Pd···H−C Interactions. Preparation and Structure of Orthometalated Tetranuclear Complexes of Palladium(II) and Platinum(II)

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Abstract
The reaction of 2-(1-naphthyl)benzothiazoline with palladium(II) acetate leads to helical mononuclear and orthometalated tetranuclear products. The molecular structures of mononuclear palladium(II) [Pd(H1-nabz)2] (1) (H21-nabz = 2-N-(1-naphthylmethylideneamino)benzenethiolate), tetranuclear palladium(II) [Pd4(1-nabz)4] (2) and tetranuclear platinum(II) [Pt4(1-nabz)4] (3) have been determined by single-crystal X-ray diffraction method. Crystal data for complex 1 are as follows: a = 14.208(3) Å, b = 18.227(4) Å, c = 14.398(8) Å; β = 94.55(3)°; V = 3717.0(23) Å3; space group = P21/n, Z = 4. Crystal data for the complex 2 are as follows: a = b = 15.798(3) Å, c = 23.728(4) Å; V = 5921.7(20) Å3; space group = I41/a, Z = 16 for the Pd(1-nabz) unit. Crystal data for the complex 3 are as follows: a = b = 15.496(2) Å, c = 24.348(3) Å; V = 5846.3(20) Å3; space group = I41/a, Z = 16 for the Pt(1-nabz) unit. The mononuclear palladium(II) complex reveals short ortho-hydrogen···palladium distances of 2.66(7) and 2.48(7) Å. These short distances and 1H NMR studies provide a M···H−C interaction which can be regarded as a three-center four-electron interaction. The molecular structures of 2 and 3 confirm the formation of unusual tetranuclear compounds featuring a rare C,N,S-tridentate ligand derived from orthometalation of pendant side arm. The structural and chemical properties of the mononuclear palladium(II) complex 1 clearly suggest that 1 is a potential intermediate in the formation of the tetranuclear complex 2 by orthometalation reactions.

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