Metal Complexes of Pyridylphenylisocyanides and Pyridylethynylphenylisocyanides as Building Blocks for Coordination Polymers and Supramolecular Assemblies

1999-02-12T00:00:00Z (GMT) by Andreas Mayr Jianhua Guo
The isocyanides 3-(4-pyridylethynyl)phenylisocyanide, <b>3</b>, 4-(4-pyridylethynyl)phenylisocyanide, <b>6</b>, 2,6-diisopropyl-4-(4-pyridylethynyl)phenylisocyanide, <b>9</b>, and 2,6-diisopropyl-4-(4-pyridyl)phenylisocyanide, <b>11</b>, were prepared. With PdI<sub>2</sub> and PtI<sub>2</sub>, these isocyanides form the complexes <i>trans</i>-[MI<sub>2</sub>(CNR)<sub>2</sub>], <b>12</b>−<b>19</b> (M = Pd, Pt; CNR = <b>3</b>, <b>6</b>, <b>9</b>, <b>11</b>). The previously prepared complex <i>trans</i>-[PdI<sub>2</sub>(CNC<sub>5</sub>H<sub>4</sub>N-3)<sub>2</sub>] and <i>trans</i>-[PdI<sub>2</sub>(CNC<sub>6</sub>H<sub>2</sub>-(<i>i</i>-Pr)<sub>2</sub>-2,6-(CC−C<sub>5</sub>H<sub>4</sub>N-4)-4)<sub>2</sub>], <b>16</b>, combine with copper bis(trifluoroacetylacetonate) in the ratio of 1:2 to form the adducts <i>trans</i>-[PdI<sub>2</sub>(CNC<sub>5</sub>H<sub>4</sub>N-3)<sub>2</sub>]·2[Cu(tfacac)<sub>2</sub>]·2CH<sub>2</sub>Cl<sub>2</sub>, <b>20</b>, and <i>trans</i>-[PdI<sub>2</sub>(CNC<sub>6</sub>H<sub>2</sub>-(<i>i</i>-Pr)<sub>2</sub>-2,6-(CC-C<sub>5</sub>H<sub>4</sub>N-4)-4)<sub>2</sub>]·2[Cu(tfacac)<sub>2</sub>], <b>21</b>, respectively. The complexes <i>trans</i>-[MI<sub>2</sub>(CNC<sub>6</sub>H<sub>2</sub>-(<i>i</i>-Pr)<sub>2</sub>-2,6-(C<sub>5</sub>H<sub>4</sub>N-4)-4)<sub>2</sub>], <b>19</b> (M = Pd) and <b>20</b> (M = Pt), react with [Pd(SO<sub>3</sub>CF<sub>3</sub>)<sub>2</sub>(dppp)] (dppp = bisdiphenylphosphinopropane) to form the molecular squares [Pd(dppp)(<i>trans</i>-[MI<sub>2</sub>(CNC<sub>6</sub>H<sub>2</sub>-(<i>i</i>-Pr)<sub>2</sub>-2,6-(C<sub>5</sub>H<sub>4</sub>N-4)-4)<sub>2</sub>]<sub>4</sub>(SO<sub>3</sub>CF<sub>3</sub>)<sub>8</sub>, <b>22</b> (M = Pd) and <b>23</b> (M = Pt). The crystal structure of <b>20</b> has been determined by X-ray crystallography. <b>20</b>:  C<sub>34</sub>H<sub>28</sub>Cl<sub>4</sub>Cu<sub>2</sub>F<sub>12</sub>I<sub>2</sub>N<sub>4</sub>O<sub>8</sub>Pd, monoclinic space group, <i>P</i>2<sub>1</sub>/n (No. 14), <i>a</i> = 10.899(3) Å, <i>b</i> = 13.903(1) Å, <i>c</i> = 17.827(6) Å, <i>β</i> = 105.50(2)°, <i>Z</i> = 2, 2618 unique reflections, <i>R</i> = 0.093, <i>R</i><sub>w</sub> = 0.091.