1,5‐Diazacyclooctane, Pendant Arm Thiolato Derivatives and [
            <i>N,N′</i>
            ‐Bis(2‐Mercaptoethyl)‐1,5‐Diazacyclooctanato]Nickel(II)

Mills, Daniel K.; Font, Ivan; Farmer, Patrick J.; Hsiao, Yui May; Tuntulani, Thawatchai; Buonomo, Rizalia M.; Goodman, Dawn C.; Musie, Ghezai T.; Grapperhaus, Craig A.; Maguire, Michael J.; Lai, Chia Huei; Hatley, Michelle L.; Smee, Jason J.; Bellefeuille, John A.; Darensbourg, Marcetta Y.; Hancock, Robert D.; Eng, Sheila; Martell, Arthur E.

doi:10.1002/9780470132630.ch15

Cited by 13 publications

(4 citation statements)

References 14 publications

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“…Diethyl ether, toluene, THF, and hexane were distilled from sodium/benzophenone under N 2 . Syntheses of N , N ‘-bis(2-mercaptoethyl)-1,5-diazacyclooctane (H 2 bme-daco), N , N ‘-bis(2-methyl-2-mercaptoethyl)-1,5-diazacyclooctane (H 2 bme*-daco), N , N ‘-bis(2-mercaptoethyl)-1,5-diazacycloheptane (H 2 bme-dach), N , N ‘-dimethyl- N , N ‘-bis(2-mercaptoethyl)-1,3-propanediamine (H 2 bme-pda),5b and their iron or cobalt complexes, [(bme-daco)Fe] 2 3g and its NO derivative, (bme- daco)Fe(NO) (complex 1 ), [(bme*-daco)Fe] 2 ,3e [(bme-dach)Fe] 2 , and [(bme-pda)Co] 2 5a were according to published procedures. S -Nitroso-triphenylmethanethiol (Ph 3 CSNO), and tetrakis(acetonitrile)copper(I) tetrafluoroborate ([Cu(CH 3 CN) 4 ]BF 4 ) were synthesized according to published procedures.…”

Section: Methodsmentioning

confidence: 99%

Synthesis and Molecular Structures of Mononitrosyl (N₂S₂)M(NO) Complexes (M = Fe, Co)

et al. 2005

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A series of tetragonally distorted square pyramids of formula N2S2M(NO) (M = Fe, Co) is prepared and characterized by nu(NO) IR and EPR spectroscopies, magnetism and electrochemical properties, as well as solid-state crystal structure determinations. While the nu(NO) IR frequencies and the angleM-N-O angles indicate differences in the electronic environment of NO consistent with the Enemark-Feltham notation of [Fe(NO)]7 and [Co(NO)]8, the reduction potentials, assigned to [Fe(NO)]7 + e- <==> [Fe(NO)]8 and [Co(NO)]8 + e- <==> [Co(NO)]9 respectively, are very similar, and in cases identical, for most members of the series. Coupled with the potential for the M(NO) units to breathe out of and into the N2S2 core plane are unique S-M-N-O torsional arrangements and concomitant pi-bonding interactions which may account for the unusual coherence of reduction potentials within the series.

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Section: Methodsmentioning

confidence: 99%

Synthesis and Molecular Structures of Mononitrosyl (N₂S₂)M(NO) Complexes (M = Fe, Co)

et al. 2005

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“…Since the first preparation of octahydro-1,5-diazocine ( 1, 1,5-diazacyclooctane, a “bis-homo-piperazine”, Scheme 1 ) in 1939 by W. L. C. Veer [ 31 ] several routes have been suggested to this compound, among them the ring cleavage reaction of 1,5-diaminobicyclo [3.3.0]octane, the condensation of propane-1,3-diamine with 1,3-dibromopropane, and the silica-supported intramolecular cyclization of propane-1,3-diamine at 350 °C [ 32 , 33 , 34 , 35 , 36 , 37 , 38 , 39 , 40 , 41 , 42 , 43 ].…”

Section: Resultsmentioning

confidence: 99%

Mitochondria-Targeting 1,5-Diazacyclooctane-Spacered Triterpene Rhodamine Conjugates Exhibit Cytotoxicity at Sub-Nanomolar Concentration against Breast Cancer Cells

Heise

Becker

Mueller

et al. 2023

IJMS

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1,5-Diazacyclooctane was prepared by a simple synthetic sequence and coupled to pentacyclic triterpenoic acids oleanolic acid, ursolic acid, betulinic acid, platanic acid, and asiatic acid; these amides were activated with oxalyl chloride and reacted with rhodamine B or rhodamine 101 to yield conjugates. The conjugates were screened in SRB assays with various human breast cancer cell lines (MDA-MB-231, HS578T, MCF-7, and T47D) and found to exert cytotoxic activity even at a low concentration. Therefore, for an asiatic acid rhodamine 101 conjugate (28), an IC50 = 0.60 nM was determined and found to induce apoptosis in MDA-MB-231 and HS578T cells. Extra experiments showed the compound to act as a mitocan and to induce inhibition of proliferation or growth arrest in MDA-MB-231 cells at lower doses followed by an induction of apoptosis at higher doses. Furthermore, differential responses to proliferation inhibition and apoptosis induction may explain differential sensitivity of mammary cell lines to compound 28.

