Use of Chelating Diphosphines To Prepare New Phosphido Clusters of Aluminum and Gallium
作者:David A. Atwood、Alan H. Cowley、Richard A. Jones、Ronald J. Powell、Christine M. Nunn
DOI:10.1021/om960122t
日期:1996.5.28
Novel phosphido cluster complexes of formula (Me(2)M)(4)(mu-(1,2-PR)(2)C6H4)(2) (M = Al, R = Me (1); M = Ga, R = t-Bu (2)) result when the chelating diphosphine ligand 1,2-bis(alkylphosphino)benzene is mixed with trialkylaluminum and -gallium reagents. When the potentially chelating ligand 1,2-bis(tert-butylphosphino)ethane is mixed with 2 equiv of AlMe(3) under the same conditions, the secondary phosphine bis-adduct complex Me(3)Al . PH(t-Bu)CH2CH2(t-Bu)HP . AlMe(3) (3) is formed.
WEISHEIT, R.;STENDEL, R.;MESSBAUER, B.;LANGER, C.;WALTHER, B., Z. ANORG. UND ALLG. CHEM., 1983, 504, N 9, 147-154
作者:WEISHEIT, R.、STENDEL, R.、MESSBAUER, B.、LANGER, C.、WALTHER, B.
DOI:——
日期:——
Mechanistic Insights into Molecular Crystalline Organometallic Heterogeneous Catalysis through Parahydrogen-Based Nuclear Magnetic Resonance Studies
作者:Matthew R. Gyton、Cameron G. Royle、Simon K. Beaumont、Simon B. Duckett、Andrew S. Weller
DOI:10.1021/jacs.2c12642
日期:2023.2.1
the efficiency of catalytic pairwise para-H2 transfer, speciation changes in the crystalline catalyst at the molecular level, and allows for high-quality single-scan 1H, 13C NMR gas-phase spectra for the products to be obtained, as well as 2D-measurements. Complex 1 reacts with H2 to form dimeric [Rh(L2)(H)(μ-H)]2[BArF4]2 (4), as probed using EXAFS; meanwhile, a single-crystal of 1 equilibrates NMR silent
[Rh(L 2 )(propene)][BAr F 4 ] ( 1 , L 2 = t Bu 2 PCH 2 CH 2 P t Bu 2 ) 晶体与 H 2和丙烯的多相固气反应,1-在 25 °C 的分批条件下,通过气相核磁共振 (NMR) 光谱法探索丁烯、丙炔或 1-丁炔。由此产生的仲氢诱导极化 (PHIP) 效应的时间演变测量催化通量,从而询问催化成对对位-H 2的效率分子水平上结晶催化剂的转移、形态变化,并允许对要获得的产品进行高质量的单扫描1 H、13 C NMR 气相光谱,以及二维测量。配合物1与 H 2反应形成二聚体 [Rh(L 2 )(H)(μ-H)] 2 [BAr F 4 ] 2 ( 4 ),如使用 EXAFS 探测的那样;同时, 1的单晶平衡NMR沉默的对位-H 2及其NMR活性邻位异构体,同时转化为4,以及1和4每个都以不同的速率将对位-H 2转化为邻位-H 2 。使用1和对位-H