Abstract

The complexes [Pt(L)Cl]₂ (1), Pt(L)(HL)Cl (2), (two conformers, 2a and 2b), Pt(L)(Ph₃P)Cl (3), Pt(L)(3,5-Me_2t-py)Cl (4) and Pt(L)(CO)Cl (5) (HL=7-chloro-1,3-dihydro-1-methyl-5-phenyl-2H-1,4-benzodiazepin-2-one, DIAZEPAM) have been prepared and characterized by IR, MS and ¹H, ¹³C, ³¹p and two-dimensional correlation NMR spectra. Complexes 1-5 contain a deprotonated DIAZEPAM coordinated to the metal through the N(4) atom and the ortho-carbon of the 5-phenyl substituent. In complex 2, as shown by a sing]e crystal X-ray structure determination, carried out on conformer 2a, in addition to the cyclometallated system, a neutral molecule of DIAZEPAM is coordinated through the N(4) atom. The crystals of compound 2a, C₃₂H₂₅Cl₃N₄O₂Pt, are monoclinic, space group P2₁/_n with a = 13.601(3), b = 15.951(5), c = 13.837(3) Å, β = 96.38(2)°, Z = 4. The structure was refined to R = 0.021 and R_w = 0.032 on the basis of 4922 unique reflections with I>3σ(I). The platinum atom is in a square planar geometry with the carbon atom trans to the chloride ligand: Pt---C=1.983(3), Pt---Cl=2.402(1), Pt---N=2.031(3) and 2.009(3) Å.

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