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Palladium(II) ortho-cyano-aminothiophenolate (ocap) complexes
Dalton Transactions ( IF 4 ) Pub Date : 2022-11-11 , DOI: 10.1039/d2dt02681c
Subhi A Al-Jibori 1 , Ahmed S Al-Janabi 1 , Ahmed A Irzoqi 2 , Ali I A Abdullah 3 , Sucharita Basak-Modi 4 , Georgia R F Orton 5 , Shishir Ghosh 4, 5 , Christof Wagner 6 , Graeme Hogarth 5
Affiliation  

A series of Pd(II) complexes containing ortho-cyano-aminothiophenolate (ocap) ligands have been prepared and their molecular structures elucidated. Hg(II) ocap complexes, [Hg{SC6H3XN(C[triple bond, length as m-dash]N)}]n (X = H, Me) (1), react with Na2S to afford HgS and Na2[ocap] which reacts in situ with K2[PdCl4] to afford palladium ocap complexes [Pd{SC6H3XN(C[triple bond, length as m-dash]N)}]n (2). A second route to these coordination polymers has also been developed from reactions of 2-aminobenzothiazole (abt) complexes, trans-PdCl2(abt)2 (3), with NaOH. We have not been able to crystallographically characterise coordination polymers 2, but addition of PPh3, a range of phosphines and cyclic diamines affords mono and binuclear complexes in which the ocap ligand adopts different coordination geometries. With PPh3, binuclear [Pd(μ-κ21-ocap)(PPh3)]2 (4) results, in which the ocap bridges the Pd2 centre acting as an S,N-chelate to one metal centre and binding the second via coordination of the cyanide nitrogen. In contrast, with diphosphines, Ph2P(CH2)nPPh2 (n = 1–4), mononuclear species predominate as shown in the molecular structures of Pd(κ2-ocap){κ2-Ph2P(CH2)nPPh2} (5–7; n = 1–3). With 2,2′-bipy and 1,10-phen we propose that related monomeric chelates Pd(κ2-ocap)(κ2-bipy) (9) and Pd(κ2-ocap)(κ2-phen) (10) result but we have been unable to substantiate this crystallographically. Addition of HgCl2(phen) to 9a (generated in situ) affords heterobimetallic Pd(κ2-phen)(μ-κ21-ocap)HgCl22-phen) (11), in which Hg(II) is coordinated through the ring sulfur.

中文翻译:

钯 (II) 邻氰基氨基苯硫酚 (ocap) 络合物

制备了一系列含有邻氰基氨基苯硫酚 (ocap) 配体的 Pd( II ) 配合物,并阐明了它们的分子结构。Hg( II ) ocap 络合物 [Hg{SC 6 H 3 XN(CN )}] n (X = H, Me) ( 1 ),与 Na 2 S 反应生成 HgS 和 Na 2 [ocap],后者与 K 2 [PdCl 4 ]原位得到钯 ocap 络合物 [Pd{SC 6 H 3 XN(C N)}] n ( 2[三键,长度为 m-dash][三键,长度为 m-dash]). 还通过 2-氨基苯并噻唑 (abt) 络合物反式-PdCl 2 ( abt) 2 ( 3 ) 与 NaOH 的反应开发了获得这些配位聚合物的第二条路线。我们无法从晶体学上表征配位聚合物2,但添加 PPh 3、一系列膦和环状二胺可提供单核和双核复合物,其中 ocap 配体采用不同的配位几何结构。对于 PPh 3,双核 [Pd(μ-κ 21 -ocap)(PPh 3 )] 2 ( 4 ) 结果,其中 ocap 桥接 Pd 2中心充当一个 S,N-螯合物到一个金属中心,并通过氰化物氮的配位结合第二个金属中心。相比之下,对于二膦,Ph 2 P(CH 2 ) n PPh 2 ( n = 1–4),单核物质占主导地位,如 Pd(κ 2 -ocap){κ 2 -Ph 2 P(CH 2 ) n PPh 2 } ( 5–7 ; n = 1–3)。对于 2,2'-bipy 和 1,10-phen,我们提出相关的单体螯合物 Pd(κ 2 -ocap)(κ 2 -bipy) ( 9 ) 和 Pd(κ2 -ocap)(κ 2 -phen) ( 10 ) 结果,但我们无法从晶体学上证实这一点。将 HgCl 2 (phen)添加到9a (原位生成)得到异双金属 Pd(κ 2 -phen)(μ-κ 2 1 -ocap)HgCl 2 2 -phen) ( 11 ),其中 Hg( II ) 通过环硫配位。
更新日期:2022-11-16
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