Influence of 1,2,4-Tri-<i>tert</i>-butylcyclopentadienyl Ligand on the Reactivity of the Thorium Bipyridyl Metallocene [η<sup>5</sup>-1,2,4-(Me<sub>3</sub>C)<sub>3</sub>C<sub>5</sub>H<sub>2</sub>]<sub>2</sub>Th(bipy)]

The thorium bipyridyl metallocene (Cp<sup>3<i>t</i>Bu</sup>)<sub>2</sub>Th(bipy) (<b>1</b>; Cp<sup>3<i>t</i>Bu</sup> = η<sup>5</sup>-1,2,4-(Me<sub>3</sub>C)<sub>3</sub>C<sub>5</sub>H<sub>2</sub>) shows a rich reactivity toward a series of small molecules. For example, complex <b>1</b> may act as a synthon for the (Cp<sup>3<i>t</i>Bu</sup>)<sub>2</sub>Th(II) fragment as illustrated by its reactivity toward to CuI, hydrazine derivative (PhNH)<sub>2</sub>, Ph<sub>2</sub><i>E</i><sub>2</sub> (<i>E</i> = S, Se), elemental sulfur (S<sub>8</sub>) and selenium (Se), organic azides, CS<sub>2</sub>, and isothiocyanates. Moreover, in the presence of polar multiple bonds, such as those in ketones Ph<sub>2</sub>CO and (CH<sub>2</sub>)<sub>5</sub>CO, aldehydes <i>p</i>-MePhCHO and <i>p</i>-ClPhCHO, seleno-ketone (<i>p</i>-MeOPh)<sub>2</sub>CSe, nitriles PhCN, Ph<sub>2</sub>CHCN, C<sub>6</sub>H<sub>11</sub>CN, and <i>p</i>-(NC)<sub>2</sub>Ph, and benzoyl cyanide PhCOCN, C-C coupling occurs to furnish (Cp<sup>3<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy)(Ph<sub>2</sub>CO)] (<b>10</b>), (Cp<sup>3<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy)((CH<sub>2</sub>)<sub>5</sub>CO)] (<b>11</b>), (Cp<sup>3<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy)(<i>p</i>-MePhCHO)] (<b>12</b>), (Cp<sup>3<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy)(<i>p</i>-ClPhCHO)] (<b>13</b>), (Cp<sup>3<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy){(<i>p</i>-MeOPh)<sub>2</sub>CSe}] (<b>14</b>), (Cp<sup>3<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy)(PhCN)] (<b>16</b>), (Cp<sup>3<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy)(Ph<sub>2</sub>CHCN)] (<b>17</b>), (Cp<sup>3<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy)(C<sub>6</sub>H<sub>11</sub>CN)] (<b>18</b>), [(Cp<sup>3<i>t</i>Bu</sup>)<sub>2</sub>Th]<sub>2</sub>{μ-(bipy)[<i>p</i>-Ph(CN)<sub>2</sub>](bipy)} (<b>20</b>), and (Cp<sup>3<i>t</i>Bu</sup>)<sub>2</sub>Th{(bipy)[PhC(CN)O]} (<b>21</b>), respectively. Nevertheless, ketazine (PhCH═N)<sub>2</sub> or benzyl nitrile PhCH<sub>2</sub>CN forms the dimeric complexes [(Cp<sup>3<i>t</i>Bu</sup>)Th]<sub>2</sub>[μ-NC(Ph)(bipy)]<sub>2</sub> (<b>15</b>) and (Cp<sup>3<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy){C(═CHPh)NH}] (<b>19</b>), respectively. In contrast, C-N bond cleavage and C-C coupling processes occur upon addition of isonitriles Me<sub>3</sub>CNC and C<sub>6</sub>H<sub>11</sub>NC to <b>1</b> to yield the thorium isocyanido amido complexes (Cp<sup>3<i>t</i>Bu</sup>)<sub>2</sub>Th[4-(Me<sub>3</sub>C)bipy](NC) (<b>22</b>) and (Cp<sup>3<i>t</i>Bu</sup>)<sub>2</sub>Th[4-(C<sub>6</sub>H<sub>11</sub>)bipy](NC) (<b>23</b>), respectively. Furthermore, a single-electron transfer (SET) process ensues when 1 equiv of CuI is added to <b>1</b> to yield the Th(VI) bipyridyl iodide complex (Cp<sup>3<i>t</i>Bu</sup>)<sub>2</sub>Th(I)(bipy) (<b>3</b>).

