Charge-separation in uranium diazomethane complexes leading to C-H activation and chemical transformation.
The reaction of diphenyldiazomethane with [((t-BuArO)3tacn)UIII] (1) results in an eta(2)-bound diphenyldiazomethane uranium complex. This complex exhibits unusual electronic properties as a charge-separated species with a radical anionic open-shell ligand, [((t-BuArO)3tacn)UIV(eta2-NNCPh2)] (2). Treating Ph2CN2 with a uranium complex that contains a sterically more demanding adamantane functionalized ligand, [((AdArO)3tacn)UIII] (3) results in an unprecedented C-H activation and nitrogen insertion to produce a five-membered heterocyclic indazole complex, [((AdArO)3tacn)UIV(eta(2)-3-phen(Ind))] (5). X-ray crystallography and spectroscopic characterization of these two compounds show that the [((t-BuArO)3tacn)UIV(eta(2)-NNCPh2)] compound is a U(IV) complex with a radical anionic ligand, whereas [((AdArO)3tacn)UIV(eta(2)-3-phen(Ind))] is a U(IV) f (2) species with a closed-shell ligand.
Lam
Oanh P
OP
University of California, San Diego, Department of Chemistry, 9500 Gilman Drive, La Jolla, California 92093, USA.
Feng
Patrick L
PL
Heinemann
Frank W
FW
O'Connor
Joseph M
JM
Meyer
Karsten
K
D018360:Crystallography, X-Ray; D003978:Diazomethane / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D013237:Stereoisomerism; D013696:Temperature; D014501:Uranium / Q000737:chemistry*
D009942:Organometallic Compounds; D014501:Uranium; D003978:Diazomethane