Synthesis and reactivity of trinuclear complexes of platinum containing the single bridging ligand SC<sub>4</sub>H<sub>8</sub>. Molecular structure of [NBu<sub>4</sub>]<sub>2</sub>[trans-PtCl<sub>2</sub>{(µ-SC<sub>4</sub>H<sub>8</sub>)Pt(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub>}<sub>2</sub>]
作者:Rafaei Usón、Juan Forniés、Milagros Tomás、Irene Ara
DOI:10.1039/dt9890001011
日期:——
Pt(C6F5)3}2](X = Cl,Br,I, or C6F5;SC4H8= tetrahydrothiphene)(1)–(4) have been prepared form trans-[PtX2(SC4H8)2] and NBu4[Pt(C6H5)3(OCMe2)](molar ratio 1:2). The SC4H8 ligands act as the single bridge between the central platinum atom and the two terminal ones. Attemps to prepare similar trinuclear complexes with singly bridging halide ligands failed since the reaction between trans-[PtCl2(py)2](py
类型为[NBu 4 ] 2 [反式-PtX 2 (µ-SC 4 H 8)Pt(C 6 F 5)3 } 2 ]的三核配合物(X = Cl,Br,I或C 6 F 5;已从反式-[PtX 2(SC 4 H 8)2 ]和NBu 4 [Pt(C 6 H 5)3(OCMe )制备了SC 4 H 8 =四氢噻吩)(1)-(4)2)](摩尔比为1:2)。SC 4 H 8配体充当中心铂原子和两个末端原子之间的单桥。由于反式-[PtCl 2(py) 2 ](py =吡啶)和NBu 4 [Pt(C 6 F 5) 3(OCMe 2)](摩尔比例1:2)不会发生,而反式-[Ptl 2(py) 2 ]或[PtBr 2(cod)](cod =环辛-1,5-二烯),在相似条件下产生顺式-[Pt(C 6 F 5)2(py)2 ]和[NBu 4 ] 2 [Pt 2(μ-I)2(C 6 F 5)4 ]或[Pt(C 6 F 5)2(鳕鱼)]和[NBu
Synthesis and reactivity of bimetallic acetylide-bridged PtPt complexes. Crystal and molecular structure of [(PPh3)(C6F5)Pt(μ-CCPh)2Pt(C6F5)(PPh3)]
double-bridged acetylide complexes [Pt(μ-CCR)(C 6 F 5 )PPh 3 )] 2 [R = Ph ( 1 ), But ( 2 ), SiMe3 ( 3 )] have been synthesized from [ trans -Pt(CCR) 2 (PPh 3 ) 2 ] and [ cis -Pt(C 6 F 5 ) 2 (THF) 2 ] (THF = tetrahydrofuran). The crystal structure of [Pt(μ-CCPh) (C 6 F 5 )(PPh 3 )] 2 ( 1 ) has been established by X-ray diffraction methods. The structure shows that two identical [(PPh 3 )(C 6 F 5 )PtCCPh] units
摘要双核双桥乙炔络合物[Pt(μ-CCR)(C 6 F 5)PPh 3)] 2 [R = Ph(1),Bu t(2),SiMe 3(3)]由[反式-Pt(CCR)2(PPh 3)2]和[顺式-Pt(C 6 F 5)2(THF)2]合成(THF =四氢呋喃)。[Pt(μ-CCPh)(C 6 F 5)(PPh 3)] 2(1)的晶体结构已经通过X射线衍射法建立。结构表明,两个相同的[(PPh 3)(C 6 F 5)PtCCPh]单元通过MCCPh单元的η2键结合在一起。这表明该络合物是通过两个金属中心之间的基团重排形成的。用L(L = PPh 3,py =吡啶)处理[Pt(μ-CCR)(C 6 F 5)(PPh 3)] 2产生简单的桥裂解反应,得到单核络合物[反式- Pt(C 6 F 5)(CCR)(PPh 3)L](4–9)。
Effect of variation in ligand ring size upon the inversion barrier at sulphur in complexes of palladium(II) and platinum(II). A dynamic hydrogen-1 nuclear magnetic resonance study
作者:Edward W. Abel、Martin Booth、Keith G. Orrell
DOI:10.1039/dt9790001994
日期:——