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Journal
Inorganic Chemistry
Published
2024-10-03
DOI
https://doi.org/10.1021/acs.inorgchem.4c02782
Citations
5
Primary Topic
Organometallic Complex Synthesis and Catalysis
Type
article
Field-Weighted Citation Impact
1.25

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article

Influence of 1,2,4-Tri-tert-butylcyclopentadienyl Ligand on the Reactivity of the Thorium Bipyridyl Metallocene [η5-1,2,4-(Me3C)3C5H2]2Th(bipy)]

Marc D. Walter, Tongyu Li, Guohua Hou, Yi Heng et al.
5 citations
Inorganic Chemistry
Organometallic Complex Synthesis and Catalysis
1.25
article

Influence of 1,2,4-Tri-tert-butylcyclopentadienyl Ligand on the Reactivity of the Thorium Bipyridyl Metallocene [η5-1,2,4-(Me3C)3C5H2]2Th(bipy)]

Marc D. Walter, Tongyu Li, Guohua Hou, Yi Heng, Wanjian Ding, Guofu Zi, Dongwei Wang
article en
5 citations

Abstract

The thorium bipyridyl metallocene (Cp<sup>3<i>t</i>Bu</sup>)<sub>2</sub>Th(bipy) (<b>1</b>; Cp<sup>3<i>t</i>Bu</sup> = η<sup>5</sup>-1,2,4-(Me<sub>3</sub>C)<sub>3</sub>C<sub>5</sub>H<sub>2</sub>) shows a rich reactivity toward a series of small molecules. For example, complex <b>1</b> may act as a synthon for the (Cp<sup>3<i>t</i>Bu</sup>)<sub>2</sub>Th(II) fragment as illustrated by its reactivity toward to CuI, hydrazine derivative (PhNH)<sub>2</sub>, Ph<sub>2</sub><i>E</i><sub>2</sub> (<i>E</i> = S, Se), elemental sulfur (S<sub>8</sub>) and selenium (Se), organic azides, CS<sub>2</sub>, and isothiocyanates. Moreover, in the presence of polar multiple bonds, such as those in ketones Ph<sub>2</sub>CO and (CH<sub>2</sub>)<sub>5</sub>CO, aldehydes <i>p</i>-MePhCHO and <i>p</i>-ClPhCHO, seleno-ketone (<i>p</i>-MeOPh)<sub>2</sub>CSe, nitriles PhCN, Ph<sub>2</sub>CHCN, C<sub>6</sub>H<sub>11</sub>CN, and <i>p</i>-(NC)<sub>2</sub>Ph, and benzoyl cyanide PhCOCN, C-C coupling occurs to furnish (Cp<sup>3<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy)(Ph<sub>2</sub>CO)] (<b>10</b>), (Cp<sup>3<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy)((CH<sub>2</sub>)<sub>5</sub>CO)] (<b>11</b>), (Cp<sup>3<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy)(<i>p</i>-MePhCHO)] (<b>12</b>), (Cp<sup>3<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy)(<i>p</i>-ClPhCHO)] (<b>13</b>), (Cp<sup>3<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy){(<i>p</i>-MeOPh)<sub>2</sub>CSe}] (<b>14</b>), (Cp<sup>3<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy)(PhCN)] (<b>16</b>), (Cp<sup>3<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy)(Ph<sub>2</sub>CHCN)] (<b>17</b>), (Cp<sup>3<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy)(C<sub>6</sub>H<sub>11</sub>CN)] (<b>18</b>), [(Cp<sup>3<i>t</i>Bu</sup>)<sub>2</sub>Th]<sub>2</sub>{μ-(bipy)[<i>p</i>-Ph(CN)<sub>2</sub>](bipy)} (<b>20</b>), and (Cp<sup>3<i>t</i>Bu</sup>)<sub>2</sub>Th{(bipy)[PhC(CN)O]} (<b>21</b>), respectively. Nevertheless, ketazine (PhCH═N)<sub>2</sub> or benzyl nitrile PhCH<sub>2</sub>CN forms the dimeric complexes [(Cp<sup>3<i>t</i>Bu</sup>)Th]<sub>2</sub>[μ-NC(Ph)(bipy)]<sub>2</sub> (<b>15</b>) and (Cp<sup>3<i>t</i>Bu</sup>)<sub>2</sub>Th[(bipy){C(═CHPh)NH}] (<b>19</b>), respectively. In contrast, C-N bond cleavage and C-C coupling processes occur upon addition of isonitriles Me<sub>3</sub>CNC and C<sub>6</sub>H<sub>11</sub>NC to <b>1</b> to yield the thorium isocyanido amido complexes (Cp<sup>3<i>t</i>Bu</sup>)<sub>2</sub>Th[4-(Me<sub>3</sub>C)bipy](NC) (<b>22</b>) and (Cp<sup>3<i>t</i>Bu</sup>)<sub>2</sub>Th[4-(C<sub>6</sub>H<sub>11</sub>)bipy](NC) (<b>23</b>), respectively. Furthermore, a single-electron transfer (SET) process ensues when 1 equiv of CuI is added to <b>1</b> to yield the Th(VI) bipyridyl iodide complex (Cp<sup>3<i>t</i>Bu</sup>)<sub>2</sub>Th(I)(bipy) (<b>3</b>).

Inorganic ChemistryVol. 63(41)
Beijing Normal University (CN), Technische Universität Braunschweig (DE)
National Natural Science Foundation of China
Openalex Percentile: Top 22%
Organometallic Complex Synthesis and Catalysis
1.25
DOIOpen Access PDFOpenAlex
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