Department of Chemistry, College of Science, University of Tikrit, Tikrit, Iraq.
Department of Chemistry, College of Education, University of Tikrit, Tikrit, Iraq.
Dalton Trans. 2022 Dec 6;51(47):18136-18142. doi: 10.1039/d2dt02681c.
A series of Pd(II) complexes containing -cyano-aminothiophenolate (ocap) ligands have been prepared and their molecular structures elucidated. Hg(II) ocap complexes, [Hg{SCHXN(CN)}] (X = H, Me) (1), react with NaS to afford HgS and Na[ocap] which reacts with K[PdCl] to afford palladium ocap complexes [Pd{SCHXN(CN)}] (2). A second route to these coordination polymers has also been developed from reactions of 2-aminobenzothiazole (abt) complexes, -PdCl(abt) (3), with NaOH. We have not been able to crystallographically characterise coordination polymers 2, but addition of PPh, a range of phosphines and cyclic diamines affords mono and binuclear complexes in which the ocap ligand adopts different coordination geometries. With PPh, binuclear [Pd(μ-κ,κ-ocap)(PPh)] (4) results, in which the ocap bridges the Pd centre acting as an S,N-chelate to one metal centre and binding the second coordination of the cyanide nitrogen. In contrast, with diphosphines, PhP(CH)PPh ( = 1-4), mononuclear species predominate as shown in the molecular structures of Pd(κ-ocap){κ-PhP(CH)PPh} (5-7; = 1-3). With 2,2'-bipy and 1,10-phen we propose that related monomeric chelates Pd(κ-ocap)(κ-bipy) (9) and Pd(κ-ocap)(κ-phen) (10) result but we have been unable to substantiate this crystallographically. Addition of HgCl(phen) to 9a (generated ) affords heterobimetallic Pd(κ-phen)(μ-κ,κ-ocap)HgCl(κ-phen) (11), in which Hg(II) is coordinated through the ring sulfur.
一系列含有 -氰基-氨硫代酚（ocap）配体的 Pd(II) 配合物已被制备，并对其分子结构进行了阐明。Hg(II)ocap 配合物 [Hg{SCHXN(C N)}]（X = H，Me）（1）与 NaS 反应生成 HgS 和 Na[ocap]，后者与 K[PdCl]反应生成钯 ocap 配合物 [Pd{SCHXN(C N)}]（2）。还开发了另一种制备这些配位聚合物的方法，即 2-氨基苯并噻唑（abt）配合物 -PdCl(abt)（3）与 NaOH 反应。我们无法通过晶体学方法对配位聚合物 2 进行表征，但加入 PPh、一系列膦和环状二胺后，会得到单核和双核配合物，其中 ocap 配体采用不同的配位几何构型。与 PPh 一起，得到双核 [Pd(μ-κ，κ-ocap)(PPh)]（4），其中 ocap 桥接 Pd 中心，作为 S，N-螯合物与一个金属中心配位，并与氰化物氮的第二个配位键合。相比之下，与二膦 PhP(CH)PPh（ = 1-4）一起，单核物种占主导地位，如 Pd(κ-ocap){κ-PhP(CH)PPh}（5-7； = 1-3）的分子结构所示。对于 2,2'-bipy 和 1,10-phen，我们提出生成相关的单核螯合物 Pd(κ-ocap)(κ-bipy)（9）和 Pd(κ-ocap)(κ-phen)（10），但我们无法通过晶体学方法证实这一点。向 9a（生成的）中加入 HgCl(phen) 可得到异双核 Pd(κ-phen)(μ-κ，κ-ocap)HgCl(κ-phen)（11），其中 Hg(II) 通过环硫原子配位。
