Department of Inorganic Chemistry, University of Santiago de Compostela, E-15702 Santiago de Compostela, Spain.
Molecules. 2023 Mar 2;28(5):2328. doi: 10.3390/molecules28052328.
Treatment of the double nuclear complex , di-μ-cloro-bis[N-(4-formylbenzylidene)cyclohexylaminato-C6, N]dipalladium, with PhPCHCH)PPh (triphos) and NHPF gave the single nuclear species , 1-N-(cyclohexylamine)-4-N-(formyl)palladium(triphos)(hexafluorophasphate). Reaction of with PhPCHCHNH in refluxing chloroform via a condensation reaction of the amine and formyl groups to produce the C=N double bond, gave , 1-N-(cyclohexylamine)-4- N-(diphenylphosphinoethylamine)palladium(triphos)(hexafluorophasphate); a potentially bidentate [,] metaloligand. However, attempts to coordinate a second metal by treatment of 3a with [PdCl(PhCN)] were to no avail. Notwithstanding, complexes and left to stand in solution spontaneously self-transformed to give in either case the double nuclear complex , 1,4-N,N-terephthalylidene(cyclohexilamine)-3,6-[bispalladium(triphos)]di(hexafluorophosphate), after undergoing further metalation of the phenyl ring, then bearing two mutually [Pd(PhPCHCH)PPh)-,,] moieties: an unprecedented and serendipitous result indeed. On the other hand, reaction of the double nuclear complex 1b, di-μ-cloro-bis[N-(3-formylbenzylidene)cyclohexylaminato-C6, N]dipalladium, with PhPCHCH)PPh (triphos) and NHPF gave the single nuclear species , 1-N-(cyclohexylamine)-4-N-(formyl)palladium(triphos)(hexafluorophasphate), Treatment of with HO/glacial MeCOOH gave cleavage of the C=N double bond and of the Pd···N interaction, yielding , isophthalaldehyde-6-palladium(triphos)hexafluorophosphate, which then reacted with PhP(CH)NH to yield complex , N,N-(isophthalylidene(diphenylphosphinopropylamine)-6-(palladiumtriphos)di(hexafluorophosphate), with two pairs of non-coordinated nitrogen and phosphorus donor atoms. Treatment of with [PdCl(PhCN)], [PtCl(PhCN)], or [PtMe(COD)] gave the new double nuclear complexes , and , palladiumdichloro-, platinumdichloro- and platinumdimethyl[N,N-(isophthalylidene(diphenylphosphinopropylamine)-6-(palladiumtriphos)(hexafluorophosphate)-P,P], respectively, showing the behavior of as a palladated bidentate [,] metaloligand. The complexes were fully characterized by microanalysis, IR, H, and P NMR spectroscopies, as appropriate. The X-ray single-crystal analyses for compounds 10 and 5b have been previously described as the perchlorate salts by JM Vila et al.
双核配合物，二μ-氯双[N-（4-甲酰基苯亚甲基）环己基氨基甲酰基-C6，N]二钯，与 PhPCHCH）PPh（三膦）和 NH4PF6 反应，得到单核物种 1-N-（环己基胺）-4-N-（甲酰基）钯（三膦）（六氟磷酸盐）。与 PhPCHCHNH 在回流氯仿中反应，通过胺和甲酰基的缩合反应生成 C=N 双键，得到 1-N-（环己基胺）-4-N-（二苯基膦基乙基胺）钯（三膦）（六氟磷酸盐）; 一种潜在的双齿 [，] 金属配体。然而，试图通过用 [PdCl（PhCN）] 处理 3a 来配位第二个金属是徒劳的。尽管如此，在溶液中放置的复合物和会自发地自我转化，在每种情况下都得到双核配合物，1,4-N,N-对苯二甲酰基（环己基胺）-3,6-[双钯（三膦）]二（六氟磷酸盐），然后对苯基环进行进一步的金属化，然后带有两个相互 [Pd（PhPCHCH）PPh）-，，] 部分：这确实是一个前所未有的意外结果。另一方面，双核配合物 1b，二μ-氯双[N-（3-甲酰基苯亚甲基）环己基氨基甲酰基-C6，N]二钯，与 PhPCHCH）PPh（三膦）和 NH4PF6 反应，得到单核物种 1-N-（环己基胺）-4-N-（甲酰基）钯（三膦）（六氟磷酸盐），用 HO/glacial MeCOOH 处理 得到 C=N 双键和 Pd···N 相互作用的断裂，生成间苯二甲醛-6-钯（三膦）六氟磷酸盐，然后与 PhP（CH）NH 反应生成配合物，N，N-（间苯二甲酰基（二苯基膦基丙基胺）-6-（钯三膦）二（六氟磷酸盐），带有两对非配位的氮和磷供体原子。用 [PdCl（PhCN）]、[PtCl（PhCN）] 或 [PtMe（COD）] 处理 得到新的双核配合物，和，钯二氯，铂二氯和铂二甲基[N，N-（间苯二甲酰基（二苯基膦基丙基胺）-6-（钯三膦）（六氟磷酸盐）-P，P]，分别表现出作为钯化双齿 [，] 金属配体的行为。根据需要，通过微分析、IR、H 和 P NMR 光谱对配合物进行了充分的表征。JM Vila 等人以前曾描述过化合物 10 和 5b 的 X 射线单晶分析为高氯酸盐盐。
