Mononuclear complexes of copper(I), palladium(II), and ruthenium(II) with oxalic amidine-type ligands by coupled cation-/anion coordination
Mononuclear complexes of copper(I), palladium(II), and ruthenium(II) with oxalic amidine-type ligands by coupled cation-/anion coordination
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DOI：
10.1002/zaac.200300181
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发表时间：
2003-11-01
影响因子：
1.4
通讯作者：
Görls, H
中科院分区：
文献类型：
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作者：
Böttcher, L;Scholz, A;Görls, H
草酰胺类化合物(RN)-N-1=C(NHR2)-C(=NHR2)=NR1(H(2)A：R-1=R-2=对甲苯基；H_2B：R-1=R-2=均三甲苯)与[Cu(CH3CN)(4)(BF4)/PPh3]反应生成单核配合物{[(Ph3p)(2)Cu]AH(2)(F4B)}(1)和{[(Ph3p)Cu]BH2(F4B)}(2)。单晶的X-射线衍射谱表明，铜-I配位于1，4-二氮二烯单元。四氟硼酸盐在1，2-二胺单元上通过氢键(“偶合阳离子-阴离子配位”)成键。[(烯丙基)PdCl](2)与H(2)A反应生成[(烯丙基)Pdah(2)...氯-2(烯丙基)Pd](3).与H_2B形成类似的化合物4。在这些络合物中，(烯丙基)Pd+片段配位于中性草酰肼配体的1，4-双氮烯部分。此外，[烯丙基PdCl(2)](-)还配位在1，2-二胺上。通过类似的阳离子-阴离子偶合配位作用，可以合成一些有机络合物，如[(P-cymolRu(Cl)CH2...Cl](6)和[(4，4‘，4“-tri-t-butyl-terpyridin)(Cl)RuAH(2)...Cl](9))。
Oxalamidines (RN)-N-1=C(NHR2)-C(=NHR2) =NR1 (H(2)A: R-1 = R-2 = p-tolyl; H2B: R-1 = R-2 = mesityl) react with [Cu(CH3CN)(4)(BF4)/PPh3 to form the mononuclear complexes {[(Ph3P)(2)Cu]AH(2)(F4B)} (1) and {[(Ph3P)Cu]BH2(F4B)} (2). X-ray diffraction measurements of single crystals show that Cu-I is coordinated at the 1,4-diazadiene unit. Tetrafluoroborat is bonded at the 1,2-diamine unit via hydrogen bonds ("coupled cation-/anion coordination"). [(allyl)PdCl](2) reacts with H(2)A to form the allyl complex [(allyl)PdAH(2)...Cl-2(allyl)Pd] (3). With H2B the analogous compound 4 is formed. In these complexes the (allyl)Pd+-fragment is coordinated at the 1,4-diazadiene part of the neutral oxalic amidine ligand. In addition, [allylPdCl(2)](-) coordinates at the 1,2-diamine site. By analogous coupled cation-/anion coordination some Run complexes, e. g. [(p-cymolRu(Cl)CH2...Cl] (6), and [(4,4',4"-tri-t-butyl-terpyridin)(Cl)RuAH(2)...Cl] (9) can be prepared.