钪和钇的PNP配合物对烯烃和炔烃的氢化和硅氢化反应具有高效且选择性的催化作用。
Efficient and selective catalysis for hydrogenation and hydrosilation of alkenes and alkynes with PNP complexes of scandium and yttrium.
作者信息
Levine Daniel S, Tilley T Don, Andersen Richard A
机构信息
Department of Chemistry, University of California, Berkeley, Berkeley, California 94720, USA.
出版信息
Chem Commun (Camb). 2017 Oct 31;53(87):11881-11884. doi: 10.1039/c7cc06417a.
Abstract
Scandium and yttrium congeneric complexes, supported by a monoanionic PNP ligand, were studied as catalysts for alkene hydrogenation and hydrosilation, and alkyne semihydrogenation and semihydrosilation. The yttrium congener was found to be much more active in all cases, but this greater activity is accompanied by more rapid catalyst decomposition and therefore higher total yields for some of the reactions with the scandium catalyst. Calculations indicate that the reactions may proceed via σ-bond metathesis of the alkyl complexes to form metal hydride intermediates into which alkenes/alkynes insert.
摘要
研究了由单阴离子PNP配体支撑的钪和钇同属配合物作为烯烃氢化和硅氢化、炔烃半氢化和半硅氢化反应的催化剂。结果发现，钇同属物在所有情况下活性都高得多，但这种更高的活性伴随着催化剂更快的分解，因此对于某些钪催化剂参与的反应，总产率更高。计算表明，反应可能通过烷基配合物的σ键复分解形成金属氢化物中间体，烯烃/炔烃插入其中。
相似文献
1
Efficient and selective catalysis for hydrogenation and hydrosilation of alkenes and alkynes with PNP complexes of scandium and yttrium.
Chem Commun (Camb). 2017 Oct 31;53(87):11881-11884. doi: 10.1039/c7cc06417a.
2
Enabling Semihydrogenation of Alkynes to Alkenes by Using a Calcium Palladium Complex Hydride.
J Am Chem Soc. 2021 Dec 15;143(49):20891-20897. doi: 10.1021/jacs.1c09489. Epub 2021 Dec 2.
3
Magnesium Pincer Complexes and Their Applications in Catalytic Semihydrogenation of Alkynes and Hydrogenation of Alkenes: Evidence for Metal-Ligand Cooperation.
J Am Chem Soc. 2022 Oct 19;144(41):19115-19126. doi: 10.1021/jacs.2c08491. Epub 2022 Oct 4.
4
Electrocatalytic Semihydrogenation of Terminal Alkynes Using Ligand-Based Transfer of Protons and Electrons.
J Am Chem Soc. 2024 Jan 10;146(1):476-486. doi: 10.1021/jacs.3c09885. Epub 2024 Jan 1.
5
Controlled Selectivity through Reversible Inhibition of the Catalyst: Stereodivergent Semihydrogenation of Alkynes.
J Am Chem Soc. 2022 Jul 27;144(29):13266-13275. doi: 10.1021/jacs.2c04233. Epub 2022 Jul 15.
6
Selective semihydrogenation of alkynes on shape-controlled palladium nanocrystals.
Chem Asian J. 2013 May;8(5):919-25. doi: 10.1002/asia.201201166. Epub 2013 Mar 6.
7
Nickel-Catalyzed Stereodivergent Synthesis of E- and Z-Alkenes by Hydrogenation of Alkynes.
ChemSusChem. 2019 Jul 19;12(14):3363-3369. doi: 10.1002/cssc.201900784. Epub 2019 Jun 18.
8
Z-selective, catalytic internal alkyne semihydrogenation under H2/CO mixtures by a niobium(III) imido complex.
J Am Chem Soc. 2011 Sep 28;133(38):14904-7. doi: 10.1021/ja206016s. Epub 2011 Aug 31.
9
Selective Semihydrogenation of Polarized Alkynes by a Gold Hydride Nanocluster.
J Am Chem Soc. 2022 Jul 13;144(27):12501-12509. doi: 10.1021/jacs.2c05046. Epub 2022 Jun 30.
10
Iron- and Cobalt-Catalyzed Alkene Hydrogenation: Catalysis with Both Redox-Active and Strong Field Ligands.
Acc Chem Res. 2015 Jun 16;48(6):1687-95. doi: 10.1021/acs.accounts.5b00134. Epub 2015 Jun 4.
引用本文的文献
1
Stereoselective Semi-Hydrogenations of Alkynes by First-Row (3d) Transition Metal Catalysts.
ChemCatChem. 2022 Oct 21;14(20):e202200886. doi: 10.1002/cctc.202200886. Epub 2022 Sep 15.
2
Backbone Dehydrogenation in Pyrrole-Based Pincer Ligands.
Inorg Chem. 2018 Aug 6;57(15):9544-9553. doi: 10.1021/acs.inorgchem.8b01643. Epub 2018 Jul 24.
本文引用的文献
1
C-H Polyaddition of Dimethoxyarenes to Unconjugated Dienes by Rare Earth Catalysts.
J Am Chem Soc. 2016 May 18;138(19):6147-50. doi: 10.1021/jacs.6b03859. Epub 2016 May 10.
2
Regio- and stereoselective hydrosilylation of alkynes catalyzed by three-coordinate cobalt(I) alkyl and silyl complexes.
J Am Chem Soc. 2014 Dec 17;136(50):17414-7. doi: 10.1021/ja510924v. Epub 2014 Dec 9.
3
Regioselective C-H alkylation of anisoles with olefins catalyzed by cationic half-sandwich rare earth alkyl complexes.
Angew Chem Int Ed Engl. 2012 Dec 14;51(51):12828-32. doi: 10.1002/anie.201206233. Epub 2012 Nov 7.
4
Nanoporous gold catalyst for highly selective semihydrogenation of alkynes: remarkable effect of amine additives.
J Am Chem Soc. 2012 Oct 24;134(42):17536-42. doi: 10.1021/ja3087592. Epub 2012 Oct 12.
5
Facile regio- and stereoselective hydrometalation of alkynes with a combination of carboxylic acids and group 10 transition metal complexes: selective hydrogenation of alkynes with formic acid.
J Am Chem Soc. 2011 Oct 26;133(42):17037-44. doi: 10.1021/ja2069246. Epub 2011 Sep 29.
6
Rare-earth metal alkyl, amido, and cyclopentadienyl complexes supported by imidazolin-2-iminato ligands: synthesis, structural characterization, and catalytic application.
Inorg Chem. 2010 Mar 1;49(5):2435-46. doi: 10.1021/ic9024052.
7
Versatile pathways for in situ polyolefin functionalization with heteroatoms: catalytic chain transfer.
Angew Chem Int Ed Engl. 2008;47(11):2006-25. doi: 10.1002/anie.200703310.
8
Organolanthanide-catalyzed hydroamination.
Acc Chem Res. 2004 Sep;37(9):673-86. doi: 10.1021/ar040051r.
9
Titanocene-catalyzed regioselective syn-hydrosilation of alkynes.
Org Lett. 2003 Sep 18;5(19):3479-81. doi: 10.1021/ol035277t.
10
Homogeneous catalysis with methane. A strategy for the hydromethylation of olefins based on the nondegenerate exchange of alkyl groups and sigma-bond metathesis at scandium.
J Am Chem Soc. 2003 Jul 2;125(26):7971-7. doi: 10.1021/ja021341a.
Zotero 插件