- Synthesis of Polyphosphazenes by a Fast Perfluoroaryl Azide-Mediated Staudinger Reaction
-
We report the synthesis of polyphosphazenes by a fast Staudinger reaction between a bis-PFAA (perfluoroaryl azide) and a bis-phospine. Polymerization was completed within 30 min after mixing the two monomers (20 mM) in CH3CN under ambient condi
- Sundhoro, Madanodaya,Park, Jaehyeung,Wu, Bin,Yan, Mingdi
-
-
Read Online
- Palladium-Catalyzed C-P(III) Bond Formation by Coupling ArBr/ArOTf with Acylphosphines
-
Palladium-catalyzed C-P bond formation reaction of ArBr/ArOTf using acylphosphines as differential phosphination reagents is reported. The acylphosphines show practicable reactivity with ArBr and ArOTf as the phosphination reagents, though they are inert to the air and moisture. The reaction affords trivalent phosphines directly in good yields with a broad substrate scope and functional group tolerance. This reaction discloses the acylphosphines' capability as new phosphorus sources for the direct synthesis of trivalent phosphines.
- Chen, Xingyu,Wu, Hongyu,Yu, Rongrong,Zhu, Hong,Wang, Zhiqian
-
p. 8987 - 8996
(2021/06/30)
-
- Development of effective bidentate diphosphine ligands of ruthenium catalysts toward practical hydrogenation of carboxylic acids
-
Hydrogenation of carboxylic acids (CAs) to alcohols represents one of the most ideal reduction methods for utilizing abundant CAs as alternative carbon and energy sources. However, systematic studies on the effects of metal-to-ligand relationships on the catalytic activity of metal complex catalysts are scarce. We previously demonstrated a rational methodology for CA hydrogenation, in which CA-derived cationic metal carboxylate [(PP)M(OCOR)]+ (M = Ru and Re; P = one P coordination) served as the catalyst prototype for CA self-induced CA hydrogenation. Herein, we report systematic trial- and-error studies on how we could achieve higher catalytic activity by modifying the structure of bidentate diphosphine (PP) ligands of molecular Ru catalysts. Carbon chains connecting two P atoms as well as Ar groups substituted on the P atoms of PP ligands were intensively varied, and the induction of active Ru catalysts from precatalyst Ru(acac)3 was surveyed extensively. As a result, the activity and durability of the (PP)Ru catalyst substantially increased compared to those of other molecular Ru catalyst systems, including our original Ru catalysts. The results validate our approach for improving the catalyst performance, which would benefit further advancement of CA self-induced CA hydrogenation.
- Saito, Susumu,Wen, Ke,Yoshioka, Shota
-
supporting information
p. 1510 - 1524
(2021/06/18)
-
- Ready Approach to Organophosphines from ArCl via Selective Cleavage of C-P Bonds by Sodium
-
The preparation, application, and reaction mechanism of sodium phosphide R2PNa and other alkali metal phosphides R2PM (M = Li and K) have been studied. R2PNa could be prepared, accurately and selectively, via the reactions of SD (sodium finely dispersed in mineral oil) with phosphinites R2POR′ and chlorophosphines R2PCl. R2PNa could also be prepared from triarylphosphines and diarylphosphines via the selective cleavage of C-P bonds. Na was superior to Li and K for these reactions. R2PNa reacted with a variety of ArCl to efficiently produce R2PAr. ArCl is superior to ArBr and ArI since they only gave low yields of the products. In addition, Ph2PNa is superior to Ph2PLi and Ph2PK since Ph2PLi did not produce the coupling product with PhCl, while Ph2PK only gave a low yield of the product. An electron-withdrawing group on the benzene ring of ArCl greatly accelerated the reactions with R2PNa, while an alkyl group reduced the reactivity. Vinyl chloride and alkyl chlorides RCl also reacted efficiently. While t-BuCl did not produce the corresponding product, admantyl halides could give the corresponding phosphine in high yields. A wide range of phosphines were prepared by this method from the corresponding chlorides. Unsymmetric phosphines could also be conveniently generated in one pot starting from Ph3P. Chiral phosphines were also obtained in good yields from the reactions of menthyl chlorides with R2PNa. Possible mechanistic pathways were given for the reductive cleavage of R3P by sodium generating R2PNa and the substitution reactions of R2PNa with ArCl generating R2PAr.
