Molecular Structures and Catalytical Performance in Suzuki-coupling Reaction of Novel Dipalladium Clip-shaped Complexes with Bifunctional Pyrazolate Ligands

A series of clip-shaped cationic molecular corners C1~C4(C1=[(bpy)_(2)Pd_(2)(L^(1))_(2)]^(2+),C2=[(dmbpy)_(2)Pd_(2)(L^(1))_(2)]^(2+),C3=(bpy)_(2)Pd_(2)(L^(2))_(2)]^(2+),C4=(dmbpy)_(2)Pd_(2)(L^(2))_(2)]^(2+),bpy=2,2-bipyridine,dmbpy=4,4΄-dimethyl-2,2-bipyridine)were synthesized through dipalladium complexes[(bpy)_(2)Pd_(2)(NO_(3))_(2)](NO_(3))_(2),[(dmbpy)_(2)Pd_(2)(NO_(3))_(2)](NO_(3))_(2)and bifunctional pyrazole ligands 4-(3,4-dimethoxyphenyl)-3,5-dimethyl-1H-pyrazol(HL^(1))and 4,4΄-(5-(^(1)H-pyrazol-4-yl)-1,3-phenylene)dipyridine(HL^(2)).Complexes C1~C4 were characterized by^(1)H and^(13)C NMR,electrospray ionization mass spectrometry(ESI-MS),elemental analysis,and IR spectroscopy.The X-ray diffraction analysis of C1∙2NO_(3)−revealed a Pd_(2)dimetallic clip-shaped structure which was synthesized by two bifunctional ligands doubly bridged by the[(bpy)Pd]_(2)dimetal units.Additionally,all of the complexes with NO_(3)−as counter anions exhibited high-efficiency catalytical performance in the Suzuki-coupling reaction attributed to the tunable impact and weak dinuclear Pd(Ⅱ)···Pd(Ⅱ)intramolecular bonding interaction.

双核钯配合物［Ph_2P（o－C_6H_4CO）PdCl］_2·2CH_2Cl_

合成了双氯桥双核钯配合物［Ｐｈ_２Ｐ（ｏ－Ｃ_６Ｈ_４ＣＯ）ＰｄＣｌ］_２·２ＣＨ_２Ｃｌ_２进行了元素分析、红外光谱表征和晶体结构测定，研究了其催化氢化性能。在３０～８０℃、氢分压１．０～５．０ＭＰａ的范围内。发现该配合物是催化氢化丙烯酸为丙酸的有效催化剂．晶体［Ｐｄ_２Ｃｌ_２（Ｃ_（１９）Ｈ_（１４）ＯＰ）_２］·２ＣＨ_２Ｃｌ_２属Ｐ１空间群，ａ＝０．９３０４（３）ｎｍ，ｂ＝１．０３９２（２）ｎｍ，ｃ＝１．１０６２（３）ｎｍ；ａ＝１０２．７８（２），Ｂ＝９７．３５（３），γ＝９５．２５（２），Ｖ＝１．０２６４ｎｍ~３，Ｍ＝１０３２．１７，２＝１，Ｄｃ＝１．６７０ｇ／ｃｍ~３，ｕ＝１３．６９５ｃｍ^（－１），Ｆ（０００）＝５１２，用１９４５个独立衍射精修结构，最终Ｒ＝０．０３６。

共平面的μ-S桥联(1,10-菲咯啉)钯(Ⅱ)双核配合物的晶体结构与π-π堆积(英文)

A novel μ-S-bridged di-palladium(Ⅱ) complex, {[(phen)Pd( μ-SPr)2Pd(phen)](NO3)2·2H2O} (1) was synthesized and characterized by the 1H NMR, element analysis and single crystal X-ray diffraction. It crystallizes in the monoclinic space group C2/c with unit cell parameters: a=2.165 1(3) nm, b=1.291 4(2) nm, c=2.716 2(3) nm, β=111.987(3)°, and V=7.041 8(16) nm3, Z=8, R=0.054 4, wR=0.127 4. The X-ray crystal structure analysis revealed that two 1,10-phenanthroline palladium(Ⅱ) moieties were bridged by two n-propylmercapatan molecules in coplanar fashion with the dimensions of 1.55 nm × 0.88 nm. The plane-to-plane distance of the complex 1 is 0.33 nm, which reveals strong aromatic-aromatic π-π interaction. CCDC: 292998.

Sμ-二氯-二(N,N-二甲基-α-萘乙胺)合二钯(Ⅱ)的合成

以α萘乙酮为原料合成了Ｓμ二氯二（Ｎ，Ｎ二甲基α萘乙胺） 合二钯（ Ⅱ） ． 对中间产物Ｒ，Ｓα萘乙胺进行了拆分，

吡唑双钯(Ⅱ,Ⅱ)配合物的合成与表征及其在Suzuki偶联反应中的催化反应（英文）

配体3,5-二(2-吡咯)吡唑(HL)与二硝酸根桥联双钯配合物在溶液中通过配位作用形成了一系列吡唑基双钯(Ⅱ,Ⅱ)夹子[Pd_2(bpy)_2L2]2+(1)、[Pd_2(dmbpy)_2L_2]^(2+)(2)和[Pd_2(phen)_2L_2]^(2+)(3)(bpy=2,2′-联吡啶,dmbpy=4,4′-二甲基-2,2′-联吡啶,phen=1,10-菲咯啉)。运用~1H NMR、^(13)C NMR、ESI-MS和X射线单晶衍射等测试手段对1~3的结构进行了表征。其晶体结构中存在弱的Pd…Pd键(0.303~0.313 nm)相互作用,通过分子间的氢键作用形成一维二重螺旋结构,可作为一种新颖的Suzuki-coupling反应的高效催化剂。

基于酰胺-吡唑双功能配体的钯配位“夹子”的自组装及其催化性能

利用配位驱动吡唑基配体在溶液中自发去质子自组装的方法,用金属转子[(bpy)_(2)Pd_(2)(NO_(3))_(2)](NO_(3))_(2)、[(dmbpy)_(2)Pd_(2)(NO_(3))_(2)](NO_(3))_(2)(bpy=2,2′-联吡啶,dmbpy=4,4′-二甲基-2,2′-联吡啶)和酰胺-吡唑双功能配体(HL_(1)、HL_(2))合成了含有Pd(Ⅱ)…Pd(Ⅱ)相互作用的[Pd_(2)L_(2)]2+类型的吡唑基双钯(Ⅱ,Ⅱ)“夹子”C1~C4。利用^(1)H和^(13)C NMR、ESI-MS、红外光谱和X射线单晶衍射等测试手段对配合物C1~C4的结构进行了表征。同时,合成的夹子状双金属配合物对Suzuki-coupling反应均表现出较好的催化活性。