Cyclometalated Osmium Compounds and beyond: Synthesis, Properties, Applications
Abstract
:1. Introduction
2. Historical Background
3. Main Precursors
3.1. [OsX2(PR3)3]
3.1.1. mono-Osmacycles
3.1.2. Pincer and bis-Cyclometalated Complexes
3.1.3. Others Osmacycles
3.2. [OsX2(CO)(PR3)3]
3.3. Osmium Hydride Complexes
3.3.1. [OsH6(PR3)2]
3.3.2. bis- and tris-Osmacycles
3.4. [Os(η6-arene)Cl2]2
3.4.1. mono-Osmacycles
3.4.2. bis- and tris-Osmacycles
3.5. Other Precursors
4. Representative Reactions of Osmacycles
4.1. Reactivity of Chelate and Pincer Complexes
4.2. Reactions of Hydride Complexes
4.3. Ligand Substitution in Osmacycles
5. Applications of Osmacycles
5.1. Catalysis
5.2. Chemical Sensors and Biosensors
5.3. Electronic Properties and Photophysics
5.4. Anticancer and Biological Properties
6. Conclusions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
Abbreviation
2-MeTHF | 2-methyl-tetrahydrofuran |
A2780 | Human ovarian cancer cell line |
A549 | Human lung cancer cell line |
AND/OR | Boolean operator for browsing in databases |
ATRP | Atom Transfer Radical Polymerization |
B3LYP | Becke three-parameter exchange and Lee–Yang–Parr correlation |
BJAB | Burkitt-like lymphoma |
Bn | Benzyl substituent |
bpy | 2,2′-bipyridine |
C~C’~N | Pincer ligand with Carbon-Carbon-Nitrogen, as donor atoms |
C~C~C | Pincer ligand with Carbon-Carbon-Carbon, as donor atoms |
C~C~C~C | Tetradentate Ligand with Carbon-Carbon-Carbon-Carbon as donor atoms |
C~E | Bidentate ligand with Carbon and E as donor atoms |
C~N | Bidentate ligand with Carbon and Nitrogen as donor atoms |
C~N~C | Pincer ligand with Carbon-Nitrogen-Carbon as donor atoms |
C~N~N | Pincer ligand with Carbon-Nitrogen-Nitrogen as donor atoms |
C~N~O | Pincer ligand with Carbon-Nitrogen-Oxygen as donor atoms |
C~O | Bidentate ligand with Carbon and Oxygen as donor atoms |
CC50 | 50% Cytotoxic concentration |
CHI/PA-1 | Human ovarian carcinoma cells |
cod | 1,4-cyclo-octadiene |
DFT | Density Funtional Theory |
DMSO | Dimethyl sulphoxide |
DNA | Deoxyribonucleic acid |
dpbH | 1,3-di(2-pyridyl)benzene |
dppb | 1,4-bis(diphenylphosphino)butane |
E | Donor atom such as: N, P, O, S, As, Se |
EC50 | 50% Effective concentration |
GO | Glucose oxidase |
HBMePI | 1,3-bis(6′-methylpyridyl-2′-imino)isoindoline |
HEK293 | Kidney adenocarnocinoma cell line |
HeLa | Cervical cancer cell line |
HOMO | Highest Occupied Molecular Orbital |
HRP | Horseradish peroxidase |
IC50 | 50% Inhibitory concentration |
ILCT | Intraligand Charge-Transfer |
log(Po/w) | N-Octanol-water partition coefficient |
LUMO | Lowest Unoccupied Molecular Orbital |
Mebib | 2-deprotonated form of 1,3-bis(N-methylbenzimidazolyl)benzene |
Mebip | bis(N-methylbenzimidazolyl)pyridine) |
MLCT | Metal-to-Ligand Charge Transfer |
MT4 | Leukemia cell line |
N~C~N | Pincer ligand with Nitrogen-Carbon-Nitrogen as donor atoms |
N~N | Bidentate ligand with Nitrogen-Nitrogen as donor atoms |
N~N~N | Terdentate ligand where the atom donors are Nitrogen |
Nalm6 | Leukemia cell line |
NHC | N-Heterocyclic Carbene |
NHE | Normal Hydrogen Electrode |
