名称:
Bis(carboxylato) complexes of platinum(II). Structural and bonding analysis of [Pt(O2CR)2(L–L)][L–L = 2PPh3, Ph2PCH2PPh2or Fe(C5H4PPh2)2; R = Me, CF3, Prior Ph]
摘要:
Treatment of [PtCl2(L-L)] [L-L = 2 PPh(3), Ph(2)PCH(2)PPh(2)(dppm) or Fe(C(5)H(4)PPh(2))(2)(dppf)] with Ag(O(2)CR) (R = Me, CF3, Pr-i or Ph) at room temperature generally gave [Pt(O(2)CR)(2)(L-L)] in moderate to good yields. The crystal and molecular structures of [Pt(O(2)CMe)(2)(dppf)]. H2O, [Pt(O(2)CPh)(2)(dppf)]. CH2Cl2 and [Pt(O2CCF3)(2)(dppm)] have been determined by single-crystal X-ray diffractometry. All these complexes show a mononuclear square-planar structure with a chelating diphosphine and two neighbouring (cis) carboxylates in a monodentate mode. These structures contrast those of the parent [Pt-4(mu-O(2)CMe)(8)] and its derivative [Pt-4(en)(4)(mu-O(2)CMe)(4)](4+) (en = ethylenediamine) which are tetrameric, based on octahedral Pt-II, and contain bridging acetates and direct Pt-Pt bonds. Fenske-Hall molecular orbital calculations of these structures confirmed the existence of Pt-Pt bonding interactions. The presence of hard and electronegative ligands like en and acetate incurs a deficiency in sigma-electron density, compared to virtually filled non-bonding orbitals; the former is alleviated by Pt-Pt bonding. d(8) Complexes with ligands like phosphines possessing both sigma-donating and pi-accepting qualities appear to favour the usual square-planar geometry.