2216-24-2Relevant articles and documents
Kikot' et al.
, (1975)
1,1′-Bis(di-tert-butylphosphino)ferrocene copper(i) complex catalyzed C-H activation and carboxylation of terminal alkynes
Trivedi, Manoj,Singh, Gurmeet,Kumar, Abhinav,Rath, Nigam P.
, p. 20874 - 20882 (2015)
Four copper(i) complexes, [CuBr(dtbpf)] (1), [CuI(dtbpf)] (2), [Cu4(μ2-I)2(μ3-I)2(μ-dtbpf)2] (3) and [Cu6(μ3-I)6(μ-dtbpf)2]·2CH3CN (4), were prepared using CuX (X = Br, I) and 1,1′-bis(di-tert-butylphosphino)ferrocene (dtbpf). These complexes have been characterized by elemental analyses, IR, 1H and 31P NMR, ESI-MS and electronic absorption spectroscopy. Molecular structures of the complexes 2 and 4 were determined crystallographically. Complex 2 is the first monomeric isolated Cu(i) complex of dtbpf with the largest P-Cu-P bite angle (120.070(19)°) to date. Complex 4 shows a centrosymmetrical dimeric unit with two [Cu3(μ3-I)3] motifs bridged by two bidentate dtbpf ligands in the κ1-manner. Each [Cu3(μ3-I)3] motif unites to form a pyramid with one copper atom at the apex and one of the triangular faces capped by an iodine atom. All the complexes were found to be efficient catalysts for the conversion of terminal alkynes into propiolic acids with CO2. Owing to the excellent catalytic activity, the reactions proceeded at atmospheric pressure and ambient temperature (25 °C). The catalytic products were obtained in moderate to good yields (80-96%) by using complex loading to 2 mol%. To the best of our knowledge, this is the first example of an active ferrocenyl diphosphine Cu(i) catalyst for the carboxylation of terminal alkynes with CO2.
Rational encapsulation of atomically precise nanoclusters into metal-organic frameworks by electrostatic attraction for CO2 conversion
Sun, Lili,Yun, Yapei,Sheng, Hongting,Du, Yuanxin,Ding, Yimin,Wu, Pei,Li, Peng,Zhu, Manzhou
, p. 15371 - 15376 (2018)
Controlled encapsulation of atomically precise nanoclusters (APNCs) into metal-organic frameworks (MOFs) has been an efficient way to create new types of multifunctional crystalline porous materials. Such hybrids (APNCs@MOFs) provide ideal candidates for studying inherent structure-catalysis relationships owing to the well-defined compositions of both components. Moreover, modeling of APNCs@MOFs with precise structures would be more reliable. Herein, we have established an "Electrostatic Attraction Strategy" to synthesize APNCs@MOF catalysts and studied their performance as catalysts for the conversion of CO2. The synthetic strategy presented here has been proved to be general, as evidenced by the syntheses of various APNCs@MOF catalysts including all the combinations of [Au12Ag32(SR)30]4-, [Ag44(SR)30]4-, and [Ag12Cu28(SR)30]4- nanoclusters with ZIF-8, ZIF-67, and MHCF frameworks. In particular, the as-obtained Au12Ag32(SR)30@ZIF-8 composite shows excellent performance in capturing CO2 and converting phenylacetylene into phenylpropiolate under mild conditions (50 °C and ambient CO2 pressure) with a TON as high as 18164, far exceeding those of most known catalysts. What's more, the catalyst is very stable and reused 5 times without loss of catalytic activity. We anticipate that this general synthetic approach may open up a new frontier in the development of promising APNCs@MOF catalysts, which can be applied in a broad range of heterogeneous catalyses in the future.
N-Heterocyclic carbene-nitrogen molybdenum catalysts for utilization of CO2
Chen, Fei,Tao, Sheng,Liu, Ning,Dai, Bin
, (2021/01/19)
Three new N-heterocyclic carbene-nitrogen molybdenum complex was synthesized, and its catalytic activity was evaluated in the cycloaddition of epoxides with CO2. The molybdenum complex combined with tetrabutyl ammonium iodide (TBAI) resulted in a catalytic system for efficient conversion of a wide range of terminal and internal epoxides under 80 °C and 5–7 bar pressure for CO2. The cooperative catalysis mechanism between molybdenum complex and TBAI was elucidated, in which molybdenum complex was used as Lewis acid, and TBAI was employed as nucleophilic reagent. In addition, the NHC-Mo catalytic system was also successfully applied for the direct carboxylation of terminal alkynes with CO2.
Organocatalytic Strategy for the Fixation of CO2via Carboxylation of Terminal Alkynes
Shi, Jun-Bin,Bu, Qingqing,Liu, Bin-Yuan,Dai, Bin,Liu, Ning
, p. 1850 - 1860 (2021/01/14)
An organocatalytic strategy for the direct carboxylation of terminal alkynes with CO2 has been developed. The combined use of a bifunctional organocatalyst and Cs2CO3 resulted in a robust catalytic system for the preparation of a range of propiolic acid derivatives in high yields with broad substrate scope using CO2 at atmospheric pressure under mild temperatures (60 °C). This work has demonstrated that this organocatalytic method offers a competitive alternative to metal catalysis for the carboxylation of terminal alkynes and CO2. In addition, this protocol was suitable for the three-component carboxylation of terminal alkynes, alkyl halides, and CO2.
