Siedle Gabriel, Kersting Berthold
Institut für Anorganische Chemie, Universität Leipzig, Johannisallee 29, D-04103, Leipzig, Germany.
Dalton Trans. 2006 May 7(17):2114-26. doi: 10.1039/b516071e. Epub 2006 Feb 7.
The thioethers 4-tert-butyl-2,6-bis((2-(dimethylamino)ethylimino)methyl)phenyl(tert-butyl)sulfane (tBu-L3) and 4-tert-butyl-2,6-bis((2-(dimethylamino)ethylimino)methyl)phenyl(tert-butyl)sulfane (tBu-L4) react with PdCl2(NCMe)2 to give the dinuclear palladium thiophenolate complexes [(L3)Pd2Cl2]+ (2) and [(L4Pd2(mu-Cl)]2+ (3) (HL3= 2,6-bis((2-(dimethylamino)ethylimino)methyl)-4-tert-butylbenzenethiol, HL4 = 2,6-bis((2-(dimethylamino)ethylamino)methyl)-4-tert-butylbenzenethiol). The chloride ligands in could be replaced by neutral (NCMe) and anionic ligands (NCS-, N3-, CN-, OAc-) to give the diamagnetic Pd(II) complexes [(L3)Pd2(NCMe)2]3+ (4), [(L3)Pd2(NCS)2]+ (5), [(L3)Pd2(N3)2]+ (6), [{(L3)Pd2(mu-CN)}2]4+ (7) and [(L3)Pd2(OAc)]2+ (9). The nitrile ligands in and in [(L3)Pd2(NCCH2Cl)2]3+ are readily hydrated to give the corresponding amidato complexes [(L3)Pd2(CH3CONH)]2+ (8) and [(L3)Pd2(CH2ClCONH)]2+ (10). The reaction of [(L3)Pd2(NCMe)2]3+ with NaBPh4 gave the diphenyl complex [(L3)Pd2(Ph)2]+ (11). All complexes were either isolated as perchlorate or tetraphenylborate salts and studied by IR, 1H and 13C NMR spectroscopy. In addition, complexes 2[ClO4], 3[ClO4]2, 5[BPh4], 6[BPh4], 7[ClO4]4, 9[ClO4]2, 10[ClO4]2 and 11[BPh4] have been characterized by X-ray crystallography.
硫醚4-叔丁基-2,6-双((2-(二甲基氨基)乙基亚氨基)甲基)苯基(叔丁基)硫烷(tBu-L3)和4-叔丁基-2,6-双((2-(二甲基氨基)乙基亚氨基)甲基)苯基(叔丁基)硫烷(tBu-L4)与PdCl2(NCMe)2反应，生成双核钯硫酚盐配合物[(L3)Pd2Cl2]+(2)和[(L4Pd2(μ-Cl)]2+(3)(HL3 = 2,6-双((2-(二甲基氨基)乙基亚氨基)甲基)-4-叔丁基苯硫酚，HL4 = 2,6-双((2-(二甲基氨基)乙氨基)甲基)-4-叔丁基苯硫酚)。中的氯配体可被中性配体(NCMe)和阴离子配体(NCS-、N3-、CN-、OAc-)取代，得到抗磁性的Pd(II)配合物[(L3)Pd2(NCMe)2]3+(4)、[(L3)Pd2(NCS)2]+(5)、[(L3)Pd2(N3)2]+(6)、[{(L3)Pd2(μ-CN)}2]4+(7)和[(L3)Pd2(OAc)]2+(9)。和[(L3)Pd2(NCCH2Cl)2]3+中的腈配体很容易水合，生成相应的酰胺基配合物[(L3)Pd2(CH3CONH)]2+(8)和[(L3)Pd2(CH2ClCONH)]2+(10) [(L3)Pd2(NCMe)2]3+与NaBPh?反应生成二苯基配合物[(L3)Pd2(Ph)2]+(11)。所有配合物均以高氯酸盐或四苯基硼酸盐形式分离出来，并通过红外光谱、1H和13C核磁共振光谱进行研究。此外，配合物2[ClO4]、3[ClO4]2、5[BPh4]、6[BPh4]、7[ClO4]4、9[ClO4]2、10[ClO4]2和11[BPh4]已通过X射线晶体学进行了表征。
