compounds could be regarded as model intermediates en route to reducing the N═C, P═O, and C═O bonds of unsaturated substrates. Heteroleptic NacNacMg(TMP) intriguingly functions as a TMP nucleophile both with t-BuNCO and t-BuNCS, producing a u ...[more]

PMID: 33830739

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Project description:Six homo- or heteroleptic tricationic Ir(R1-tpy)(R2-tpy)3+ complexes (Ir1-Ir6, R1/R2 = Ph, 4'-N(CH3)2Ph, pyren-1-yl, or 4'-{2-[2-(2-methoxyethoxy)ethoxy]ethoxy}Ph, tpy = 2,2';6',2"-terpyridine) were synthesized and tested for photodynamic therapy (PDT) effects. The ground- and excited-state characteristics of these complexes were studied systematically via spectroscopic methods and quantum chemistry calculations. All complexes possessed intraligand charge transfer (1ILCT) / metal-to-ligand charge transfer (1MLCT) dominated transition(s) in their low-energy absorption bands, which red-shifted with the increased electron-releasing strength of the R1/R2 substituent. Five of the complexes exhibited ligand-centered 3 π,π*/3ILCT/3MLCT emission. With a stronger electron-releasing R1/R2 substituent, the degree of charge transfer contribution increased, leading to a decrease of the emission quantum yield. When the 4'-N(CH3)2Ph substituent was introduced on both tpy ligands, the emission of Ir3 was completely quenched. Our study on the transient absorption of these complexes demonstrated that they all possessed broadband triplet excited-state absorption in the 400-800 nm region. Pyrenyl substitution of one or more tpy ligands, as in Ir4 and Ir5, increased the lifetimes of the lowest triplet excited state and the singlet oxygen (1O2) production efficiencies. Ir1-Ir5 were nontoxic toward SK-MEL-28 cells, with photocytotoxicities that varied from 0.18 to 153 µM. Among them, Ir4 had the highest 1O2 quantum yield (0.81) in cell-free conditions, showing the largest photocytotoxicity against SK-MEL-28 cells for Ir(III) PSs to date, and was the most efficient generator of reactive oxygen species (ROS) in vitro. Ir4 possessed a very large phototherapeutic index (PI = dark EC50 / light EC50) of >1657, the largest reported for an Ir(III) complex photosensitizer upon broadband visible light (400-700 nm) activation. Ir4 also exhibited a very strong PDT effect toward MCF-7 breast cancer cells and its xenograft tumor model. Upon 450-nm light activation, Ir4 dramatically inhibited the xenograft tumor growth and exhibited negligible side effects upon PDT treatment.

Dataset Information

Expected and Unexpected Reactivities of Homoleptic LiNacNac and Heteroleptic NacNacMg(TMP) β-Diketiminates toward Various Small Unsaturated Organic Molecules.

Publications

Expected and Unexpected Reactivities of Homoleptic LiNacNac and Heteroleptic NacNacMg(TMP) β-Diketiminates toward Various Small Unsaturated Organic Molecules.

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