Synthetic and Structural Investigations on the Reactivity of the Cd–I Bond in [ICd{Zr<sub>2</sub>(OPr<sup><i>i</i></sup>)<sub>9</sub>}] to Construct New Mixed-Metal Alkoxides

Abstract

New mixed-metal alkoxides of general formula [XCd­{Zr<sub>2</sub>(OPr<sup><i>i</i></sup>)<sub>9</sub>}]<sub><i>n</i></sub> (X = −C<sub>2</sub>F<sub>5</sub>, −C<sub>6</sub>F<sub>5</sub>, −C<sub>6</sub>F<sub>4</sub>-4-H, −NO<sub>3</sub>, −NCO, −SO<sub>3</sub>CF<sub>3</sub>, −O<sub>2</sub>CCF<sub>3</sub>, −O<sub>2</sub>CC<sub>2</sub>F<sub>5</sub>, −O<sub>2</sub>CCH<sub>3</sub>, −ClO<sub>4</sub>, −CN, −SO<sub>4</sub>; <i>n</i> = 1, 2) were obtained by the scission of the Cd–I bond in the iodo heterobimetallic isopropoxide [ICd­{Zr<sub>2</sub>(OPr<sup><i>i</i></sup>)<sub>9</sub>}] (<b>1</b>), whereby the underlying synthetic strategies involve metathesis reactions with silver salts or Lewis acid–base interactions between the Brønsted acid [Zr­(OPr<sup><i>i</i></sup>)<sub>4</sub>(HOPr<sup><i>i</i></sup>)]<sub>2</sub> and bis­(fluoroorgano)cadmium (Cd­(R<sub><i>f</i></sub><i>)</i><sub>2</sub>) compounds. The new compounds were characterized by multinuclear NMR spectroscopy, elemental analysis, and mass spectrometry. The results of X-ray diffraction analysis of [(F<sub>5</sub>C<sub>6</sub>)­Cd­{Zr<sub>2</sub>(OPr<sup><i>i</i></sup>)<sub>9</sub>}] (<b>2</b>), [(4-H-F<sub>4</sub>C<sub>6</sub>)­Cd­{Zr<sub>2</sub>(OPr<sup><i>i</i></sup>)<sub>9</sub>}] (<b>3</b>), [(F<sub>5</sub>C<sub>2</sub>)­Cd­{Zr<sub>2</sub>(OPr<sup><i>i</i></sup>)<sub>9</sub>}]<sub>2</sub> (<b>4</b>), [(ONO<sub>2</sub>)­Cd­{Zr<sub>2</sub>(OPr<sup><i>i</i></sup>)<sub>9</sub>}]<sub>2</sub> (<b>5</b>), [(CH<sub>3</sub>CO<sub>2</sub>)­Cd­{Zr<sub>2</sub>(OPr<sup><i>i</i></sup>)<sub>9</sub>}] (<b>6</b>), [(O<sub>2</sub>ClO<sub>2</sub>)­(H<sub>5</sub>C<sub>3</sub>N)­Cd­{Zr<sub>2</sub>(OPr<sup><i>i</i></sup>)<sub>9</sub>}] (<b>7</b>), [(μ-O<sub>2</sub>ClO<sub>2</sub>)­Cd­{Zr<sub>2</sub>(OPr<sup><i>i</i></sup>)<sub>9</sub>}]<sub>2</sub> (<b>8</b>), [(μ-O<sub>2</sub>CCF<sub>3</sub>)­Cd­{Zr<sub>2</sub>(OPr<sup><i>i</i></sup>)<sub>8</sub>(O<sub>2</sub>CCF<sub>3</sub>)}]<sub>2</sub> (<b>9</b>), [(μ-O<sub>2</sub>CC<sub>2</sub>F<sub>5</sub>)­Cd­{Zr<sub>2</sub>(OPr<sup><i>i</i></sup>)<sub>8</sub>(O<sub>2</sub>CC<sub>2</sub>F<sub>5</sub>)}]<sub>2</sub> (<b>10</b>), [(μ­(<i>O</i>,<i>N</i>)-OCN)­Cd­{Zr<sub>2</sub>(OPr<sup><i>i</i></sup>)<sub>9</sub>}]<sub>2</sub> (<b>11</b>), and [(μ-O<sub>2</sub>SOCF<sub>3</sub>)­Cd­{Zr<sub>2</sub>(OPr<sup><i>i</i></sup>)<sub>9</sub>}]<sub>2</sub> (<b>12</b>) revealed the molecular framework to be formally constituted by tetradentate coordination of a nonaisopropoxo dizirconate unit, {Zr<sub>2</sub>(OPr<sup><i>i</i></sup>)<sub>9</sub>}<sup>−</sup>, to a CdX<sup>+</sup> unit. In solution and in the solid state, <b>1</b>–<b>7</b> exist as monomers, whereas compounds <b>8</b>–<b>12</b> form dimers

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