Sylvain Dutremez

Solid state 31P NMR spectroscopic studies of tertiary phosphines and their complexes

A. Introduction . . . . . . . . . . . . . . . B. Solid state NMR methods . . (i) The MAS experiment . . . . (ii) The CP/MAS experiment. . . C. Tertiary phosphines . . . . . . . . . . . . D. Transition metal complexes . . . . (i) Complexes of the Group 8 metals. (ii) Complexes of the Group 9 metals. (iii) Complexes of the Group IO metals (iv) Complexes of the Group I I metals (v) Complexes of the Group 12 metals E. Concluding remarks . . . . . . Note added in proof. . . . . . References . . . .

Solid state NMR studies of d-block and p-block metal nuclei: Applications to organometallic and coordination chemistry

A. Introductio B. Properties of metal nuclei . . 204 C. Solid state NMR . . . 204 D. Studies of metal nuclei 209 (i) The d-block metals . 209 (a) Group 3 (SC, Y, La) . 209 (b) Group 4 (Ti, Zr, Hf) . . . . 211 (c) Group 5 (V, Nb, Ta) . 213 (d) Group 6 (Cr, MO, W) . . 214 (e) Group 7 (Mn, Tc, Re) . . 217 (f) Group 8 (Fe, Ru, OS) . 219 (g) Group 9 (Co, Rh, Ir) . . . 220 (h) Group 10 (Ni, Pd, Pt) 220 (i) Group 11 (Cu, Ag, Au) 222 (j) Group 12 (Zn, Cd, Hg) 223 (ii) The p-block metals . . 229 (a) Group 13 (Al, Ga, In, Tl) 229 (b) Group 14 (Ge, Sn, Pb) 230 (c) Group 15 (Sb, Bi) 238 E. Concluding remarks 238 References . . . . . . 239

Iron-based Second-sphere Contrast Agents for Magnetic Resonance Imaging: Development of a Model System and Evaluation of Iron (III) Tris (tironate) Complex in Rats

RATIONALE AND OBJECTIVESnIron(III) complexes have been developed as magnetic resonance (MR) contrast agents based on the use of ligands capable of providing coordinative saturation at iron and allowing the second-sphere hydrogen bonding of water molecules.nnnMETHODSnStudies of solution-phase binding of a probe ion to a diamagnetic metal catecholate complex and molecular orbital calculations were performed. R1 values were determined. Toxicity studies of iron(III) tris(tironate) were conducted with rats. Excretion studies were performed by analysis of urine samples. MR measurements were made.nnnRESULTSnSecond-sphere coordination of a probe ion to a metal catecholate complex occurred in solution. Molecular orbital calculations suggested flexibility in design. Iron(III) tris (catecholate) complexes were shown to have high R1 values. Images of the kidneys and liver showed dose-dependent enhancement in T1-weighted images. The onset of toxicity was at approximately 0.30 mmol/kg. Urine analysis indicated essentially complete clearance (0.1-0.2 mmol/kg) within 24-48 hours.nnnCONCLUSIONnInteractions between water molecules and basic sites within a paramagnetic metal-ligand complex allow for application of suitable complexes as T1 agents.