Cis-diammineplatinum(II) forms a macrochelate with 2′-deoxycytidine 5′-monophosphate (dCMP2–)! Reactivity and acid-base properties of cis-Pt(NH3)2(dCMP)

Oswald, G.; Rombeck, Ingo; Song, Bin; Sigel, Helmut; Lippert, Bernhard

doi:10.1007/s007750050227

Cited by 5 publications

(5 citation statements)

References 2 publications

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“…The ancillary ligand also plays a role since [Cu(tpy)(T)] 2+ ions were formed, whereas the corresponding dien species were not. These results are consistent with a wealth of previous condensed phase work,16, 17 which shows that the binding of metal ions and their complexes to nucleic acids is quite complex and depends on a number of factors including: (i) the acid base properties of the nucleic acid;18 (ii) which of the tautomeric forms of the nucleobase binds to the metal; (iii) the number of vacant coordination sites available at the metal centre; (iv) the ability to form macrochelates via coordination of two or more sites of the nucleic acid onto the metal centre;19 and (v) the ability of intramolecular hydrogen bonding to stabilize the complex 20. Although a detailed discussion of the literature is beyond the scope of this work, we note the following: [Pt(dien)Cl] + undergoes slower ligand substitution than [Pt(tpy)Cl] + ,21 consistent with the need for longer incubation times; thymine and its derivatives prefer binding to metals in the deprotonated form 18c…”

Section: Resultsmentioning

confidence: 99%

Can radical cations of the constituents of nucleic acids be formed in the gas phase using ternary transition metal complexes?

Wee

O’Hair

McFadyen

2005

Rapid Comm Mass Spectrometry

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Electrospray ionization (ESI) tandem mass spectrometry (MS/MS) of ternary transition metal complexes of [M(L(3))(N)](2+) (where M = copper(II) or platinum(II); L(3) = diethylenetriamine (dien) or 2,2':6',2''-terpyridine (tpy); N = the nucleobases: adenine, guanine, thymine and cytosine; the nucleosides: 2'deoxyadenosine, 2'deoxyguanosine, 2'deoxythymine, 2'deoxycytidine; the nucleotides: 2'deoxyadenosine 5'-monophosphate, 2'deoxyguanosine 5'-monophosphate, 2'deoxythymine 5'-monophosphate, 2'deoxycytidine 5'-monophosphate) was examined as a means of forming radical cations of the constituents of nucleic acids in the gas phase. In general, sufficient quantities of the ternary complexes [M(L(3))(N)](2+) could be formed for MS/MS studies by subjecting methanolic solutions of mixtures of a metal salt [M(L(3))X(2)] (where M = Cu(II) or Pt(II); L(3) = dien or tpy; X = Cl or NO(3)) and N to ESI. The only exceptions were thymine and its derivatives, which failed to form sufficient abundances of [M(L(3))(N)](2+) ions when: (a) M = Pt(II) and L(3) = dien or tpy; (b) M = Cu(II) and L(3) = dien. In some instances higher oligomeric complexes were formed; e.g., [Pt(tpy)(dG)(n)](2+) (n = 1-13). Each of the ternary complexes [M(L(3))(N)](2+) was mass-selected and then subjected to collision-induced dissociation (CID) in a quadrupole ion trap. The types of fragmentation reactions observed for these complexes depend on the nature of all three components (metal, auxiliary ligand and nucleic acid constituent) and can be classified into: (i) a redox reaction which results in the formation of the radical cation of the nucleic acid constituent, N(+.); (ii) loss of the nucleic acid constituent in its protonated form; and (iii) fragmentation of the nucleic acid constituent. Only the copper complexes yielded radical cations of the nucleic acid constituent, with [Cu(tpy)(N)](2+) being the preferred complex due to suppression, in this case, of the loss of the nucleobase in its protonated form. The yields of the radical cations of the nucleobases from the copper complexes follow the order of their ionization potentials (IPs): G (lowest IP) > A > C > T (highest IP). Sufficient yields of the radical cations of each of the nucleobases allowed their CID reactions (in MS(3) experiments) to be compared to their even-electron counterparts.

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Section: Resultsmentioning

confidence: 99%

Can radical cations of the constituents of nucleic acids be formed in the gas phase using ternary transition metal complexes?

Wee

O’Hair

McFadyen

2005

Rapid Comm Mass Spectrometry

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“…[6] In this paper we report the synthesis and characterisation of some platinum(II) complexes with phosphonate ligands have attracted some interest for their biological activity, [10,11] though there are very few studies in contrast to related complexes containing phosphate ligands, because of the significance of the latter to the interactions of platinumbased anticancer drugs with DNA. [12,13,14,15] Results and discussion…”

Section: Reactions Of Cis-[ptclmentioning

confidence: 99%

“…H (300.13 MHz) and13 C{ 1 H} (75.47 MHz) NMR spectra were recorded on a Bruker AC300P spectrometer in CDCl 3 (unless otherwise specified), with chemical shifts relative to CD(H)Cl 3 ( 1 H 7.26 and 13 C 77.06). Scheme 1 shows the atom numbering scheme used in NMR assignments.…”

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confidence: 99%

“…COSY45 NMR spectra were acquired with 1K increments in the F2 dimension, 256 increments zero filled to 512 increments in the F1 dimension and 32 scans per increment. After transformation the data matrix was symmetrised 13. C-1 H correlation spectra were acquired with 1K increments in F2 and 128 increments zero filled to 1K increments in F1 with 32 or 128 scans per increment.…”

mentioning

confidence: 99%

“…13 C{ 1 H} NMR data ¶ for the platinum-phosphonate complexes 2, 3 and 4, together with data for camphanylphosphonic acid 1  ¶ Refer Scheme 1 for atom numbering scheme. Excluding aromatic resonances between ca.…”

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confidence: 99%

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Platinum(II) phosphonate complexes derived from endo-8-camphanylphosphonic acid

Leach

Henderson

Wilkins

et al. 2011

Inorganica Chimica Acta

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The reactions of cis-[PtCl 2 L 2 ] [L = PPh 3 , PMe 2 Ph or L 2 = Ph 2 P(CH 2) 2 PPh 2 (dppe)] with endo-8-camphanylphosphonic acid (CamPO 3 H 2) and Ag 2 O in refluxing dichloromethane gave platinum(II) phosphonate complexes [Pt(O 3 PCam)L 2 ]. The X-ray crystal structure of [Pt(O 3 PCam)(PPh 3) 2 ]•2CHCl 3 shows that the bulky camphanyl group, rather than being directed away from the platinum, is instead directed into a pocket formed by the Pt and the two PPh 3 ligands. This allows the O 3 P-CH 2 group to have a preferred staggered conformation. The complexes were studied in detail by NMR spectroscopy, which demonstrates nonfluxional behaviour for the sterically bulky PPh 3 and dppe derivatives, which contain inequivalent phosphine ligands in their 31 P NMR spectra. These findings are backed up by theoretical calculations on the PPh 3 and PPhMe 2 derivatives, which show respectively high and low energy barriers to rotation of the camphanyl group in the PPh 3 and PPhMe 2 complexes. The X-ray crystal structure of CamPO 3 H 2 is also reported, and consists of hydrogen-bonded hexameric aggregates, which assemble to form a columnar structure containing hydrophilic phosphonic acid channels surrounded by a sheath of bulky, hydrophobic camphanyl groups.

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