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
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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
