Phosphorus-Nitrogen Compounds. Part 85. Design and Synthesis of Novel Hybrid Multiheterocyclic spiro- and 2-cis-4-ansa-Ferrocenyl-(N/O)-cyclotetraphosphazene Conjugates Bearing Piperonal Pendant Arms: Structural Characterizations, Carbonic Anhydrase Activation, and Antioxidant Activity Studies
APPLIED ORGANOMETALLIC CHEMISTRY, cilt.40, sa.6, 2026 (SCI-Expanded, Scopus)
- Yayın Türü: Makale / Tam Makale
- Cilt numarası: 40 Sayı: 6
- Basım Tarihi: 2026
- Doi Numarası: 10.1002/aoc.70595
- Dergi Adı: APPLIED ORGANOMETALLIC CHEMISTRY
- Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus, BIOSIS, Chemical Abstracts Core, Chimica, Compendex, DIALNET, Academic Search Ultimate (EBSCO), Biomedical Reference Collection: Corporate Edition (EBSCO)
- Ankara Üniversitesi Adresli: Evet
Özet
The reaction of octachlorocyclotetraphosphazene, N4P4Cl8, OCCP-(1), with sodium-3-(N-ferrocenylmethylamino)-1-propanoxide-(L1) in an equimolar ratio of 1:1 led to the formation of the starting compounds, mono-ferrocenyl-spiro-(spiro-2) and 2-cis-4-dichloro-ansa-(ansa-3) (N/O)cyclotetraphosphazenes. The piperonal pendant armed cyclotetraphosphazenes were prepared from the reactions of spiro-2 and ansa-3 with bidentate ligands, N-(piperonalyl)-N '-methyl-1,3-diamino-propane-(L2) and sodium-3-(piperonalylamino)-1-propanoxide-(L3). Spiro-2 was separately reacted with L2 and L3 to afford trispiro-2a (ctt-2a and tct-2a; c: cis and t: trans) and tetraspiro-2a (cctt-2a and tctc-2a), and tetraspiro-2b (cctt-2b) cyclotetraphosphazenes, respectively. However, the reactions of ansa-3 with excess L2 and L3 resulted in the formation of ansa-dispiro-3a (ctt-3a) and ansa-dispiro- 3b (ctt-3b) cyclotetraphosphazenes, respectively. These novel products were synthesized to investigate their spectroscopic, stereogenic, crystallographic and bioactivity properties. The structures of piperonalyl-cyclotetraphosphazenes were evaluated by elemental analysis, ESI-MS, FTIR, 1H, 13C{1H} and 31P{1H} NMR techniques. The compounds had two (ansa-3, cctt-2a/tctc-2a and cctt-2b), three (ctt-2a) and four (ctt-3a and ctt-3b) stereogenic P-centers. The molecular and crystal structures of ctt-3a were confirmed by X-ray crystallography and its Hirshfeld surface (HS) analysis was performed. Thus, the crystal structure of ctt-3a revealed the absolute configuration of one enantiomer (RS'R ' S ''). Carbonic anhydrase activator and antioxidant activities of the cyclotetraphosphazenes were evaluated. Based on the in vitro activator effects of these compounds on the esterase activities of hCA I and hCA II isoenzymes, trispiro-2a was found to have the strongest activator (K A = 17.53 +/- 2.63 mu M). Additionally, among the derivatives evaluated, trispiro-2a (91.3% +/- 0.2%) and tetraspiro-2b (89.3% +/- 0.1%) demonstrated exceptionally high free radical scavenging (antioxidant) activities (FRSAs), approaching those of standard antioxidants (BHA 94.0% +/- 0.3% and alpha-tocopherol 97.1% +/- 0.1%).