Formation of a high valent di-μ-oxo manganese dimer in aqueous solution

✍ Scribed by Rajesh Manchanda; Gary W. Brudvig; Robert H. Crabtree; Joseph E. Sarneski; Mary Didiuk

• Book ID: 104138733
• Publisher: Elsevier Science
• Year: 1993
• Tongue: English
• Weight: 291 KB
• Volume: 212
• Category: Article
• ISSN: 0020-1693
• DOI: 10.1016/s0020-1693(00)92318-1

✦ Synopsis

We find an unusual example in which different clusters can be isolated from the same reaction mixture depending on the choice of counter-ion.

The complex [(bipy),Mn(III)(~-O),Mn(IV)(bipy),]3+

(1

is isolated from Mn(II) and permanganate in acetate buffer with C104-, but [(blpy)(H,O)Mn(III)(~-O)(p-OAc),Mn(III)(bipy)(H,O)]'+ (2) with NO,-. le-/2H+ or le-/lH+ proton-coupled electron transfer chemistry is found for 2 according to the type of buffer used. The new complex [(bipy)(H,0)Mn(III)(~-0)2(~-OAc)Mn(IV)(bipy)(H,O)]" (3) 1s also postulated as an intermediate in the formation of 1.