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1.
Preparation and Molecular Structures of Oligofunctional Dirhenium Carbonyl Derivatives from Dirhenium Nonacarbonylphosphane Starting with dirheniumdecacarbonyl, one CO-Ligand was eliminated oxidatively and substituted by the labile acetonitrile ligand. As an intermediate eq-Re2(CO)9NCCH3 was received. The reaction of this labilised carbonyl with tris(trimethylsilyl)phosphine and subsequent methanolysis gave ax-Re2(CO)9PH3, which was isolated and characterized for the first time. Photochemical and thermal reaction of ax-Re2(CO)9PH3 led to the new bi- and trinuclear complexes Re2(μ-H)(μ3-PHRe(CO)5)(CO)8, Re2(μ-PH2)2(CO)8 and Re2(μ-H) · (μ-PH2)(CO)8, which were characterized by IR-, 1H- and 31P-NMR spectroscopy. The structures of ax-Re2(CO)9PH3, Re2(μ-H)(μ3-PHRe(CO)5)(CO)8 and Re2(μ-PH2)2(CO)8 were confirmed by single-crystal X-ray analysis. ax-Re2(CO)9PH3 has a very short Re? P bond length of 228(2) pm. 相似文献
2.
A cobalt‐containing monodentate phosphine [(μ2‐PPh2CH2PPh2‐κ2P)Co2(CO)4][μ2‐η2‐PhC≡CP(i‐Pr)2] 2f , was prepared from the reaction of (μ2‐PPh2CH2PPh2‐κ2P)Co2(CO)6 1 with PhC≡CP(i‐Pr)2. It was accompanied by an oxidized compound, [(μ2‐PPh2CH2PPh2‐κ2P)Co2(CO)4][μ2‐η2‐PhC≡CP(=O)(i‐Pr2)] 2fo during the chromatographic process. Further reaction of 2f with Mo(CO)6 resulted in the formation of a 2f ‐ligated molybdenum complex 4 , [(μ2‐PPh2CH2PPh2‐κ2P)Co2(CO)4][μ2‐η2‐PhC≡CP(i‐Pr2)‐κP]‐Mo(CO)5. 相似文献
3.
4.
报道从D-甘露醇出发合成手性双膦(2S,5S)-3,6-双(二苯膦)-1,4:3,6-双脱水-2,5-双去氧-L-艾杜醇,原位下BDPI与3种铑配合物作用生成手性非螯合型双膦铑催化剂,常压下对4种脱氢苯丙氨酸衍生物进行不对称催化化反主尖,对反应结果及e.e.值进行了讨论。 相似文献
5.
Gáti T Simon A Tóth G Magiera D Moeller S Duddeck H 《Magnetic resonance in chemistry : MRC》2004,42(7):600-604
Adducts of four phosphine chalcogenides with the chiral dirhodium complex ([Rh-Rh]) were investigated by variable-temperature 1H and 31P NMR spectroscopy in order to compare their properties as axial ligands. Whereas the selenide (1) and the sulfide (2) are strong ligands with electrostatic attraction and, in addition, a significant orbital (HOMO-LUMO) interaction, the phosphine oxide compounds (P=O) bind primarily via electrostatic attraction and are relatively weak donors. Moreover, the overall bond strength in these adducts depends on steric congestion around the P=O group. 相似文献
6.
A. N. Chekhlov 《Journal of Structural Chemistry》2005,46(1):182-184
The crystal and molecular structure of tris(m-chlorophenyl)phosphine selenide, C18H12Cl3PSe (I), was investigated by X-ray diffraction (XRD) analysis. The trigonal rhombohedral structure of I (space group \(R\overline 3 c\), a = 14.110(2) Å, c = 32.360(4) Å, Z = 12) was solved by direct methods and refined by least squares in an anisotropic approximation (R = 0.029) for 1319 averaged measured reflections (CAD-4 automatic diffractometer, λCuKα). 相似文献
7.
M. R. Yaftian M. Burgard D. Matt C. Wieser C. Dieleman 《Journal of inclusion phenomena and macrocyclic chemistry》1997,27(2):127-140
The complexing, extracting and mobile carrier properties of the tetra(phosphine oxide)-calix[4]arene 1 and the hybrid diamide-di(phosphine oxide)-calix[4]arene 2 were studied. Both ligands give 1 : 1 complexes with alkali cations in THF as shown by the picrate method. 1H NMR experiments were run to follow encapsulation of sodium and potassium cations. The corresponding spectra indicate C2-symmetrical structure. The observed extraction orders of the alkali picrates were as follows K+>Rb+>Li+>Cs+>Na+ for 1 and Li+>Na+>K+>Rb++ for 2. Transport kinetics was analysed by means of a model which assumes pure diffusion and which allows the evaluation of mass transfer coefficients in all systems. These coefficients and their influences on the transport rate are discussed in terms of size of the transporting species in the liquid membrane. 相似文献
8.
The first MCM-41-supported bidentate phosphine palladium(0) complex has been prepared. This complex is a highly efficient catalyst for Sonogashira reaction and can be reused at least 10 times without any decrease in activity. 相似文献
9.
担载液相催化剂的研究——Ⅳ.催化剂的原位红外光谱表征 总被引:1,自引:0,他引:1
本文利用原位红外光谱方法对铑基担载液相催化剂(SLPC)在接近于实际反应条件下进行了表征。结果表明,新鲜催化剂上,铑膦络合物主要以二聚物的形式存在,如Rh_2(CO)_2(PPh_3)_4而在合成气或反应气氛中,催化剂铑膦络合物以单核络合物HRh(CO)_2(PPh_3)_2的形式存在。文中还对SLPC在CO,H_2,C_2-H_4,空气和HCl中处理时铑络合物种的变化进行了原位观察。实验结果表明,SLPC上活性铑络合物与对应的均相过程完全一致,进一步证实了SLPC催化在微观上就是一个均相催化过程。 相似文献
10.
Zareen Ahkter Andrew J. Edwards Scott L. Ingham Jack Lewis Ana M. Martin Castro Paul R. Raithby Gregory P. Shields 《Journal of Cluster Science》2000,11(1):217-226
The reaction of the di-gold cation [Au2(dppx)]2+ with the heptanuclear cluster dianion [Os7(CO)20]2– affords the mixed metal cluster [Os7(CO)20{Au2(dppx)}] (x=m (1), e (2), b (3)). On standing, in solution, this complex undergoes decarbonylation to give the cluster [Os7(CO)19{Au2(dppx)}] (x=m (4), e (5), b (6)). The complexes have been characterised spectroscopically, and an X-ray structure determination of the dppm derivative shows that it contains a metal core based on an Os7 edge-bridged bicapped tetrahedron with the two
3-Au atoms capping adjacent triangular Os3 faces of the central tetrahedron. In an analogous reaction, the carbido anion [Os7(H)C(CO)19]– affords the neutral cluster [Os7C(CO)19{Au2(dppm)}] (7) when treated with [Au2(dppm)]2+ in the presence of base. 相似文献