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54 Arkles, B Silicon, Germanium, Tin and Lead Compounds: Metal Alkoxides, Diketonates, and Carboxylates; Gelest, Inc: Tullytown, PA, 1998 55 Hinsberg, W D, Wallraff, G W, Allen, R D in Kirk Othmer Concise Encyclopedia of Chemical Technology; Kroschwitz, J I and Howe-Grant, M, Ed, John Wiley & Sons, Inc: New York, 1999, pp 1208 1211 56 Reichmanis, E, Neenan, T X in Chemistry of Advanced Materials: An Overview; Interrante, L V and Hampden-Smith, J J, Ed, Wiley-VCH, Inc: New York, 1998, pp 99 141 57 Reichmanis, E, Novembre, A E, Tarascon, R G, Shugard, A, Thompson, L F in Silicon-based polymer science: a comprehensive resource; Zeigler, J M and Fearon, F W G, Ed, American Chemical Society: Washington, DC, 1990; Vol 224 Advances in Chemistry Series, pp 265 281 58 Miller, R D.

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, Rabolt, J F, Sooriyakumaran, R, Fleming, W, Fickes, G N, Farmer, B L, Kuzmany, H in Inorganic and Organometallic Polymers: Macromolecules containing Silicon, Phosphorus, and Other Inorganic Elements; Zeldin, M, Wynne, K J and Allcock, H R, Ed, American Chemical Society: Washington, DC, 1987; No 360 in ACS Symposium Series, pp 43 60 59 Willson, C G Polymers for microlithography: The race goes on, American Chemical Society National Meeting, New Orleans, March 2000, MACR 44 60 Archer, R D, Tramontano, V J, Ochaya, V O, West, P V, Cumming, W G in Inorganic and Metal-Containing Polymeric Materials; Carraher, C E, Jr, Pittman, C U, Jr, Sheats, J E, Zeldin, M and Currell, B, Ed, Plenum Publishing Co: New York, 1991, pp 161 71 61 Archer, R D.

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The organometallic reactions depicted in Figure 211 produce NaCl, and the coordination reactions in Figure 212 produce either an alcohol or a -diketone in addition to the polymer; thus, they are all condensation reactions The hot DMSO solvent used in the reactions shown in Figure 212 solubilizes the bridging ligand, the metal monomer, and the growing polymer chain Note that d 0 and f 0 electron con gurations are considered labile metal ions The large charge and small size of titanium(IV) provide more inertness than might be anticipated for d 0 species, but the tetradentate chelation in the cerium(IV) polymer provides even more inertness A large number of dihaloorganometallic species in addition to the titanium species shown in Figure 211 have also been polymerized with diamines, dithiols, diols, hydrazines, dithioamides, dioximes, dithiohydrazides, hydrazides, and urea (13).

, Hardiman, C J, Lee, A Y in Photochemistry and Photophysics of Coordination Compounds; Yersin, H and Vogler, A, Ed, Springer-Verlag: Berlin, 1987, pp 285 290 62 Archer, R D, Hardiman, C J, Grybos, R, Chien, J C W, Transition and inner transition metal chelate polymers for high energy lithographic resists, U S Patent no 4,693,957, Sept 15, 1987 63 Livage, J, Sanchez, C, Babonneau, F in Chemistry of Advanced Materials; Interrante, L V and Hampden-Smith, M J, Ed, Wiley-VCH, Inc: New York, 1998, pp 429 448 64 Seyferth, D in Silicon-based polymer science: a comprehensive resource; Zeigler, J M and Fearon, F W G, Ed, American Chemical Society: Washington, DC, 1990; Vol 224 Advances in Chemistry Series, pp 565 591 65 Atwell, W H in Silicon-based polymer science: a comprehensive resource; Zeigler, J M.

However, virtually no organometallic polymers that are soluble with high molecular mass have been prepared via this route Reactions analogous to those in Figure 212 with trivalent lanthanide species and sodium salts of bridging Schiff-base ligands form lanthanide polyelectrolytes as shown in Figure 213 (14, 15) The sodium polyelectrolytes are more soluble than either the lithium or the potassium polyelectrolytes (cf Exercise 22) Again, DMSO is used to solubilize the bridging ligand, the metal monomer, and the growing polymer chains Once again, f n ions are expected to be quite labile, but the tetradentate chelation provides more inertness A reaction that mixes a functionalized metal-containing species with a second metal-containing species that can accept two bridging donors from the rst species to complete its coordination sphere is shown in Figure 214.

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