790655-23-1Relevant academic research and scientific papers
Actinide-Mediated Catalytic Addition of E-H Bonds (E=N, P, S) to Carbodiimides, Isocyanates, and Isothiocyanates
Karmel, Isabell S.R.,Tamm, Matthias,Eisen, Moris S.
, p. 12422 - 12425 (2015)
Unprecedented catalytic reactivity of actinide coordination complexes toward heterocumulenes, such as carbodiimides, isocyanates, and isothiocyanates is reported. The mono(imidazolin-2-iminato) thorium(IV) complex [Th(ImDippN){N(SiMe3)2}3] (1) was applied as a precatalyst for the addition of E-H (E=N, P, S) bonds to the Y≡C≡X core (Y=R2N; X=NR2, O, S) of carbodiimides, isocyanates, and isothiocyanates. The respective insertion products were obtained in high yields under mild reaction conditions, with complex 1 displaying high tolerance toward functional groups and heteroatoms. New reactivity: The mono(imidazolin-2-iminato) thorium complex [Th(ImDippN){N(SiMe3)2}3] was successfully applied as an active catalyst for the addition of E-H (E=N, P, S) bonds across the central Y≡N≡C≡X linkage of carbodiimides, isocyanates and isothiocyanates, yielding the respective insertion products in high yields and under mild reaction conditions.
An efficient catalytic method for hydrophosphination of heterocumulenes with diethylzinc as precatalyst without a solvent
Ma, Xiaoli,Ni, Congjian,Roesky, Herbert W.,Yan, Ben,Yang, Zhi,Yu, Hailong,Zhang, Bingyi
supporting information, p. 15488 - 15492 (2021/11/30)
Commercially available compound ZnEt2 acts as an efficient precatalyst for the solvent-free hydrophosphinations of heterocumulenes using Ph2PH as reagent. As far as we knew, this has been not reported in group 12 metal catalyzing reactions. A suggested mechanism of this reaction is explored, and the intermediate [{Ph2PC(NiPr)2}ZnEt]2 is obtained and characterized by a single-crystal X-ray structural analysis. This journal is
Application of disilazane rare earth complex in hydrogenation reaction of catalytic carbodiimides and diphenylphosphines
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Paragraph 0023; 0024, (2020/07/24)
The invention relates to an application of a disilicon amine and rare earth complex to catalysis of a phosphine hydrogenation reaction of carbodiimide and diphenylphosphine. The application comprisesthe following steps: sequentially uniformly mixing diphe
Lithium-Aluminate-Catalyzed Hydrophosphination Applications
Pollard, Victoria A.,Young, Allan,McLellan, Ross,Kennedy, Alan R.,Tuttle, Tell,Mulvey, Robert E.
supporting information, p. 12291 - 12296 (2019/08/02)
Synthesized, isolated, and characterized by X-ray crystallography and NMR spectroscopic studies, lithium phosphidoaluminate iBu3AlPPh2Li(THF)3 has been tested as a catalyst for hydrophosphination of alkynes, alkenes, and carbodiimides. Based on the collective evidence of stoichiometric reactions, NMR monitoring studies, kinetic analysis, and DFT calculations, a mechanism involving deprotonation, alkyne insertion, and protonolysis is proposed for the [iBu3AlHLi]2 aluminate catalyzed hydrophosphination of alkynes with diphenylphosphine. This study enhances further the development of transition-metal-free, atom-economical homogeneous catalysis using common sustainable main-group metals.
Neutral and Cationic Zirconium Complexes Bearing Multidentate Aminophenolato Ligands for Hydrophosphination Reactions of Alkenes and Heterocumulenes
Zhang, Yu,Qu, Liye,Wang, Yaorong,Yuan, Dan,Yao, Yingming,Shen, Qi
, p. 139 - 149 (2018/01/11)
Zirconium complexes supported by multidentate aminophenolato ligands were synthesized and characterized. The catalytic activities of neutral zirconium complexes and their cationic derivatives in the hydrophosphination of alkenes as well as heterocumulenes have been investigated and compared. Neutral complex 1 bearing a multidentate amino mono(phenolato) ligand exhibited high activity in hydrophosphination of simple alkenes, and anti-Markovnikov products were obtained in 37-94% yields at room temperature. Cationic species generated in situ from complex 3 stabilized by a bis(phenolato) ligand were found to be more active for hydrophosphination of heterocumulenes, i.e., carbodiimides and isocyanates, and gave phosphaguanidines and phosphaureas in 67-93% yields. The Lewis acidity and coordination space of metal centers are modified through changes in the ligand structure, which is found to significantly influence catalytic activity. These complexes are among the most active group 4 metal-based catalysts for hydrophosphination reactions.
