3 research outputs found

    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))

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    The reaction of <i>C</i>erium <i>A</i>mmonium <i>N</i>itrate (CAN) with varying amounts of KO<sup><i>t</i></sup>Bu produced homometallic Ce­(O<sup><i>t</i></sup>Bu)<sub>4</sub>(NC<sub>5</sub>H<sub>5</sub>)<sub>2</sub> (<b>1</b>) and the heterometallic derivative KCe<sub>2</sub>(O<sup><i>t</i></sup>Bu)<sub>10</sub> (<b>3</b>) characterized by X-ray diffraction and NMR spectroscopy. The oxo-alkoxide cluster Ce<sub>3</sub>O­(O<sup><i>t</i></sup>Bu)<sub>9</sub> (<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<sup><i>t</i></sup>Bu)<sub>4</sub>(THF)<sub>2</sub> (THF = tetrahydrofuran) with bi- and trivalent metal alkoxides [<i>M</i>(O<sup><i>t</i></sup>Bu)<sub><i>x</i></sub>]<sub><i>n</i></sub> (<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<sup><i>t</i></sup>Bu)<sub>4+<i>x</i></sub> (<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<sup><i>t</i></sup>Bu)<sub>7</sub>(NC<sub>5</sub>H<sub>5</sub>) (<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)<sub>6</sub> in boiling toluene to yield the termetallic complexes (CO)<sub>5</sub>Mo<i>M</i>(μ<sub>2</sub>-O<sup><i>t</i></sup>Bu)<sub>3</sub>Ce­(O<sup><i>t</i></sup>Bu)<sub>3</sub> (<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))

    No full text
    The reaction of <i>C</i>erium <i>A</i>mmonium <i>N</i>itrate (CAN) with varying amounts of KO<sup><i>t</i></sup>Bu produced homometallic Ce­(O<sup><i>t</i></sup>Bu)<sub>4</sub>(NC<sub>5</sub>H<sub>5</sub>)<sub>2</sub> (<b>1</b>) and the heterometallic derivative KCe<sub>2</sub>(O<sup><i>t</i></sup>Bu)<sub>10</sub> (<b>3</b>) characterized by X-ray diffraction and NMR spectroscopy. The oxo-alkoxide cluster Ce<sub>3</sub>O­(O<sup><i>t</i></sup>Bu)<sub>9</sub> (<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<sup><i>t</i></sup>Bu)<sub>4</sub>(THF)<sub>2</sub> (THF = tetrahydrofuran) with bi- and trivalent metal alkoxides [<i>M</i>(O<sup><i>t</i></sup>Bu)<sub><i>x</i></sub>]<sub><i>n</i></sub> (<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<sup><i>t</i></sup>Bu)<sub>4+<i>x</i></sub> (<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<sup><i>t</i></sup>Bu)<sub>7</sub>(NC<sub>5</sub>H<sub>5</sub>) (<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)<sub>6</sub> in boiling toluene to yield the termetallic complexes (CO)<sub>5</sub>Mo<i>M</i>(μ<sub>2</sub>-O<sup><i>t</i></sup>Bu)<sub>3</sub>Ce­(O<sup><i>t</i></sup>Bu)<sub>3</sub> (<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

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    Six novel homoleptic palladium­(II) and platinum­(II) complexes of donor-substituted alkenol ligands [PyCHC­(R)­OH; Py = pyridine, R = CH<sub>3</sub>, CF<sub>3</sub>, C<sub>2</sub>F<sub>5</sub>, C<sub>3</sub>F<sub>7</sub>] of the general formula M­[PyCHC­(R)­O]<sub>2</sub> (M = Pd, Pt) were synthesized by reacting the deprotonated ligands with PdCl<sub>2</sub> and K<sub>2</sub>PtCl<sub>4</sub>, 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 (<sup>1</sup>H, <sup>13</sup>C, and <sup>19</sup>F) 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<sub><i>x</i></sub>F<sub><i>y</i></sub> groups, resulting in an effective steric shielding of the metal atoms
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