The structures of (phenylato)( N-2-thiophenecarboxamido- meso-tetraphenylporphyrinato)mercury(II) and bisphenylmercury(II) complex of 21-(4- tert-butyl-benzenesulfonamido)-5,10,15,20-tetraphenylporphyrin

Abstract

The reaction of PhHgOAc with N-NHCO-2-C 4H 3S-Htpp ( 5) and N- p-HNSO2C6H4 tBu-Htpp ( 4) gave a mercury (II) complex of (phenylato) ( N-2-thiophenecarboxamido- meso-tetra phenylporphyrinato)mercury(II) 1.5 methylene chloride solvate [HgPh( N-NHCO-2-C 4H 3S-tpp) · CH 2Cl 2 · 0.5C 6H 14; 6 · CH 2Cl 2 · 0.5C 6H 14] and a bismercury complex of bisphenylmercury(II) complex of 21-(4- tert-butyl-benzenesulfonamido)-5,10,15,20-tetraphenylporphyrin, [(HgPh)2( N- p-NSO 2C 6H 4 t Bu-tpp); 7], respectively. The crystal structures of 6 · CH 2Cl 2 · 0.5C 6H 14 and 7 were determined. The coordination sphere around Hg(1) in 6 · CH 2Cl 2 · 0.5C 6H 14 and Hg(2) in 7 is a sitting-atop derivative with a seesaw geometry, whereas for the Hg(1) in 7, it is a linear coordination geometry. Both Hg(1) in 6 · CH 2Cl 2 · 0.5C 6H 14 and Hg(2) in 7 acquire 4-coordination with four strong bonds [Hg(1)–N(1) = 2.586(3) Å, Hg(1)–N(2) = 2.118(3) Å, Hg(1)–N(3) = 2.625(3) Å, and Hg(1)–C(50) = 2.049(4) Å for 6 · CH 2Cl 2 · 0.5C 6H 14; Hg(2)–N(1) = 2.566(6) Å, Hg(2)–N(2) = 2.155(6) Å, Hg(2)–N() = 2.583(6) Å, and Hg(2)–C(61) = 2.064(7) Å for 7]. The plane of the three pyrrole nitrogen atoms [i.e., N(1)–N(3)] strongly bonded to Hg(1) in 6 · CH 2Cl 2 · 0.5C 6H 14 and to Hg(2) in 7 is adopted as a reference plane 3N. For the Hg 2+ complex in 6 · CH 2Cl 2 · 0.5C 6H 14, the pyrrole nitrogen bonded to the 2-thiophenecarboxamido ligand lies in a plane with a dihedral angle of 33.4° with respect to the 3N plane, but for the bismercury(II) complex in 7, the corresponding dihedral angle for the pyrrole nitrogen bonded to the NSO 2C 6H 4 t Bu group is found to be 42.9°. In the former complex, Hg(1) 2+ and N(5) are located on different sides at 1.47 and −1.29 Å from its 3N plane, and in the latter one, Hg(2) 2+ and N(5) are also located on different sides at −1.49 and 1.36 Å form its 3N plane. The Hg(1)⋯Hg(2) distance in 7 is 3.622(6) Å. Hence, no metallophilic Hg(II)⋯Hg(II) interaction may be anticipated. NOE difference spectroscopy, HMQC and HMBC were employed to unambiguous assignment for the 1H and 13C NMR resonances of 6 · CH 2Cl 2 · 0.5C 6H 14 in CD 2Cl 2 and 7 in CDCl 3 at 20 °C. The 199Hg chemical shift δ for a 0.05 M solution of 7 in CDCl 3 solution is observed at −1074 ppm for Hg(2) nucleus with a coordination number of four and at −1191 ppm for Hg(1) nucleus with a coordination number of two. The former resonance is consistent with that chemical shift for a 0.01 M solution of 6 in CD 2Cl 2 having observed at −1108 ppm for Hg(1) nucleus with a coordination number of four.