- Ye, Jingjing,Zhang, Jian-Qiu,Saga, Yuta,Onozawa, Shunya,Kobayashi, Shu,Sato, Kazuhiko,Fukaya, Norihisa,Han, Li-Biao
-
p. 2682 - 2694
(2020/07/30)
-
- Novel AuI polyynes and their high optical power limiting performances both in solution and in prototype devices
-
Three novel AuI polyynes have been prepared in high yield by copolymerization between an AuI complex precursor and different ethynyl aromatic ligands. The investigation of their photophysical behavior has indicated that forming polyynes through polymerization not only maintains the high transparency of the corresponding AuI polyynes similar to those of their corresponding small molecular AuI acetylides, but also effectively enhances their triplet (T1) emission ability. Critically, owing to their enhanced T1 emission ability, all the AuI polyynes exhibit a stronger optical power limiting (OPL) ability against a 532 nm laser than the corresponding small molecular AuI acetylides. The AuI polyynes based on fluorene and triphenylamine ligands show even better OPL performance than the state-of-the-art OPL material C60, indicating their great potential in the field of laser protection. More importantly, in a prototype OPL device made by doping the fluorene-based AuI polyyne into a polystyrene (PS) solid matrix, substantially improved OPL activity has been observed compared with that in the solution, demonstrating its great potential for practical application. All these results have provided a new strategy to achieve a balance between high OPL activity and good transparency for OPL materials, representing a valuable attempt towards developing new OPL materials with high performance to cope with the key problems in the field of nonlinear optics.
- Tian, Zhuanzhuan,Yang, Xiaolong,Liu, Boao,Zhao, Jiang,Zhong, Daokun,Wu, Yong,Zhou, Guijiang,Wong, Wai-Yeung
-
supporting information
p. 6023 - 6032
(2018/06/15)
-
- New heterobimetallic Au(i)-Pt(ii) polyynes achieving a good trade-off between transparency and optical power limiting performance
-
Two series of new heterobimetallic Au(i)-Pt(ii) polyynes have been easily synthesized by cross-coupling under mild conditions. The absorption profiles of these two series of Au(i)-Pt(ii) polyynes are quite similar. However, the Au(i)-Pt(ii) polyynes with a 1,4-bis(diphenylphosphino)benzene ligand show stronger triplet (T1) emission and superior optical power limiting (OPL) performance than the corresponding Au(i)-Pt(ii) polyynes with a 1,3-bis(diphenylphosphino)propane ligand. Hence, the 1,4-bis(diphenylphosphino)benzene ligand is more effective than the 1,3-bis(diphenylphosphino)propane ligand for optimizing the transparency and OPL ability of OPL materials. When compared with the corresponding homometallic Pt(ii) polyynes, these heterobimetallic Au(i)-Pt(ii) polyynes display a blue shift in their absorption spectra, showing better transparency in the visible-light region. Besides, these heterobimetallic Au(i)-Pt(ii) polyynes show stronger OPL ability than their corresponding homometallic Pt(ii) polyynes as well as the state-of-the-art OPL material C60, demonstrating their enormous application potential in the nonlinear optics field. In brief, the introduction of Au(i) precursors with tetrahedral diphosphine ligands into the backbone of Pt(ii) polyynes can simultaneously achieve enhanced transparency and high OPL ability for OPL materials, providing a new strategy to optimize OPL materials.
- Tian, Zhuanzhuan,Yang, Xiaolong,Liu, Boao,Zhong, Daokun,Zhou, Guijiang,Wong, Wai-Yeung
-
supporting information
p. 11416 - 11426
(2018/11/20)
-
- Self-loading diphosphine-palladium catalyst and preparation method and application thereof
-
The invention relates to a self-loading diphosphine-palladium catalyst and a preparation method and application thereof. According to the preparation method, diphenyl phosphorous chloride is used as a raw material, and after the chloride is replaced by a
- -
-
Paragraph 0017; 0018; 0019
(2017/10/05)
-
- Convenient Formation of Triarylphosphines by Nickel-Catalyzed C-P Cross-Coupling with Aryl Chlorides
-
A convenient strategy has been developed for the preparation of various phosphine ligands in good to excellent yields through a nickel-catalyzed C-P bond-forming step. This reaction proceeded smoothly and tolerated a variety of functional groups to provide a new method for the synthesis of important phosphine ligands through the direct cleavage of a C-Cl bond. A convenient strategy has been developed for the preparation of various phosphine ligands in good to excellent yields through a nickel-catalyzed C-P bond-forming step. This reaction proceeded smoothly and tolerated a variety of functional groups to provide a new method for the synthesis of important phosphine ligands through the direct cleavage of a C-Cl bond.
- Sun, Meng,Zang, Yu-Shi,Hou, Le-Kai,Chen, Xiang-Xiang,Sun, Wei,Yang, Shang-Dong
-
supporting information
p. 6796 - 6801
(2016/02/18)
-
- Nickel-catalyzed C-P cross-coupling by C-CN bond cleavage
-
Prosperous coupling: A nickel-catalyzed C-P cross-coupling reaction with Me3SiPPh2 by carbon-cyano bond cleavage has been developed. This method is characterized by its simplicity and wide application to the synthesis of various monophosphorus and P,N bidentate ligands (see scheme).
