10.1021/ic9803053.s001 Andreas Mayr Andreas Mayr Jianhua Guo Jianhua Guo Metal Complexes of Pyridylphenylisocyanides and Pyridylethynylphenylisocyanides as Building Blocks for Coordination Polymers and Supramolecular Assemblies American Chemical Society 1999 Coordination Polymers PdI 2 tran Pr Supramolecular Assemblies MI PtI 2 Building Blocks space group 3 CF 3 CH isocyanides form CC 2 N 4 O 8 Pd Cu crystal structure CNR CNC metal Complexes 1999-02-12 00:00:00 Journal contribution https://acs.figshare.com/articles/journal_contribution/Metal_Complexes_of_Pyridylphenylisocyanides_and_Pyridylethynylphenylisocyanides_as_Building_Blocks_for_Coordination_Polymers_and_Supramolecular_Assemblies/3622053 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.