Abstract
A series of rhenium and manganese carbonyl complexes of a heteroscorpionate ligand with an atypical N2P-donor set has been prepared to better understand their electronic and CO releasing properties. Thus, the ligand, pz2TTP, with an a,a-bis(pyrazol-1-yl)tolyl group decorated with an ortho-situated di(p-tolyl)phosphanyl reacts with carbonyl group 17 reagents to give [fac-(κ2NP-pz2TTP)Re(CO)3Br], 1, and [fac-(κ3N2P-pz2TTP)M(CO)3](OTf = O3SCF3), 2-M (M = Re, Mn), if care is taken during the preparation of the manganeses derivative. When heated in CH3CN, 2-Mn slowly transforms to [fac,cis-(κ3N2P-pz2TTP)Mn(CO)2(NCCH3)](OTf), 3-Mn. In contrast, the corresponding 3-Re can only be prepared from 2-Re using Me3NO; pure 3-Mn can also be prepared by this method. Experimental and density functional calculations at the M06L/Def2-TZVP/PCM(CH3CN) level show that the replacement of a carbonyl with an acetonitrile solvent decreases the oxidation potential by around 0.8 V per carbonyl released, making decarbonylated species potent reductants. At the same time, the electronic spectrum broadens and undergoes a red-shift, making dicarbonyl complexes more susceptible to photo-initiated decarbonylation reactions than tricarbonyls. When 2-Mn or 3-Mn are irradiated in with 390 nm LED light in aerated solutions, [trans-Mn(pz2TTP = O)2](OTf)2, 4, along with insoluble manganese oxides are rapidly formed.