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“…An efficient and general means of synthesis of diamino dithiolate(2−) ligands ( l -N 2 S 2 (2−)) with saturated connections between heteroatoms is by a ring-opening S N 2 reaction between the corresponding diamine and the appropriate thiirane. ,− When implemented with N 1 , N 2 -dimethylethylene-1,2-diamine in neat isobutylene sulfide, this approach reproducibly provides N 1 , N 2 - bis (2-methyl-2-mercaptopropane)- N 1 , N 2 -dimethylethane-1,2-diamine, L-N 2 (S Me 2 H) 2 (1 in Scheme ), in essentially quantitative yields . Compared to its analogues without the geminal methyl substituents, 1 offers both greater solubility and convenient simplicity by 1 H NMR spectroscopy.…”

Section: Resultsmentioning

confidence: 99%

Fully Reduced and Mixed-Valent Multi-Copper Aggregates Supported by Tetradentate Diamino Bis(thiolate) Ligands

Wang,

Barnes,

Ferrara

et al. 2023

Inorg. Chem.

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Tetradentate diamino bis(thiolate) ligands (L-N 2 S 2 (2−)) with saturated linkages between heteroatoms support fully reduced [(Cu(L-N 2 S 2 )) 2 Cu 2 ] complexes that bear relevance as an entry point toward molecules featuring the Cu 2 I Cu 2 II (μ 4 -S) core composition of nitrous oxide reductase (N 2 OR). Tetracopper [(Cu(L-N 2 (S Me 2 ) 2 )) 2 Cu 2 ] (L-N 2 (S Me 2 H) 2 = N 1 ,N 2 -bis(2-methyl-2mercaptopropane)-N 1 ,N 2 -dimethylethane-1,2-diamine) does not support clean S atom oxidative addition but undergoes Cl atom transfer from PhICl 2 or Ph 3 CCl to afford [(Cu(L-N 2 (S Me 2 ) 2 )) 3 (CuCl) 5 ], 14. When introduced to Cu(I) sources, the L-N 2 (S Ar H) 2 ligand (L-N 2 (S Ar H) 2 = N 1 ,N 2 -bis(2-mercaptophenyl)-N 1 ,N 2 -dimethylethane-1,2-diamine), made by a newly devised route from N 1 ,N 2 -bis(2fluorophenyl)-N 1 ,N 2 -dimethylethane-1,2-diamine, ultimately yields the mixed-valent pentacopper [(Cu(L-N 2 S Ar 2 )) 3 Cu 2 ] (19), which has 3-fold rotational symmetry (D 3 ) around a Cu 2 axis. The single Cu II ion of 19 is ensconced within an equatorial L-N 2 (S Ar ) 2 (2−) ligand, as shown by 14 N coupling in its EPR spectrum. Formation of 19 proceeds from an initial, fully reduced product, [(Cu(L-N 2 S Ar 2 )) 3 Cu 2 (Cu(MeCN))] (17), which is C 2 symmetric and exceedingly air-sensitive. While unreactive toward chalcogen donors, 19 supports reversible reduction to the all-cuprous state; generation of [19] 1− and treatment with S atom donors only return 19 because structural adjustments necessary for oxidative addition are noncompetitive with outer-sphere electron transfer. Oxidation of 19 is marked by intense darkening, consistent with greater mixed valency, and by dimerization in the crystalline state to a decacopper species ([20] 2+ ) of S 4 symmetry.

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1,5‐Diazacyclooctane, Pendant Arm Thiolato Derivatives and [ N,N′ ‐Bis(2‐Mercaptoethyl)‐1,5‐Diazacyclooctanato]Nickel(II)

Cited by 13 publications

References 14 publications

Synthesis and Molecular Structures of Mononitrosyl (N₂S₂)M(NO) Complexes (M = Fe, Co)

Synthesis and Molecular Structures of Mononitrosyl (N₂S₂)M(NO) Complexes (M = Fe, Co)

Mitochondria-Targeting 1,5-Diazacyclooctane-Spacered Triterpene Rhodamine Conjugates Exhibit Cytotoxicity at Sub-Nanomolar Concentration against Breast Cancer Cells

Fully Reduced and Mixed-Valent Multi-Copper Aggregates Supported by Tetradentate Diamino Bis(thiolate) Ligands

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1,5‐Diazacyclooctane, Pendant Arm Thiolato Derivatives and [ N,N′ ‐Bis(2‐Mercaptoethyl)‐1,5‐Diazacyclooctanato]Nickel(II)

Cited by 13 publications

References 14 publications

Synthesis and Molecular Structures of Mononitrosyl (N2S2)M(NO) Complexes (M = Fe, Co)

Synthesis and Molecular Structures of Mononitrosyl (N2S2)M(NO) Complexes (M = Fe, Co)

Mitochondria-Targeting 1,5-Diazacyclooctane-Spacered Triterpene Rhodamine Conjugates Exhibit Cytotoxicity at Sub-Nanomolar Concentration against Breast Cancer Cells

Fully Reduced and Mixed-Valent Multi-Copper Aggregates Supported by Tetradentate Diamino Bis(thiolate) Ligands

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Product

Resources

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Synthesis and Molecular Structures of Mononitrosyl (N₂S₂)M(NO) Complexes (M = Fe, Co)

Synthesis and Molecular Structures of Mononitrosyl (N₂S₂)M(NO) Complexes (M = Fe, Co)