Linear Bidentate Ligands (L) with Two Terminal Pyridyl N-Donor Groups Forming Pt(II)LCl₂ Complexes with Rare...

NMR and X-ray diffraction studies were conducted on Pt(II)LCl₂ complexes prepared with the new N-donor ligands N(SO₂R)Me _ndpa (R = Me, Tol; n = 2, 4). These ligands differ from N(H)dpa (di-2-picolylamine) in having the central N within a tertiary sulfonamide group instead of a secondary amine group and having Me groups at the 6,6'-positions ( n = 2) or 3,3',5,5'-positions ( n = 4) of the pyridyl rings. The N(SO₂R)3,3',5,5'-Me₄dpa ligands are coordinated in a bidentate fashion in Pt( N(SO₂R)3,3',5,5'-Me₄dpa)Cl₂ complexes, forming a rare eight-membered chelate ring. The sulfonamide N atom did not bind to Pt(II), consistent with indications in the literature that tertiary sulfonamides are unlikely to anchor two meridionally coordinated five-membered chelate rings in solutions of coordinating solvents. The N(SO₂R)6,6'-Me₂dpa ligands coordinate in a monodentate fashion to form the binuclear complexes [ trans-Pt(DMSO)Cl₂]₂( N(SO₂R)6,6'-Me₂dpa). The monodentate instead of bidentate N(SO₂R)6,6'-Me₂dpa coordination is attributed to 6,6'-Me steric bulk. These binuclear complexes are indefinitely stable in DMF- d₇, but in DMSO- d₆ the N(SO₂R)6,6'-Me₂dpa ligands dissociate completely. In DMSO- d₆, the bidentate ligands in Pt( N(SO₂R)3,3',5,5'-Me₄dpa)Cl₂ complexes also dissociate, but incompletely; these complexes provide rare examples of association-dissociation equilibria of N,N bidentate ligands in Pt(II) chemistry. Like typical cis-PtLCl₂ complexes, the Pt( N(SO₂R)3,3',5,5'-Me₄dpa)Cl₂ complexes undergo monosolvolysis in DMSO- d₆ to form the [Pt( N(SO₂R)3,3',5,5'-Me₄dpa)(DMSO- d₆)Cl]⁺ cations. However, unlike typical cis-PtLCl₂ complexes, the Pt( N(SO₂R)3,3',5,5'-Me₄dpa)Cl₂ complexes surprisingly do not react readily with the excellent N-donor bioligand guanosine. A comparison of the structural features of over 50 known relevant Pt(II) complexes having smaller chelate rings with those of the very few relevant Pt(II) complexes having eight-membered chelate rings indicates that the pyridyl rings in Pt( N(SO₂R)3,3',5,5'-Me₄dpa)Cl₂ complexes are well positioned to form strong Pt-N bonds. Therefore, the dissociation of the bidentate ligand and the poor biomolecule reactivity of the Pt( N(SO₂R)3,3',5,5'-Me₄dpa)Cl₂ complexes arise from steric consequences imposed by the -CH₂-N(SO₂R)-CH₂- chain in the eight-membered chelate ring.