The “Busch Catalyst”: A Remarkably Diverse Oxidation Catalyst 1)Original Goals and Rationale 2)Ethyl Cross-Bridged Cyclams are successful tight-binding ligands 3)Mn(Bcyclam)Cl 2 identified as active oxidation catalyst a)Alkene Epoxidation b) Hydrogen Atom Abstraction US Patents: 6,218,351 B1; 6,387,862 B2; 6,606,015 B2; 6,906,189; 7,125,832 Topologically constrained like a cryptate Short cross-bridge rigidifies the macrocycle Tunable: ring size and Me group can be modified Simple, high yielding organic synthesis Leaves octahedral metal ions coordinatively unsaturated Neutral ligand giving charged complexes Resistant to oxidation Tertiary amines Saturated Hubin, et al., JACS, 2000, Hubin, et al., Inorg. Chem., 2001, 435. Hubin, et al., Inorg, Chim. Acta, 2003, 76.

4)Synthesis of the Mn(Bcyclam)(OH) 2 2+ complex (activated form of the catalyst) 5)Changing the pH of the aqueous solution changes the major species present H 2 O, H 2 O 2, NH 4 PF 6 Yin, et al., Inorg. Chem., 2006, Yin, et al., JACS, 2007, Shi, et al., Angew. Chem. Int. Ed., 2011, 7321.

6)Electron Transfer Mechanism a)At pH = 1.5, [LMn IV (H 2 O)(OH)] 3+ is the major species (Mn IV —OH for short) b)Oxidation of Ph 3 P: to Ph 3 P=O is a commonly studied reaction 7)Concerted Oxygen Transfer a)Oxidation of Ph 3 P: at pH = 13.4 [LMn IV (=O) 2 ] o (Mn IV =O for short) Xu, et al., Chem. Eur. J., 2009,

8)Hydrogen Atom Abstraction Mechanism a)Similar to phosphine oxidation, low pH (Mn IV —OH) and high pH (Mn IV =O) are active catalysts b)9,10-Dihydroanthracene is a common substrate; oxidizes to anthracene c)Two successive H-atom abstractions occur; the first step is rate limiting Yin, et al., JACS, 2008,

9)The Oxygen Rebound Mechanism a)Suspected mechanism of oxidation by Cytochrome P450 Enzymes, which protect organisms against toxic organic compounds b)Hydroxylation of Hydrocarbons by High-Valent Metal ions

c)Mn IV (Bcyclam) is capable of Oxygen Rebound Oxidations as well d)Mn IV =O i)Is capable of Oxygen Rebound to produce hydroxylated products ii)Does not follow the Electron Transfer Mechanism e)Mn IV —OH i)Is an efficient Electron Transfer catalyst ii)Is incapable of Oxygen Rebound Shi, et al., Angew. Chem. Int. Ed., 2011, 7321.

10)Epoxidation of Alkenes by a Concerted Oxygen Transfer from the Hydrogen Peroxide Adduct a)Organic Peracids (like MCPBA) can epoxidize alkenes b)“Inorganic Peracids” are known to react similarly ( Acc. Chem. Res. 2004, 646 ) c)Mn IV (Bcyclam), epoxidizes alkenes in the presence of H 2 O 2 by this mech. Yin, et al., JACS, 2005, Yin, et al., Inorg. Chem., 2006, 3467.

11)Que has recently studied Fe(Bcyclam) as a catalyst for epoxidation and cis-dihydroxylation of alkenes (Feng, et al., ACS Catalysis, 2011, 1035.) a)Naphthalene 1,2-dioxegenase cis-dihydroxylates aromatic groups b)Que wanted to determine if two available cis sites on the metal were required Fe(Bcyclam)Cl 2 + AgOTf c)Tested against Fe(TMC) (tetramethylcyclam) due to cis/trans only difference

d)Fe(Bcyclam) was a much better catalyst than Fe(TMC) e)Mechanistic investigation showed activation with Acetic Acid, but loss of dihydroxylation and only epoxidation f)Without Acetic Acid, dihydroxylation is favored g)Que suggests an Fe V =O active catalyst for both Feng, et al., ACS Catalysis, 2011, 1035.)

Supplementary information from Busch 2006 Inorg. Chem. p8052