Ternary palladium(II)–glycylmethionine-nucleobase complexes: solution studies and crystal structure of the 9-methylguanine compound
1997
Ternary complex formation between model nucleobases and
[Pd(gly-L-met)] 1
(gly-L-met = dianion of glycylmethionine,
deprotonated at the amide N and at the met carboxylate terminus) has
been studied by 1
H NMR spectroscopy and potentiometry. A
representative example,
[Pd(gly-L-metH)(Hmgua)]NO
3
·H
2
O
3 (Hmgua = 9-methylguanine), has been
characterized by X-ray crystallography. Co-ordination of Pd is through
the terminal amino group of the glycyl entity, the deprotonated amide
nitrogen, S of the methionine, and N
7
of the purine
nucleobase. The carboxylic acid group of methionine is protonated. In
aqueous solution binding of Pd to other nucleobases occurs via
N
3
in the case of 1-methylcytosine (Hmcyt) and of
deprotonated 1-methyluracil, N
7
of 9-ethylguanine (Hegua) or
N
1
, N
7
/N
1
of the guanine anion (egua).
Discrete rotamers form on binding of Pd to N
3
of the
pyrimidine nucleobases and to N
1
of the guanine. The
gly-L-metH resonances provide no evidence for the existence
of stable diastereomers, suggesting that inversion at the chiral S atom
of met is fast. In contrast, both [Pt(gly-L-metH)Cl] and its
ternary derivative with Hmcyt appear to be present in solution as
diastereomeric mixtures. Stability constants have been determined for
ternary complexes formed from 1 and
[Pd(gly-L-metH)Cl], respectively, with nucleobases.
Keywords:
- Correction
- Source
- Cite
- Save
- Machine Reading By IdeaReader
44
References
19
Citations
NaN
KQI