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Víctor Varela-Izquierdo Dr. Ana M. Geer Prof. Dr. Bas de Bruin Dr. José A. López Prof. Dr. Miguel A. Ciriano Dr. Cristina Tejel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(69):15915-15928
The feasibility of oxidative addition of the P−H bond of PHPh2 to a series of rhodium complexes to give mononuclear hydrido-phosphanido complexes has been analyzed. Three main scenarios have been found depending on the nature of the L ligand added to [Rh(Tp)(C2H4)(PHPh2)] (Tp= hydridotris(pyrazolyl)borate): i) clean and quantitative reactions to terminal hydrido-phosphanido complexes [RhTp(H)(PPh2)(L)] (L=PMe3, PMe2Ph and PHPh2), ii) equilibria between RhI and RhIII species: [RhTp(H)(PPh2)(L)]⇄[RhTp(PHPh2)(L)] (L=PMePh2, PPh3) and iii) a simple ethylene replacement to give the rhodium(I) complexes [Rh(κ2-Tp)(L)(PHPh2)] (L=NHCs-type ligands). The position of the P−H oxidative addition–reductive elimination equilibrium is mainly determined by sterics influencing the entropy contribution of the reaction. When ethylene was used as a ligand, the unique rhodaphosphacyclobutane complex [Rh(Tp)(η1-Et)(κC,P-CH2CH2PPh2)] was obtained. DFT calculations revealed that the reaction proceeds through the rate limiting oxidative addition of the P−H bond, followed by a low-barrier sequence of reaction steps involving ethylene insertion into the Rh−H and Rh−P bonds. In addition, oxidative addition of the P−H bond in OPHPh2 to [Rh(Tp)(C2H4)(PHPh2)] gave the related hydride complex [RhTp(H)(PHPh2)(POPh2)], but ethyl complexes resulted from hydride insertion into the Rh−ethylene bond in the reaction with [Rh(Tp)(C2H4)2]. 相似文献
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Crystallography Reports - The crystal structures of two monopentamethylcyclopentadienylhafnium(IV) derivatives have been determined by X-ray diffraction analysis. The [Hf(η5-C5Me5)Cl3] complex... 相似文献
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Víctor Varela-Izquierdo Dr. José A. López Prof. Dr. Bas de Bruin Dr. Cristina Tejel Prof. Dr. Miguel A. Ciriano 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(15):3270-3274
The isolation of simultaneously low-coordinate and low-valent compounds is a timeless challenge for preparative chemists. This work showcases the preparation and full characterization of tri-coordinate rhodium(-I) and rhodium(0) complexes as well as a rare rhodium(I) complex. Reduction of [{Rh(μ-Cl)(IPr)(dvtms)}2] ( 1 , IPr=1,3-bis(2,6-diisopropylphenyl)imidazolyl-2-ylidene; dvtms=divinyltetramethyldisiloxane) with KC8 gave the trigonal complexes K[Rh(IPr)(dvtms)] and [Rh(IPr)(dvtms)], whereas the cation [Rh(IPr)(dvtms)]+ results from their oxidation or by abstraction of chloride from 1 with silver salts. The paramagnetic Rh0 complex is a unique fully metal-centered radical with the unpaired electron in the dz2 orbital. The Rh(-I) complex reacts with PPh3 with replacement of the NHC ligand, and behaves as a nucleophile, which upon reaction with [AuCl(PPh3)] generates the trigonal pyramidal complex [(IPr)(dvtms)Rh-Au(PPh3)] with a metal–metal bond between two d10 metal centers. 相似文献
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Dr. Anne-Frédérique M. Pécharman Erika M. Roberts Dr. Fedor M. Miloserdov Dr. Victor Varela-Izquierdo Dr. Mary F. Mahon Prof. Michael K. Whittlesey 《欧洲无机化学杂志》2023,26(12):e202300037
Addition of an excess of ZnMe2 to a mixture of [Ru(PPh3)3HCl] and IMes (IMes=1,3-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene) yields the bis-cyclometallated complex, [Ru(IMes)“(PPh3)2] 2 , together with the mono-cyclometallated, Ru−Zn heterobimetallic complex [Ru(IMes)′(PPh3)2(ZnMe)] 3 . Treatment of 2 with H2, PhSiH3 or pinacolborane yields the previously reported complex, [Ru(IMes)′(PPh3)2H] 1 , the synthesis of which has been reinvestigated. Further studies of small molecule reactivity show that 1 adds H2 to give [Ru(IMes)(PPh3)2H4] 4 , whilst 2 reacts with catecholborane to give [Ru(IMes-Bcat)′(PPh3)2H] 5 , in which (IMes-Bcat)′ signifies a borylated NHC ligand that is singly-metallated onto Ru. Treatment of 2 with CO gives the 18-electron dicarbonyl product [Ru(IMes)”(PPh3)(CO)2] 6 . Compounds 1 – 3 , 5 and 6 have been structurally characterised. 相似文献
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