The phosphinoboration of carbodiimides, isocyanates, isothiocyanates and CO2
Geier, Stephen J.,Lafortune, James H. W.,Zhu, Diya,Kosnik, Stephanie C.,Macdonald, Charles L.B.,Stephan, Douglas W.,Westcott, Stephen A.
, p. 10876 - 10885 (2017/08/30)
The transition metal-free addition of phosphinoboronate ester Ph2PBpin (pin = 1,2-O2C2Me4) to heterocumulenes including carbodiimides, isocyanates, isothiocyanates and carbon dioxide has been investigated. The corresponding 1,2-addition products were readily prepared at room temperature without the need of a catalyst or added base. Addition of methanol to the compounds derived from addition of Ph2PBpin to carbodiimides, isocyanates, and isothiocyanates resulted in traditional hydrophosphination products. The methodology developed in this study provides a simple and elegant route for the generation of a wide range of functionalized phosphines. The phosphinoboronate ester Ph2PBpin also selectively and reversibly adds to CO2 at room temperature in a 1,2-manner.
Structural and Mechanistic Insights into s-Block Bimetallic Catalysis: Sodium Magnesiate-Catalyzed Guanylation of Amines
De Tullio, Marco,Hernán-Gómez, Alberto,Livingstone, Zoe,Clegg, William,Kennedy, Alan R.,Harrington, Ross W.,Anti?olo, Antonio,Martínez, Antonio,Carrillo-Hermosilla, Fernando,Hevia, Eva
supporting information, p. 17646 - 17656 (2016/11/29)
To advance the catalytic applications of s-block mixed-metal complexes, sodium magnesiate [NaMg(CH2SiMe3)3] (1) is reported as an efficient precatalyst for the guanylation of a variety of anilines and secondary amines with
Catalytic insertion of E-H bonds (E = C, N, P, S) into heterocumulenes by amido-actinide complexes
Batrice, Rami J.,Eisen, Moris S.
, p. 939 - 944 (2016/02/05)
We report herein the actinide-mediated insertion of E-H bonds (E = C, N, P, S) into various heterocumulenes including carbodiimides, isocyanates, and isothiocyanates. The precatalysts are prepared by a simple, one-pot procedure using readily available sta
Half-sandwich rare-earth metal tris(alkyl) ate complexes catalyzed phosphaguanylation reaction of phosphines with carbodiimides: An efficient synthesis of phosphaguanidines
Ma, Wangyang,Xu, Ling,Zhang, Wen-Xiong,Xi, Zhenfeng
, p. 7649 - 7655 (2015/10/12)
The phosphaguanylation reaction of phosphines with carbodiimides catalyzed by half-sandwich yttrium tris(trimethylsilylmethyl) ate complexes is achieved for the first time to efficiently prepare phosphaguanidines. The catalyst system of the yttrium ate complex displays better catalytic activity than those of neutral yttrium complexes.
Synthesis of Bis(NHC)-Based CNC-Pincer Rare-Earth-Metal Amido Complexes and Their Application for the Hydrophosphination of Heterocumulenes
Gu, Xiaoxia,Zhang, Lijun,Zhu, Xiancui,Wang, Shaowu,Zhou, Shuangliu,Wei, Yun,Zhang, Guangchao,Mu, Xiaolong,Huang, Zeming,Hong, Dongjing,Zhang, Feng
, p. 4553 - 4559 (2015/10/06)
The bis(NHC) (NHC = N-heterocyclic carbene)-based CNC-pincer rare-earth-metal amido complexes LRE[N(SiMe3)2]2 (L = 4-CH3-2-{R-[N(CH)2CN]}C6H3]2N; L2, R = CH
