Heterobi- and Trimetallic Cerium(IV) <i>tert</i>-Butoxides with Mono‑, Di‑, and Trivalent Metals (<i>M</i> = K(I), Ge(II), Sn(II), Pb(II), Al(III), Fe(III))

The reaction of <i>C</i>erium <i>A</i>mmonium <i>N</i>itrate (CAN) with varying amounts of KO^<i>t</i>Bu produced homometallic Ce­(O^<i>t</i>Bu)₄(NC₅H₅)₂ (<b>1</b>) and the heterometallic derivative KCe₂(O^<i>t</i>Bu)₁₀ (<b>3</b>) characterized by X-ray diffraction and NMR spectroscopy. The oxo-alkoxide cluster Ce₃O­(O^<i>t</i>Bu)₉ (<b>2</b>) was obtained from a solution of cerium­(IV) tetrakis­(<i>tert</i>-butoxide) in <i>n</i>-heptane under stringent precautions to avoid any adventitious hydrolysis. Lewis acid-base reactions of in situ generated Ce­(O^<i>t</i>Bu)₄(THF)₂ (THF = tetrahydrofuran) with bi- and trivalent metal alkoxides [<i>M</i>(O^<i>t</i>Bu)_<i>x</i>]_<i>n</i> (<i>M</i> = Ge, Sn; <i>x</i> = 2; <i>n</i> = 2; <i>M</i> = Pb, <i>x</i> = 2; <i>n</i> = 3; <i>M</i> = Al, Fe; <i>x</i> = 3; <i>n</i> = 2) resulted in volatile products of the general formula <i>M</i>Ce­(O^<i>t</i>Bu)_4+<i>x</i> (<i>M</i> = Al (<b>4</b>), Fe (<b>5</b>); <i>x</i> = 3; <i>M</i> = Ge (<b>8</b>), Sn (<b>9</b>), Pb (<b>10</b>); <i>x</i> = 2) in high yields. By dissolving <b>4</b> and <b>5</b> in pyridine the solvent adducts <i>M</i>Ce­(O^<i>t</i>Bu)₇(NC₅H₅) (<i>M</i> = Al (<b>6</b>), Fe (<b>7</b>)) were formed, whereas <b>8</b> and <b>9</b> reacted with Mo­(CO)₆ in boiling toluene to yield the termetallic complexes (CO)₅Mo<i>M</i>(μ₂-O^<i>t</i>Bu)₃Ce­(O^<i>t</i>Bu)₃ (<i>M</i> = Ge (<b>11</b>), Sn (<b>12</b>)). The new compounds were characterized by comprehensive spectral studies, mass spectroscopy, and single crystal X-ray diffraction analysis

Heterobi- and Trimetallic Cerium(IV) <i>tert</i>-Butoxides with Mono‑, Di‑, and Trivalent Metals (<i>M</i> = K(I), Ge(II), Sn(II), Pb(II), Al(III), Fe(III))

The reaction of <i>C</i>erium <i>A</i>mmonium <i>N</i>itrate (CAN) with varying amounts of KO^<i>t</i>Bu produced homometallic Ce­(O^<i>t</i>Bu)₄(NC₅H₅)₂ (<b>1</b>) and the heterometallic derivative KCe₂(O^<i>t</i>Bu)₁₀ (<b>3</b>) characterized by X-ray diffraction and NMR spectroscopy. The oxo-alkoxide cluster Ce₃O­(O^<i>t</i>Bu)₉ (<b>2</b>) was obtained from a solution of cerium­(IV) tetrakis­(<i>tert</i>-butoxide) in <i>n</i>-heptane under stringent precautions to avoid any adventitious hydrolysis. Lewis acid-base reactions of in situ generated Ce­(O^<i>t</i>Bu)₄(THF)₂ (THF = tetrahydrofuran) with bi- and trivalent metal alkoxides [<i>M</i>(O^<i>t</i>Bu)_<i>x</i>]_<i>n</i> (<i>M</i> = Ge, Sn; <i>x</i> = 2; <i>n</i> = 2; <i>M</i> = Pb, <i>x</i> = 2; <i>n</i> = 3; <i>M</i> = Al, Fe; <i>x</i> = 3; <i>n</i> = 2) resulted in volatile products of the general formula <i>M</i>Ce­(O^<i>t</i>Bu)_4+<i>x</i> (<i>M</i> = Al (<b>4</b>), Fe (<b>5</b>); <i>x</i> = 3; <i>M</i> = Ge (<b>8</b>), Sn (<b>9</b>), Pb (<b>10</b>); <i>x</i> = 2) in high yields. By dissolving <b>4</b> and <b>5</b> in pyridine the solvent adducts <i>M</i>Ce­(O^<i>t</i>Bu)₇(NC₅H₅) (<i>M</i> = Al (<b>6</b>), Fe (<b>7</b>)) were formed, whereas <b>8</b> and <b>9</b> reacted with Mo­(CO)₆ in boiling toluene to yield the termetallic complexes (CO)₅Mo<i>M</i>(μ₂-O^<i>t</i>Bu)₃Ce­(O^<i>t</i>Bu)₃ (<i>M</i> = Ge (<b>11</b>), Sn (<b>12</b>)). The new compounds were characterized by comprehensive spectral studies, mass spectroscopy, and single crystal X-ray diffraction analysis

Novel Air-Stable and Volatile Bis(pyridylalkenolato)palladium(II) and -platinum(II) Derivatives

Six novel homoleptic palladium­(II) and platinum­(II) complexes of donor-substituted alkenol ligands [PyCHC­(R)­OH; Py = pyridine, R = CH₃, CF₃, C₂F₅, C₃F₇] of the general formula M­[PyCHC­(R)­O]₂ (M = Pd, Pt) were synthesized by reacting the deprotonated ligands with PdCl₂ and K₂PtCl₄, respectively. Molecular structures, revealed by single-crystal X-ray diffraction analyses, showed a square-planar arrangement of ligands around palladium and platinum centers, with the pyridine-ring nitrogen atoms situated in a mutually <i>trans</i> position. The monomeric nature of the compounds in the solution state was confirmed by multinuclear (¹H, ¹³C, and ¹⁹F) NMR spectroscopy. Thermal decomposition profiles recorded under a nitrogen atmosphere suggested their potential as volatile precursors to palladium and platinum materials. The volatility was increased upon elongation of the perfluoroalkyl chain, which suppressed the intermolecular interactions, as is evident in crystal packings. The volatility of these compounds was attributed to bidentate chelation of the alkenol units and cooperativity among the electron-back-donating nitrogen atom and interplay of electron-withdrawing C_<i>x</i>F_<i>y</i> groups, resulting in an effective steric shielding of the metal atoms