Self-Assembly of Cationic Pd(II)/Pt(II) Metallomacrocycles Containing Tetrahedral C<sub>2</sub>Co<sub>2</sub> Clusters from Rigid Cluster-Bridged Bipyridine (4-C<sub>5</sub>H<sub>4</sub>N)<sub>2</sub>C<sub>2</sub>Co<sub>2</sub>(CO)<sub>6</sub> and Diphosphine- or Diarsine-Chelated Pd(II)/Pt(II) Complexes [M(dppb)(H<sub>2</sub>O)<sub>2</sub>][OTf]<sub>2</sub> (M = Pd, Pt), [Pd(dpab)(H<sub>2</sub>O)(OTf)][OTf], and [Pt(dpab)(H<sub>2</sub>O)<sub>2</sub>][OTf]<sub>2</sub>
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The preparation, characterization, and some properties of the C2Co2 cluster-bridged bipyridine ligand (4-C5H4N)2C2Co2(CO)6 (1), diphosphine-chelated Pd(II)/Pt(II) complexes [M(dppb)(H2O)2][OTf]2 (dppb = 1,4-bis(diphenylphosphino)butane, OTf = SO3CF3; 2, M = Pd; 3, M = Pt), and the unique cationic cluster-containing Pd(II)/Pt(II) macrocycles {[M(dppb)]-μ-[(4-C5H4N)2C2Co2(CO)6]}2[OTf]4 (4, M = Pd; 5, M = Pt) and {[M(dpab)]-μ-[(4-C5H4N)2C2Co2(CO)6]}2[OTf]4 (dpab = 1,4-bis(diphenylarsino)butane; 6, M = Pd; 7, M = Pt) are reported. While ligand 1 is prepared by reaction of bis(4-pyridyl)acetylene with Co2(CO)8 in 61% yield, complexes 2 and 3 are prepared by reaction of M(dppb)Cl2 with silver triflate followed by hydrolysis of the intermediates M(dppb)(OTf)2 in 96% and 94% yields, respectively. Particularly interesting is that the self-assembly of ligand 1 with 2 and 3 results in formation of the C2Co2 cluster-containing macrocycles 4 and 5 in 62% and 65% yields, whereas 6 and 7 can be produced by self-assembly of 1 with diarsine-chelated complexes [Pd(dpab)(H2O)(OTf)][OTf] and [Pt(dpab)(H2O)2][OTf]2 in 79% and 68% yields, respectively. 1−7 have been fully characterized by elemental analysis, spectroscopy, and particularly for 2−7 X-ray crystallography, and for 1, 4, and 7 by cyclic voltammetric techniques.
