With lutetium

The unsymmetrical complexes LnPcPc can also be prepared in a stepwise manner (Scheme 8.1, D, upper part) [87, 112-114]. Treatment of phthalonitrile with excess of Lu(OAc)3- H2Oand DBU gives the half-sandwich compound LuPc(0Ac)(H20)2. The latter complex reacts with Na2Nc in 1-chloronaphthalene leading to the formation of LuPcNc [87]. Similarly, the template reaction of unsubstituted and crown-substituted phthalonitriles with lutetium acetate was carried out in boding w-hexanol in the presence of DBU [115-117]. Bi- and tri-nuclear [118] lutetium complexes could also be obtained following this approach [111, 119]. 

Renschler, M.F. et al. (1998) Photodynamic therapy trials with lutetium texaphyrin (Iai-Tex) in patients with locally recurrent breast cancer, Proceedings of SPIE-The International Society for Optical Engineering 3247, 35-39. 

The complex has a tetrahedral configuration with Lu-C bonds of 2.42-2.50 A bond length. The bulky 2,6-dimethylphenyl group provides steric limitations in the complex. Ytterbium complex isomorphous with lutetium is also known. The electronic structure and the nature of chemical bonding of the lutetium complex was studied by the INDO method [26]. The MO s of Lu(CgH9)4 ion and the charge distribution are shown in Figs 5.4 and 5.5, respectively. 

In recent clinical and preclinical work, researchers at Pharmacyclics Inc., have demonstrated that texaphyrins selectively localize in atheromatous plaque and not in the normal aortic wall [243,300,301]. In the case of gadolinium texaphyrin PCI-0120 (3), this has been shown in human populations via MRl. With lutetium texaphyrin PCI-0123 (4), spectral bioimaging of intact rabbit aortas (i.e. after PCI-0123 injection and subsequent sacrifice) served to reveal plaque-to-normal vessel retention ratios on the order of 34 to 1 [300]. Further, extensive preclinical studies have helped establish that PCI-0123 (4) may be used in a PDT sense to effect selective photodamage of atheromatous plaque lesions in diet-induced hypercholes-terolemic New Zealand white rabbits [243,300,301]. For instance, Woodbum et al. reported that a protocol involving i.v. injection of PCI-0123 (lOpmolkg per day... 

Figure 15 Three microscopic hematoxylin and eosin (H E) stained cross-sections of a rabbit artery two weeks post PDT treatment with lutetium(III) texaphyrin PCI-0123 (lOpmol/kg per day for three days and illumination with 200J/cm, 250mW/cm and 732 nm laser light 5 h post injection). Here, (A) and (C) are above and below the treatment site and (B) is at the treatment site. The aorta, above the treatment zone, is shown. The intima (i) is extensively thickened and heavily ladened with foam cells. The atheroma completely lines the wall, thereby significantly narrowing the lumen (1). The outer wall, adventitia (a), and media (m) are normal and show no evidence of infiltrating disease. The photoirradiated site (B) is now normal (i.e., devoid of lesions), while the media muscular wall is intact with no necrotic regions being visible. The field below the treatment site (C) is heavily burdened with plaque (x40). Reproduced from [243] by permission of Mary Aim Liebert, Inc. Publishers...

The scope of the reaction includes the formation of five-, six-, and seven-membered heterocycles from primary, secondary, and aromatic amines as the starting compounds, giving exclusively the exo-methyl product in agreement with Markovnikov s rule. All reactions are found to proceed equally well in toluene, benzene, pentane, and related hydrocarbon solvents. In donor solvents such as THF, catalytic rates are significantly slower. In the series of bisfpenta-methylcyclopentadienyl)lanthanide catalysts, the highest activity was observed with lanthanum and with lutetium the lowest the variation of TON spans over three orders of magnitude. 

The first bridged aminotroponiminate complexes of lutetium were synthesized by the reaction of dipotassium-1,3-di[2-(isopropylamino)troponiminato]propane, K2[(Pr )TP], with lutetium trichloride (Scheme 20). The complex was... 

Metathetical routes using bulky lithium guanidinates as starting materials have also been employed to synthesize bis(guanidinato) lanthanide halides (e.g., with lutetium. Scheme 21) as well as reactive alkyls and hydrides [6,7,11],... 

Figure 3. Equilibrium constants for Equation 1, from kinetics of the reaction of propene with lutetium complexes. ...

Woodburn, K.W., Fan, Q., Kessel, D., Luo, Y., and Young, S.W. (1998) Photodynamic therapy of B16F10 murine melanoma with lutetium texaphyrin, J. Invest Dermatol., 110 746-751. 

Meredith RF, Partridge EE, Alvarez RD, Khazaeli MB, Plott G, Russell CD, et al. In-traperitoneal radioimmunotherapy of ovarian cancer with lutetium-177-CC49. J Nucl Med 1996 37 1491-1496. 

T.J. Wieman, T. Panella, R. Lustig, J. Liebmann, R. Carlson, L. Esserman, S. Dougherty, V. Fingar, D. Hoth, M. Renschler, D. Adelman (1999). Photodynamic therapy (PDT) of locally recurrent breast cancer (LRBC) with lutetium texaphyrin (lutrin) a phase IB/IIA trial. Proc. Am. Soc. Clin. Oncol., 18, 418. 

The 5d group can most conveniently be said to start with lutetium, followed by... 

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