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, 3, 4-(4-pyridylethynyl)phenylisocyanide, 6, 2,6-diisopropyl-4-(4-pyridylethynyl)phenylisocyanide, 9, and 2,6-diisopropyl-4-(4-pyridyl)phenylisocyanide, 11, were prepared. With PdI2 and PtI2, these isocyanides form the complexes trans-[MI2(CNR)2], 1219 (M = Pd, Pt; CNR = 3, 6, 9, 11). The previously prepared complex trans-[PdI2(CNC5H4N-3)2] and trans-[PdI2(CNC6H2-(i-Pr)2-2,6-(CC−C5H4N-4)-4)2], 16, combine with copper bis(trifluoroacetylacetonate) in the ratio of 1:2 to form the adducts trans-[PdI2(CNC5H4N-3)2]·2[Cu(tfacac)2]·2CH2Cl2, 20, and trans-[PdI2(CNC6H2-(i-Pr)2-2,6-(CC-C5H4N-4)-4)2]·2[Cu(tfacac)2], 21, respectively. The complexes trans-[MI2(CNC6H2-(i-Pr)2-2,6-(C5H4N-4)-4)2], 19 (M = Pd) and 20 (M = Pt), react with [Pd(SO3CF3)2(dppp)] (dppp = bisdiphenylphosphinopropane) to form the molecular squares [Pd(dppp)(trans-[MI2(CNC6H2-(i-Pr)2-2,6-(C5H4N-4)-4)2]4(SO3CF3)8, 22 (M = Pd) and 23 (M = Pt). The crystal structure of 20 has been determined by X-ray crystallography. 20:  C34H28Cl4Cu2F12I2N4O8Pd, monoclinic space group, P21/n (No. 14), a = 10.899(3) Å, b = 13.903(1) Å, c = 17.827(6) Å, β = 105.50(2)°, Z = 2, 2618 unique reflections, R = 0.093, Rw = 0.091.