Ní Dhubhghaill Orla M, Lennon Joanne, Drew Michael G B
Analytical and Biological Chemistry Research Facility and Department of Chemistry, University College Cork, Cork, Ireland.
Dalton Trans. 2005 Oct 7(19):3213-20. doi: 10.1039/b509834c. Epub 2005 Aug 30.
The previously synthesised Schiff-base ligands 2-(2-Ph(2)PC(6)H(4)N[double bond, length as m-dash]CH)-R'-C(6)H(3)OH (R'= 3-OCH(3), HL(1); 5-OCH(3), HL(2); 5-Br, HL(3); 5-Cl, HL(4)) were prepared by a faster, more efficient route involving a microwave assisted co-condensation of 2-(diphenylphosphino)aniline with the appropriate substituted salicylaldehyde. HL(1-4) react directly with M(II)Cl(2)(M = Pd, Pt) or Pt(II)I(2)(cod) affording neutral square-planar complexes of general formula [M(II)Cl(eta(3)-L(1-4))](M = Pd, Pt, 1-8) and [Pt(II)I(eta(3)-L(1-4))](M = Pd, Pt, 9-12). Reaction of complexes 1-4 with the triarylphosphines PR(3)(R = Ph, p-tolyl) gave the novel ionic complexes [Pd(II)(PR(3))(eta(3)-L(1-4))]ClO(4)(13-20). Substituted platinum complexes of the type [Pt(II)(PR(3))(eta(3)-L(1-4))]ClO(4)(R = P(CH(2)CH(2)CN)(3)21-24) and [Pt(II)(P(p-tolyl)(3))(eta(3)-L(3,4))]ClO(4)( 25 and 26 ) were synthesised from the appropriate [Pt(II)Cl(eta(3)-L(1-4))] complex (5-8) and PR(3). The complexes are characterised by microanalytical and spectroscopic techniques. The crystal structures of 3, 6, 10, 15, 20 and 26 were determined and revealed the metal to be in a square-planar four-coordinate environment containing a planar tridentate ligand with an O,N,P donor set together with one further atom which is trans to the central nitrogen atom.
先前合成的席夫碱配体2-(2-Ph(2)PC(6)H(4)N═CH)-R'-C(6)H(3)OH(R' = 3-OCH(3),HL(1);5-OCH(3),HL(2);5-Br,HL(3);5-Cl,HL(4))是通过一种更快、更有效的路线制备的,该路线涉及2-(二苯基膦基)苯胺与适当取代的水杨醛的微波辅助共缩合反应。HL(1 - 4)直接与M(II)Cl(2)(M = Pd,Pt)或Pt(II)I(2)(cod)反应,得到通式为[M(II)Cl(η(3)-L(1 - 4))](M = Pd,Pt,1 - 8)和[Pt(II)I(η(3)-L(1 - 4))](M = Pd,Pt,9 - 12)的中性平面四方配合物。配合物1 - 4与三芳基膦PR(3)(R = Ph,对甲苯基)反应得到新型离子配合物[Pd(II)(PR(3))(η(3)-L(1 - 4))]ClO(4)(13 - 20)。通过适当的[Pt(II)Cl(η(3)-L(1 - 4))]配合物(5 - 8)与PR(3)合成了[Pt(II)(PR(3))(η(3)-L(1 - 4))]ClO(4)类型的取代铂配合物(R = P(CH(2)CH(2)CN)(3) 21 - 24)和[Pt(II)(P(对甲苯基)(3))(η(3)-L(3,4))]ClO(4)(25和26)。这些配合物通过微量分析和光谱技术进行表征。测定了3、6、10、15、20和26的晶体结构,结果表明金属处于平面四方配位环境中,其中包含一个具有O、N、P供体集的平面三齿配体以及一个与中心氮原子相对的另外一个原子。