the iodo-complexes. The pyramidal inversion energies are very dependent upon ligand ring size; those for five- and six-membered rings are comparable with complexes of linear sulphides, but the complexes of four-membered rings show a considerable heightening of the pyramidal sulphurinversion barrier. For the complexes of the three-membered ring sulphides no inversion was detectable up to the temperature
该系列复合物的反式- [MX 2 [图形省略] R 2)Ñ } 2 ](M =钯II或Pt II ; X =氯,溴,或I; R = H和/或Me; ñ = 2 –5)已合成,并且已通过带形拟合方法对它们的可变温度nmr光谱进行了精确分析,以确定在硫原子处发生金字塔倒置的势垒。氯配合物中的势垒能比相应的溴化物高2–3 kJ mol –1,而溴化物则为4–5 kJ mol –1高于碘复合物。金字塔形反转能量非常依赖于配体环的大小。五元环和六元环的那些与线性硫化物的配合物相当,但是四元环的配合物显示出金字塔形硫转化阻挡层的显着提高。对于三元环硫化物的络合物,直到分解开始的温度都没有检测到反转,这是在二烷基硫化物金属络合物中这种刚性的第一个报道实例。
Synthesis, characterization and luminescence properties of homoleptic platinum(<scp>ii</scp>) acetylide complexes
作者:José Benito、Jesús R. Berenguer、Juan Forniés、Belén Gil、Julio Gómez、Elena Lalinde
DOI:10.1039/b308291a
日期:——
A family of homoleptic tetraalkynylplatinate(II) complexes (NBu4)2[Pt(CCR)4] containing various arylsubstituted (R = C6H4X), where X is an electron-donating, -withdrawing or -delocalizing substituent, and ethynylpyridine (C5H4N-2, C5H4N-4) ligands have been prepared. The structures of complexes with R = (4-CF3)C6H4 (4·2HCCl3), (4-CN)C6H4 (6·H2O) and C5H4N-4 (9b·HCCC5H4N-4·2H2O) have been determined
含多个被芳基取代的(R = C 6 H 4 X)的均化四炔基铂(II)配合物(NBu 4)2 [Pt(C CR)4 ] ,其中X是供电子,吸电子或离域取代基,和乙炔基吡啶(C 5 H 4 N-2,C 5 H 4 N-4)配体已经准备好了。R =(4-CF 3)C 6 H 4 (4 ·2HCCl 3),(4-CN)C 6 H 4 (6 ·H 2 O)和C 5 H 4 N-4(9b)的配合物的结构·HC CC 5 H 4 N-4·2H 2 O)通过单晶X射线衍射求出。在4种情况下,通过短的CHmoleculesπ相互作用将两个分子的CHCl 3结合到阴离子中,而对-吡啶基乙炔基衍生物高氧2分子通过适度的N⋯H–O–H⋯N分子间相互作用连接不同的阴离子,从而形成延伸的一维链。已经检查了配合物的光物理和电化学性质。它们都在液态和固态下显示出77和298 K时的发射,寿命在微秒范围内。在某些情况下,
Functional isocyanide metal complexes as building blocks for supramolecular materials: hydrogen-bonded liquid crystals
Gold, palladium and platinum complexes with an unusual isocyanide ligand containing a carboxylic acid function, [AuCl(CNC6H4COOH)], cis-[MI2(CNC6H4COOH)2] and trans-[MI2(CNC6H4COOH)2] (M = Pd, Pt) have been isolated. The carboxylic acid group of the coordinated isocyanide acts as a hydrogen donor for hydrogen-bonding and three series of stable hydrogen-bonded liquid crystalline metal complexes have been prepared with decyloxystilbazole. Although all the metal acid derivatives used are not mesomorphic, and decyloxystilbazole only shows an ordered Smectic E phase, four out of the five hydrogen-bonded decyloxystilbazole complexes studied display enantiotropic smectic A or nematic mesophases. The single crystal X-ray diffraction structure of trans-[PdI2(CNC6H4COOH)2]·C4H8O2 has been determined and confirms the formation of a supramolecular array in the solid state supported by hydrogen-bonding.