Amine-functionalised aminophosphines: synthesis, reversible co-ordination to platinum and use in heteronuclear dimer formation
作者:Andrew D. Burrows、Mary F. Mahon、Mark T. Palmer
DOI:10.1039/b005899h
日期:——
Amine functionalised aminophosphines Ph2PN(R)CH2CH2NMe2 (R = H L1 or Me L2) were prepared from the reaction of PPh2Cl with NHRCH2CH2NMe2 in the presence of the base n-butyllithium (L1) or triethylamine (L2). Reaction of two equivalents of L1,2 with [PtCl2(cod)] gave the complexes cis-[PtCl2L2] (L = L11 or L22), which were shown to be fluxional with one of the amine groups reversibly co-ordinating to displace a chloride. Removal of a chloride in 1 by metathesis gave cis-[PtCl(L1-P)(L1-P,N)]PF63 which was not fluxional on the NMR timescale. Reaction of one equivalent of L2 with [PtCl2(cod)] gave the complex cis-[PtCl2(L2-P,N)] 4 in which L2 is acting as a bidentate ligand. The reaction of L2 with [Pt(dmba)(μ-Cl)}2] (Hdmba = N,N-dimethylbenzylamine) gave [Pt(dmba)Cl(L2)] 5, which exists as a mixture of the two geometric isomers. Reaction of 5 with TlPF6 gave [Pt(dmba)(L2-P,N)]-PF66 as a single isomer in which the phosphorus atom is co-ordinated trans to the N,N-dimethylbenzylamine nitrogen atom. Complex 2 reacts with CoCl2·6H2O and ZnCl2 to give cis-[(L2-P,N)ClPt(μ-L2)MCl3] (M = Co 7 or Zn 8). The zwitterionic structure of 7 was confirmed by a single-crystal X-ray analysis, which showed no metal–metal interaction between the platinum and cobalt centres.
胺官能化氨基膦 Ph2PN(R)CH2CH2NMe2(R = H L1 或 Me L2)由 PPh2Cl 与 NHRCH2CH2NMe2 在碱正丁基锂 (L1) 或三乙胺 (L2) 存在下反应制备。两当量的 L1,2 与 [PtCl2(cod)] 反应,得到配合物 cis-[PtCl2L2](L = L11 或 L22),该配合物被证明与其中一个胺基团可逆地配位以取代一个胺基团。氯化物。通过复分解除去1中的氯化物得到顺式-[PtCl(L1-P)(L1-P,N)]PF63,其在NMR时间尺度上不流动。一当量的 L2 与 [PtCl2(cod)] 反应得到配合物 cis-[PtCl2(L2-P,N)] 4,其中 L2 充当二齿配体。 L2 与 [Pt(dmba)(μ-Cl)}2] (Hdmba = N,N-二甲基苄胺) 反应得到 [Pt(dmba)Cl(L2)] 5,它作为两种几何形状的混合物存在异构体。 5与TlPF6反应得到单一异构体[Pt(dmba)(L2-P,N)]-PF66,其中磷原子与N,N-二甲基苄胺氮原子反式配位。配合物 2 与 CoCl2·6H2O 和 ZnCl2 反应生成顺式-[(L2-P,N)ClPt(μ-L2)MCl3](M = Co 7 或 Zn 8)。单晶X射线分析证实了7的两性离子结构,表明铂和钴中心之间没有金属-金属相互作用。