Phosphoryl transfer enzymes and hypervalent phosphorus chemistry

Area of Science:

• Biochemistry
• Chemical Biology
• Enzyme Mechanisms

Background:

• Phosphoryl transfer enzymes are crucial in biological processes.
• Understanding the coordination chemistry of phosphorus is key to elucidating their mechanisms.
• Previous studies have explored enzyme promiscuity and moonlighting activities.

Purpose of the Study:

• To delineate the coordination tendencies of phosphorus in forming hexacoordinated states from pentacoordinated states.
• To identify factors influencing these coordination tendencies relevant to enzyme mechanisms.
• To propose a role for donor action in active site interactions of phosphoryl transfer enzymes.

Main Methods:

• Review and discussion of factors influencing phosphorus coordination.
• Analysis of substrate and transition/intermediate state anionicity.
• Consideration of hydrogen bonding, van der Waals forces, and pseudorotation.

Main Results:

• Factors such as anionicity, hydrogen bonding, packing effects, and ease of formation influence phosphorus coordination.
• The pseudorotation of non-rigid pentacoordinate phosphorus presents a challenge.
• Donor action is suggested as a significant factor in active site interactions.

Conclusions:

• The coordination tendencies of phosphorus are complex and influenced by multiple factors.
• A deeper understanding of these tendencies aids in describing the mechanistic action of phosphoryl transfer enzymes.
• Donor action is proposed as a critical element in active site interactions for these enzymes.