- Sun, Meng,Zhang, Hong-Yu,Han, Qi,Yang, Kuo,Yang, Shang-Dong
-
supporting information; experimental part
p. 9566 - 9570
(2011/10/05)
-
- Novel phosphite palladium complexes and their application in C-P cross-coupling reactions
-
A mono- and a 1,3-bis-phosphite arene ligand based on 2,2′-biphenol have been synthesized in order to study the synthesis of the corresponding palladium(II) complexes starting from different Pd precursors. Novel bis-phosphite palladium complex 1 [PdCl2(L)2] (L = dibenzo[d,f][1,3,2]dioxaphosphepin, 6-phenoxy), C,P-chelate bonded monophosphite palladium complex 2 [Pd(κ2-L)(μ-Cl)]2, and PCP-pincer palladium complex 3 have been prepared from these ligands in promising to excellent yields (50-95%). Additionally, complexes 1 and 3 have been characterized by X-ray crystal structure determinations. The application of 2,6-bis-phosphite pincer palladium(II) complex 3 in C-P cross-coupling between diphenylphosphine-borane and a wide range of various aryl iodides under very mild conditions is reported. Kinetic investigations indicate that 3 merely acts as a pre-catalyst and that Pd nanoparticles are the actual catalytically active species.
- Li, Jie,Lutz, Martin,Spek, Anthony L.,Van Klink, Gerard P.M.,Van Koten, Gerard,Klein Gebbink, Robertus J.M.
-
experimental part
p. 2618 - 2628
(2010/11/21)
-
- Copper-catalyzed synthesis of unsymmetrical triarylphosphines
-
Various triarylphosphines have been prepared by coupling diphenylphosphine with aryl iodides with catalytic amounts of CuI in the presence of either K2CO3 or CS2CO3, in good yields. This method can tolerate a variety of functional groups and does not require the use of expensive additives, or harsh reaction conditions, and is palladium free.
- Van Allen, Derek,Venkataraman
-
p. 4590 - 4593
(2007/10/03)
-
- Water soluble phosphines Part XV. Syntheses of multiply functionalized and chiral phospine ligands by Pd-catalyzed P-C and C-C coupling reactions
-
Phosphine ligands containing mono- and multiply substituted aromatic substituents (1-13, 19a and 19b) are accessible in high yields by palladium-catalyzed P-C coupling reactions between primary, secondary or disecondary phosphines and iodo- or bromoaromatic compounds. The reaction is of broad applicability and compatible with electron donor or electron acceptor substituents in ortho, meta or para position to the halogen in the aromatic ring systems. It may be performed in protic and aprotic solvents. The chiral spirocyclic boronato complex 15a is formed upon reaction of 3 with boric acid, while with benzeneboronic acid 15c with a peripheral Lewis acid group is obtained. The Pd-mediated P-C coupling reaction of primary phosphines proceeds stepwise, tailor-made chiral secondary (16) and tertiary phosphines (17) being formed in high yield. Through combination with Suzuki-type C-C coupling reactions, the scope of Pd-catalyzed P-C coupling may be extended further, novel ligands (20a, 20b, 21a, 21b) with biphenylyl substituents being accessible. The X-ray structures of the salicylic acid derivative 3 (space group P1) and of ortho-iso-propylphenyl-diphenylphosphine 6 (space group Pbca) have been determined.
- Brauer, David J.,Hingst, Martin,Kottsieper, Konstantin W.,Liek, Christian,Nickel, Thomas,Tepper, Michael,Stelzer, Othmar,Sheldrick, William S.
-
-
- (para-Diphenylphosphino)benzenesulfonic acid and its ruthenium(II) complexes: An old water soluble phosphine ligand in a new perspective
-
Chloro- and hydrido-complexes of ruthenium(II) with potassium (4-diphenylphosphino)benzenesulfonate (pTPPMS) were prepared and their properties were compared with those of the related complexes of (3-diphenylphosphino)benzenesulfonates. An X-ray crystal structure determination revealed that the para-sulfonated ligand has a Tolman cone angle slightly smaller than that of PPh3. It was established by pH-potentiometric measurements and by 1H and 31P NMR studies that the distribution of the hydride derivatives [RuClH(pTPPMS)3] and [RuH2(pTPPMS)3,4] is strongly pH-dependent. Hydrogenation of trans-cinnamaldehyde in aqueous-organic mixtures is catalyzed by [RuCl2(pTPPMS)4] and is also strongly influenced by the pH of the aqueous phase due to the pH-dependent formation of the above hydrides. In acidic solutions (pH 6) a selective C=O hydrogenation was observed.
- Papp,Kovacs,Benyei,Laurenczy,Nadasdi,Joo
-
p. 635 - 641
(2007/10/03)
-
- Palladium-Catalyzed Coupling of Aryl Halides with (Trimethylstannyl)diphenylphosphine and (Trimethylsilyl)diphenylphosphine
-
The palladium-catalyzed reaction of aryl halides with either (trimethylsilyl)diphenylphosphine or (trimethylstannyl)diphenylphosphine gives aryldiphenylphosphines in good yields, under relatively mild conditions (50-70 deg C, benzene).The reaction tolerates a number of functional groups including methyl ethers, esters, ketones, nitriles, anilides, and certain halogens.The nitro and aldehyde groups as well as compounds containing groups such as amino and hydroxyl are not tolerated.
- Tunney, S. E.,Stille, J. K.
-
p. 748 - 753
(2007/10/02)
-
