Syntheses, spectroscopic and crystallographic characterizations ofcis- andtrans-dispirocyclic ferrocenylphosphazenes: molecular dockings, cytotoxic and antimicrobial activities

Abstract

The crystallographic and molecular docking investigations and the determinations of the cytotoxic activities of the dispirocyclic ferrocenylphosphazenes were performed.

Phosphorus-nitrogen compounds- (Part 50): correlations between structuralparameters for cylophosphazene derivatives containing ferrocenyl pendant arm(s)

“…Fully Van-substituted spiro-bisferrocenyl cyclotriphosphazene (V) was synthesized from the reaction carried out with excess potassium vanillinate [37]. The Cl-replacement reactions of trimer with 2 equimolar amounts of mono-ferrocenyldiamines resulted in the formation of the corresponding partly substituted cis-(meso) and trans-(racem) dispiro-bisferrocenyl cyclotriphosphazenes (VIII) as the major products and spiro-mono (I) ferrocenyl cyclotriphosphazenes as minor products [36]. Three products were separated performing column chromatography.…”

“…However, the difference between the ∆ (P-N) values of cis-and trans-structures of the phosphazenes with 5-membered spiro-rings (VIIIb and IXa) is slightly larger than that of the phosphazene with 6-membered spiro-rings (VIIIc). That could be significantly attributed to the fact that 5-membered spiro-rings of c-VIIIb, t-VIIIb, c-IX and t-IX are in envelope conformation and 6-membered spiro-rings of c-VIIIc and t-VIIIc are in the chair conformation [36,39]. Figure 1ii).…”

“…According to these studies, it was observed that geminal vanillinato (Van)-substituted spiro-monoferrocenyl cyclotriphosphazenes [31], tetra pyrrolidine (Pyr)-substituted spiro-mono [32,33] and bisferrocenyl [33] cyclotriphosphazenes and hexa Pyr-substituted spiro-monoferrocenyl cyclotetraphosphazenes [34] inhibited the growth of Mycobacterium tuberculosis H37Rv. While 1,4-dioxa-8-azaspiro [4,5]decane (DASD)-substituted spiro-bisferrocenyl [35] and partly substituted dispiro-bisferrocenyl [36] cyclotriphosphazenes, the fully and nongeminal (cis) [37] Van-substituted spiro-monoferrocenyl cyclotriphosphazenes, were effective against the human cervical cancer cell line (HeLa), bis(diamino) substituted dispiro-bisferrocenyl cyclotetraphosphazene was found to be more active against colon cancer DLD-1 cells than Doxorubicin [38]. It was also found that the DASD and Pyr-substituted ferrocenyl cyclotriphosphazenes were active against some gram-positive and gram-negative bacteria [32,33,35] and Pyrsubstituted ferrocenyl cyclotetraphosphazenes were more effective than the commercial antifungal drug Ketoconazole against fungi [34].…”

“…It was found that the systematic variations in the 31 P NMR chemical shifts depend fundamentally on some electronic (electron-releasing and electron-withdrawing capacities of substituent groups), steric (the steric hindrance between the exocyclic groups) and conformational factors, and on the changes in bond lengths and bond angles around the phosphorus atoms [especially endocyclic ( α) and exocyclic ( α ′ ) bond angles] in cyclotriphosphazene derivatives. The current study deals with a number of correlations between structural parameters [e.g., 31 P NMR spectral data and X-ray crystallographic data (endocyclic and exocyclic NPN bond angles, and bond lengths)] in spirocyclic ferrocenyl cyclophosphazenes introduced to the literature from our research group (Table 1) [33][34][35][36][37][38][39][40][41]52]. Therefore the content of this report includes: (i) a brief description of the synthesis methods of 11 different structural types and a total of 28 spirocyclic ferrocenyl phosphazenes with 5-to 7 −membered spiro-rings used for the graph construction, (ii) the relationship between the δ P spiro shifts and the values of electron density transfer parameters ∆(P-N), and (iii) the correlation of δ P spiro shifts and endocyclic ( α) and exocyclic ( α ′ ) NPN bond angles of the compounds.…”

Phosphorus-nitrogen compounds (Part 51): the relationship betweenspectroscopic and crystallographic data of mono- and di-spirocyclophosphazenederivatives with 4-fluoro/nitrophenylmethyl pendant arm/arms

“…In recent years, cyclotri and cyclotetraphosphazenes have started to attract much attention due to their potential stereogenic properties, and biological activities such as antibacterial, antifungal and anti-cancer activities [8][9][10][11][12]. Our group has spent many years on designating and synthesizing novel partly substituted cyclotri and cyclotetraphosphazene derivatives with bidentate ligands {dibenzo-diaza-crown ethers [13][14][15][16][17], dibenzo N 2 O n (n =2-4) [18][19][20][21] and benzo NO [22][23][24][25][26][27][28] donor * Correspondence: sbilge@science.ankara.edu.tr type aminopodands, mono-and bis-ferrocenyldiamines [29][30][31][32][33][34][35][36][37], sodium (ferrocenylmethylamino)-1-alkoxide [38][39][40][41][42][43]}and multidentate N 2 O 2 -donor type dibenzo aminopodands [44][45][46]. Some interesting phosphazene derivatives such as monotopic and ditopic spiro-crypta phosphazenes, spirocyclic phosphaza (PNP-lariat) ethers, cyclophosphazenes possessing 6-membered spiro ring/rings, mono and bisferrocenylspirocyclophosphazenes, and spiro-ansa-spiro-, spiro-bino-spiro-and ansa-spiro-ansa-phosphazenes were synthesized.…”