title: Inside or outside a ligand cleft? Synthetic, structural, and kinetic inertness studies of zinc, cadmium, and mercury complexes of cross-bridged cyclam and cyclen.
abstract: Ethylene cross-bridging of the popular tetraazamacrocyclic ligand cyclam has led to metal complexes with enhanced kinetic inertness. The synthesis and spectral characterization of zinc(II), cadmium(II), and mercury(II) complexes of cross-bridged cyclam (L1) as well as cross-bridged cyclen (L2) are reported along with the details of our synthetic route to L2. X-ray structural studies revealed that all Zn(II) and Cd(II) cations are fully kappa(4)N-coordinated inside the respective ligand's molecular cleft with L1 providing the better fit for Zn(II). While Hg(II) is similarly coordinated to L2, it has been found to complex L1 outside the ligand cleft in a novel exo-kappa(2)N-mode. Solution NMR data of the kappa(4)N complexes are consistent with the presence of only a single cis-folded isomer in each case. Ligand (1)H and (13)C coupling to both (111,113)Cd and (199)Hg in their complexes can be clearly discerned. The relative kinetic inertness of representative cross-bridged complexes in acidic aqueous solution has been assessed and found to be in the following order: Zn(II) > Cd(II)[dbl greater-than] Hg(II). The data also reaffirm that cross-bridged cyclam ligand L1 forms a substantially more inert complex with zinc(II) than either the smaller cyclen analogue L2 or the unbridged 1,4,8,11-tetramethyl-cyclam L3.
authors.affiliation: Department of Chemistry, University of New Hampshire, Durham 03824, USA.
authors.forename: Weijun
authors.initials: W
authors.lastname: Niu
authors.forename: Edward H
authors.initials: EH
authors.lastname: Wong
authors.forename: Gary R
authors.initials: GR
authors.lastname: Weisman
authors.forename: Daniel C
authors.initials: DC
authors.lastname: Hill
authors.forename: David J
authors.initials: DJ
authors.lastname: Tranchemontagne
authors.forename: Kim-Chung
authors.initials: KC
authors.lastname: Lam
authors.forename: Roger D
authors.initials: RD
authors.lastname: Sommer
authors.forename: Lev N
authors.initials: LN
authors.lastname: Zakharov
authors.forename: Arnold L
authors.initials: AL
authors.lastname: Rheingold
mesh_terms: D001952:Bridged-Ring Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D002104:Cadmium / Q000737:chemistry*; D018360:Crystallography, X-Ray; D000080027:Cyclams; D006571:Heterocyclic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D007700:Kinetics; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D008628:Mercury / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009941:Organomercury Compounds / Q000138:chemical synthesis / Q000737:chemistry; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D013055:Spectrophotometry, Infrared; D015032:Zinc / Q000737:chemistry*
chemical_list: D001952:Bridged-Ring Compounds; D000080027:Cyclams; D006571:Heterocyclic Compounds; D008024:Ligands; D009941:Organomercury Compounds; D009942:Organometallic Compounds; D002104:Cadmium; C024560:cyclam; C038072:cyclen; D008628:Mercury; D015032:Zinc