Palladium complexes of azines, -diazines and -2-pyridylazines containing (1R)-(+)-camphor or (1R)-()-fenchone groups
Palladium complexes of azines, -diazines and -2-pyridylazines containing (1R)-(+)-camphor or (1R)-()-fenchone groups
复制标题
含有 (1R)-( )-樟脑或 (1R)-()-小茴香酮基团的吖嗪、-二嗪和-2-吡啶嗪的钯络合物
DOI：
10.1039/dt9950001697
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发表时间：
1995
期刊：
影响因子：
--
通讯作者：
J. Vessey
中科院分区：
文献类型：
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作者：
B. Shaw;M. Thornton;J. Vessey
混合monoazines类型H2CN-NC10H16 (C10H16 (1 r) -(+)樟脑残渣(L1),或(1 r) -(-)葑酮残渣(L2)]或Me2CN-NC10H16 (C10H16 (1 r) -(+)樟脑残渣(L3)],或α-diazines C10H16N-NCH-CHN-NC10H16 (C10H16 (1 r) -(+)樟脑残渣(L4)或(1 r) -(-)葑酮残渣(L5)],或α2-pyridyl吖嗪C10H16N-NCHC5H4N (C10H16 (1 r) -(+)樟脑残渣(16种)或(1 r) -(-)葑酮残渣(地级)]对Na2PdCl4给L1 (PdCl2Ln2)类型的化合物,L2或L3为单齿氮供体配体，L4、L5、L6或L7为[PdCl2Ln]型的螯合单核配合物。单齿嘧啶的配合物L1和L2在溶液中以连接氮不同的异构体混合物的形式存在。化合物L1、L2和L4-L7也与[Pd2Cl4(PR3)2]反应生成[PdCl2(PR3)Ln](n= 1, R3= Me2Ph或Me2(C6H4OMe-4)；n= 2, R3= Me2Ph, Me2（C6H4OMe-4）或Ph3；n= 4或5，R3= Me2Ph；n= 6, R3= Bun3；n= 7, R3= Bun3或Me2Ph)，其中配体为单齿，或[{PdCl2(PR3)}2Ln](Ln= L4-L7, R3= Me2Ph)，其中配体为双齿桥接。膦配合物在溶液中进行了表征，但仅在[PdCl2(PR3)Ln]（Ln= L6, R3= Bun3; L7, R3= Bun3或Me2Ph； L2, R3= Ph3）中分离得到。化合物L4、L6或L7与η - 3-甲基烯基钯络合物[{PdCl(η3-CH2CMeCH2)}2]和NH4PF6反应生成[Pd(η3-CH2CMeCH2)Ln] PF6（Ln= L4、L6或L7）。通过x射线衍射分析确定了[PdCl2L6]·0.5CH2Cl2的晶体结构：晶体为单斜晶，空间群为P21， a= 9.5830(13), b= 13.9720(14), c= 14.726(2) a, β= 97.610（11）°，Z= 4。它显示了不对称单元中配合物的两个分子仅在N-N键周围的扭转角不同。
Mixed monoazines of types H2CN–NC10H16[C10H16 is a (1R)-(+)-camphor residue (L1), or a (1R)-(–)-fenchone residue (L2)] or Me2CN–NC10H16[C10H16 is a (1R)-(+)-camphor residue (L3)], or α-diazines C10H16N–NCH–CHN–NC10H16[C10H16 is a (1R)-(+)-camphor residue (L4) or a (1R)-(–)-fenchone residue (L5)], or α-2-pyridyl azines C10H16N–NCHC5H4N [C10H16 is a (1R)-(+)-camphor residue (L6) or a (1R)-(–)-fenchone residue (L7)] reacted with Na2PdCl4 to give compounds of type [PdCl2Ln2] for L1, L2 or L3 as monodentate nitrogen-donor ligands and chelated mononuclear complexes of the type [PdCl2Ln] for L4, L5, L6 or L7. The complexes of the monodentate azines L1 and L2 exist in solution as mixtures of isomers differing in the ligating nitrogens. The compounds L1, L2 and L4–L7 also reacted with [Pd2Cl4(PR3)2] to give [PdCl2(PR3)Ln](n= 1, R3= Me2Ph or Me2(C6H4OMe-4); n= 2, R3= Me2Ph, Me2(C6H4OMe-4) or Ph3; n= 4 or 5, R3= Me2Ph; n= 6, R3= Bun3; n= 7, R3= Bun3 or Me2Ph), in which the ligands are monodentate, or [{PdCl2(PR3)}2Ln](Ln= L4–L7, R3= Me2Ph), in which the ligands are bidentate bridging. The phosphine complexes were characterised in solution but were isolated only for [PdCl2(PR3)Ln](Ln= L6, R3= Bun3; L7, R3= Bun3 or Me2Ph; L2, R3= Ph3). Compounds L4, L6 or L7 reacted with the η3-methylallylpalladium complex [{PdCl(η3-CH2CMeCH2)}2] and NH4PF6 to give [Pd(η3-CH2CMeCH2)Ln] PF6(Ln= L4, L6 or L7). The crystal structure of [PdCl2L6]·0.5CH2Cl2 was determined by X-ray diffraction analysis: the crystals are monoclinic, space group P21 with a= 9.5830(13), b= 13.9720(14) and c= 14.726(2)A, β= 97.610(11)° and Z= 4. It shows two molecules of the complex in the asymmetric unit differing only in the torsion angles around the N–N bond.