Treatment of a diblock copolymer containing an alkyne-functional block (polystyrene-block-poly(4-(phenylethynyl)styrene)) with dicobalt octacarbonyl (Co2(CO)8) leads to selective incorporation of Co2(CO)6 groups in the alkyne block. Examination of these composites in bulk and thin films by transmission electron microscopy reveals the formation of ordered phase-separated morphologies typical of block copolymers. Heating the polymer−cobalt carbonyl adducts at moderate temperatures (110 °C) leads to loss of CO and formation of insoluble polymer cobalt composites. High-temperature thermolysis of these materials leads to formation of carbonaceous materials containing cobalt nanoparticles.

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The cerium(IV) alkoxide complex Ce(OCMe2-i-Pr)4, a volatile, nonfluorinated source of cerium, was used as a chemical vapor deposition precursor to cerium oxide films. A conventional thermal chemical vapor deposition process deposited cerium(IV) oxide films from Ce(OCMe2-i-Pr)4 on silicon, glass, quartz, lanthanum aluminum oxide (001), and roll-textured nickel (001) substrates at low substrate temperatures (<550 °C). The films were highly oriented when the depositions were carried out on lanthanum aluminum oxide and textured nickel substrates. An X-ray crystallographic study of Ce(OCMe2-i-Pr)4, which melts at just below room temperature, shows that it is a loosely bound dimer in the solid state with five-coordinate cerium centers and two bridging alkoxide ligands. The synthesis and X-ray crystal structures of Ce(OCMe2-i-Pr)4(DMAP)2 (DMAP = 4-(dimethylamino)pyridine) and Ce2(OCMe2-i-Pr)5(acac)3 are also reported. The cerium atoms in Ce(OCMe2-i-Pr)4(DMAP)2 and Ce2(OCMe2-i-Pr)5(acac)3 have, respectively, distorted octahedral and pentagonal bipyramidal coordination geometries.

Reactions of indium amide complexes with fluorinated alcohols give indium fluoroalkoxide complexes. In[N-t-Bu(SiMe(3))](3) reacts with 3 equiv of (CF(3))Me(2)COH to give the homoleptic alkoxide dimer [In{&mgr;-OCMe(2)(CF(3))}{OCMe(2)(CF(3))}(2)](2), but reactions involving the more acidic alcohols (CF(3))(2)MeCOH and (CF(3))(2)CHOH yield products containing t-BuNH(2), which is derived from the amide ligands. Thus, In[N-t-Bu(SiMe(3))](3) reacts with (CF(3))(2)MeCOH to give In[OCMe(CF(3))(2)](3)(H(2)N-t-Bu) and with (CF(3))(2)CHOH to yield In[OCH(CF(3))(2)](3)(H(2)N-t-Bu)(3) and [H(3)N-t-Bu][In{OCH(CF(3))(2)}(4)(H(2)N-t-Bu)]. Reactions of (CF(3))(2)MeCOH and (CF(3))(2)CHOH with In(tmp)(3) (tmp = the anion derived from 2,2,6,6-tetramethylpiperidine) and In(NEt(2))(3) are less complicated. In(tmp)(3) reacts with 3 equiv of (CF(3))(2)CHOH to give In[OCH(CF(3))(2)](3)(Htmp) and with 4 equiv of (CF(3))(2)CHOH or (CF(3))(2)MeCOH to yield the salt compounds [H(2)tmp][In{OCR(CF(3))(2)}(4)] (R = H, Me). Trigonal bipyramidal [H(2)NEt(2)][In{OCH(CF(3))(2)}(4)(HNEt(2))] and octahedral mer-In[OCMe(CF(3))(2)](3)(py)(3) are isolated from reactions involving In(NEt(2))(3). Crystal structure determinations of [In{&mgr;-OCMe(2)(CF(3))}{OCMe(2)(CF(3))}(2)](2), [H(3)N-t-Bu][In{OCH(CF(3))(2)}(4)(H(2)N-t-Bu)].EtOEt, In[OCH(CF(3))(2)](3)(Htmp), [H(2)tmp][In{OCMe(CF(3))(2)}(4)], In[OCMe(CF(3))(2)](3)(py)(3), and [H(2)NEt(2)][In{OCH(CF(3))(2)}(4)(HNEt(2))] were carried out.