NMR | Nuclear Magnetic Resonance |
OLED | Organic Light-Emitting Diode |
Otf | Triflate |
P~C(H)~P | Ligand with only phosphorous as donor atoms |
P~C~P | Pincer ligand with phosphorous–carbon–phosphorous as donor atoms |
PDT | Photodynamic Therapy |
PhMeBIm | 1-Phenyl-3-methyl-1H-benzimidazolium |
phen | 1,10-Phenanthroline |
phpyH | 2-Phenylpyridine |
PMMA | Polymethylmethacrylate |
ROS | Reactive Oxygen Species |
SCE | Saturated Calomel Electrode |
SW480 | Colon adenocarcinoma cell line |
TAML | Tetra-Amido Macrocyclic Ligand |
TD-DFT | Time-Dependent Density Functional Theory |
TOF | Turnover Frequency |
tterpy | 4′-tolyl-2,2′,6′,2”-terpyridine ligand |
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Precursor | Cyclometalated Ligand | Osmacycle | Ref. |
---|---|---|---|
[Os3(CO)12] | L1 | 1 speculative mixture of cis or trans | [28] |
[OsH(O2CCF3)(CO)(PPh3)2] | L2 | 2 | [29] |
cis-[Os(PMe3)4H(CH2C(Me)3)] | PMe3 L3 | 3 | [30] |
[Os(p-cymene)Me(Cl)(Me2SO)] prepared from [Os(p-cymene)Cl2]2 | L4 | 4 | [31] |
[Os(tterpy)(O)2(OH)(NO3)] prepared from K2[Os(O)2(OH)4] | L5 | 5 | [32] |
[Os(tterpy)(O)2(OH)(NO3)] prepared from K2[Os(O)2(OH)4] | L6 | 6 | [32] |
[Os(tterpy)C13] prepared from [OsCl3] | L6 | 7 * | [33] |
[Os(Cp)(PPh3)2]OTf | L7 | 8 | [34] |
[Os(N~N~N)Cl3] prepared from [OsCl3] | L8 | 9 | [35] |
Cyclometalated Ligand | Osmacycle | Yield | Ref. | ||
---|---|---|---|---|---|
L9 | 60 | 62% | [55] | ||
L10 | 61 | 61% | [54] | ||
X = H, F; R = Ph, CH3 L11 | 62 | 62% (X = H, R = Ph) 74% (X = F, R = CH3) 60% (X = F, R = Ph) | [54] | ||
L12 | 63 | 92% | [56] | ||
L13 | 64 | 55% | [56] | ||
L14 | 65 | 97% | [57] | ||
L15, L16 | 66 | 23% (E = N) 45% (E = CH) | [58] | ||
L17 | 67 | 77% | [59] | ||
L18 | 68 | 50% | [59] | ||
L18 | 69 | 91% | [59] | ||
L19 | 70 | 99% | [59] | ||
L20 | 71 | 90% | [59] | ||
L21 | 72 | 60% | [60] | ||
L22 | L23 | L24 | 73 | 71% (L22) 60% (L23) 63% (L24) | [61] |
L25 | 74 | 64% | [62] | ||
L26 | 75 | 80% | [62] | ||
L27 | 76 | 53% | [63] | ||
L27 | 77 | 60% | [63] | ||
L28 | 78 | 73% (R = iPr3) 74% (R = Ph) R = Ph prepared from [OsH6(PiPr3)(PPh3)] | [64] | ||
L29 | 79 | 60–75% | [65] | ||
L12 | 80 | 83% | [56] |
Complex | E° (mV) | k2 (M−1s−1) |
---|---|---|
162 | −51 | 0.67 × 106 |
163 | 13 | 4.80 × 106 |
161 | 32 | 2.00 × 106 |
94 | 84 | 2.90 × 106 |
95 | 31 | 1.80 × 106 |
159 | 109 | 2.90 × 106 |
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Cerón-Camacho, R.; Roque-Ramires, M.A.; Ryabov, A.D.; Le Lagadec, R. Cyclometalated Osmium Compounds and beyond: Synthesis, Properties, Applications. Molecules 2021, 26, 1563. https://doi.org/10.3390/molecules26061563
Cerón-Camacho R, Roque-Ramires MA, Ryabov AD, Le Lagadec R. Cyclometalated Osmium Compounds and beyond: Synthesis, Properties, Applications. Molecules. 2021; 26(6):1563. https://doi.org/10.3390/molecules26061563
Chicago/Turabian StyleCerón-Camacho, Ricardo, Manuel A. Roque-Ramires, Alexander D. Ryabov, and Ronan Le Lagadec. 2021. "Cyclometalated Osmium Compounds and beyond: Synthesis, Properties, Applications" Molecules 26, no. 6: 1563. https://doi.org/10.3390/molecules26061563