Synthesis, cytotoxic and hydrolytic studies of titanium complexes anchored by a tripodal diamine bis(phenolate) ligandElectronic supplementary information (ESI) available: Detailed ESI-MS data for compounds 3, 4 and 5, tables with atomic coordinates of the optimized molecules 1, 3, 5, HOiPr, Net3, NEt3·HCl and H2O and detailed X-ray data for compound 4. Data for structures 2, 4 and 5 were deposited at the CCDC. CCDC 994885-994887. For ESI and crystallographic data in CIF or other electronic form
The reactivity, cytotoxic studies and hydrolytic behaviour of diamine bis(phenolate) titanium complexes are reported. The reactions of [Ti( t Bu 2 O 2 NN′)Cl] 2 (μ-O) ( 1 ) with LiO i Pr or HO i Pr in the presence of NEt 3 , aiming at the synthesis of the alkoxido derivative of 1 led to no reaction...
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| Main Authors | , , , , , , |
|---|---|
| Format | Journal Article |
| Language | English |
| Published |
04.11.2014
|
| Online Access | Get full text |
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| Summary: | The reactivity, cytotoxic studies and hydrolytic behaviour of diamine bis(phenolate) titanium complexes are reported. The reactions of [Ti(
t
Bu
2
O
2
NN′)Cl]
2
(μ-O) (
1
) with LiO
i
Pr or HO
i
Pr in the presence of NEt
3
, aiming at the synthesis of the alkoxido derivative of
1
led to no reaction or to the synthesis of the monomeric complex [Ti(
t
Bu
2
O
2
NN′)(O
i
Pr)
2
] (
3
), respectively. A small amount of the alkoxidotitanium dimer [Ti(
t
Bu
2
O
2
NN′)(O
i
Pr)]
2
(μ-O) (
2
) crystallized out of a solution of
3
and DFT calculations showed that the transformation of
1
into
3
is a thermodynamically favorable process in the presence of a base (NEt
3
) (Δ
G
= −14.7 kcal mol
−1
).
2
was quantitatively obtained through the direct reaction of the ligand precursor H
2
(
t
Bu
2
O
2
NN′) with titanium tetra(isopropoxido). Further reaction of
2
with an excess of TMSCl was revealed to be the most suitable method for the preparation of [Ti(
t
Bu
2
O
2
NN′)Cl
2
] (
4
).
1
and
3
disclosed cytotoxic activity towards HeLa, Fem-x, MDA-MB-361 and K562 cells and
1
exhibited moderate binding affinity to FS-DNA.
1
H NMR hydrolysis studies attested the fast decomposition of
4
in the presence of D
2
O. The hydrolysis of
3
is slower and proceeds through the formation of [Ti(
t
Bu
2
O
2
NN′)(OH)]
2
(μ-O) (
5
) that was crystallographically characterized. Upon D
2
O addition
1
immediately forms complex new species, stable in solution for long periods (weeks).
The reactivity, cytotoxic studies and hydrolytic behaviour of diamine bis(phenolate) titanium complexes are reported. |
|---|---|
| Bibliography: | 994885-994887 HCl and H O and detailed X-ray data for compound HO i * , Electronic supplementary information (ESI) available: Detailed ESI-MS data for compounds Pr, Net 1 For ESI and crystallographic data in CIF or other electronic format see DOI Data for structures 2 were deposited at the CCDC. CCDC 3 4 tables with atomic coordinates of the optimized molecules 5 and 10.1039/c4dt00975d NEt |
| ISSN: | 1477-9226 1477-9234 |
| DOI: | 10.1039/c4dt00975d |