Reactivity of coordinated phosphate esters: pentaamminecobalt(III) complexes

Aqueous Phosphoester Bond Cleavage of Dimethyl Phosphate by Cp2MoCl2: First Reported Case of Hydrolytic Cleavage on an Unactivated Phosphate Diester by an Organometallic Complex

“…Lewis acid activation by Cp 2 Mo coordination alone is not sufficient to explain the observed rate acceleration, for it has been found that Co(III)-phosphate coordination yields only a 10 2 enhancement in phosphate hydrolysis. 17 This implies Co(III) coordination complexes that accelerate phosphate hydrolysis by 10 10 provide an additional 7-8 orders of magnitude rate acceleration through intramolecular attack of Co(III)-bound hydroxide. If the assumption that DMeP is degraded by Cp 2 -MoCl 2 via a hydrolytic process at pD 7, then the rate acceleration (10 8 ) can be attributed to Cp 2 Mo providing Lewis acid activation (10 2 ) and a nucleophilic hydroxide/water (10 6 ).…”

Cleavage of phosphate diesters mediated by Zn(II) complex in Gemini surfactant micelles

“…In general, a metal-OH-promoted hydrolytic mechanism of phosphate diesters has been widely accepted [24]. Nevertheless, in the cleavage reaction of HPNP, the cleavage mechanism does not involve a direct nucleophilic attack by metal-coordinated hydroxide, which participates as a base for the deprotonation of a substrate alcohol group serving as the intramolecular nucleophile [25][26][27][28][29][30].…”

Structures, spectra, and DNA-binding properties of mixed ligand copper(II) complexes of iminodiacetic acid: The novel role of diimine co-ligands on DNA conformation and hydrolytic and oxidative double strand DNA cleavage

“…Sigman and co-worker have shown that copper complexes of 1,10-phenanthroline (phen) act as effective chemical nuclease with a high preference for double-stranded DNA in the presence of molecular oxygen and a reducing agent [18]. A number of metal complexes have been shown to hydrolyze phosphate ester [19] as well as RNA with varying efficiencies [20]; however, they are unable to hydrolyze the phosphate diester backbone of DNA. Burstyn and co-worker reported that copper(II)-macrocyclic triamine complexes promote the hydrolytic cleavage of plasmid DNA [21].…”