Lapshin Ivan V, Cherkasov Anton V, Lyssenko Konstantin A, Fukin Georgy K, Trifonov Alexander A
Institute of Organometallic Chemistry of Russian Academy of Sciences, 49 Tropinina Street, GSP-445, Nizhny Novgorod 630950, Russia.
Institute of Organoelement Compounds of Russian Academy of Sciences, 28 Vavilova Street, Moscow 119334, Russia.
Inorg Chem. 2022 Jun 20;61(24):9147-9161. doi: 10.1021/acs.inorgchem.2c00698. Epub 2022 Jun 9.
A series of NHC-stabilized amido compounds (NHC)M[N(SiMe)] (M = Yb(II), Sm(II), Ca(II); = 1, 2) showed remarkable catalytic efficiency in addition of PhPH and PH to alkenes under mild conditions and low catalyst loading. The effect of σ-donor capacity of NHCs on catalytic activity in hydrophosphination of styrene with PhPH and PH was revealed. For the series of three-coordinate complexes , a tendency to increase the catalytic activity with growth of σ-donating strength of the carbene ligand was clearly demonstrated. The complex (NHC)Sm[N(SiMe)] (NHC = 1,3-diisopropyl-2-imidazole-2-ylidene) () proved to be the most efficient catalyst, which enabled hardly realizable transformations such as PhPH addition across internal C═C bonds of norbornene and - and -stilbenes, providing the highest reaction rate for addition of PH to styrene. Excellent regio- and chemoselectivities of alkylation of PH with styrenes allow for a selective and good-yield synthesis of desired organophosphines─either primary, secondary, or tertiary. Stepwise alkylation of PH with various substituted styrenes can be efficiently applied as an approach to nonsymmetric secondary phosphines. The rate equation of the addition of styrene to PH promoted by was found: rate = [styrene][5Sm].
一系列NHC稳定的酰胺化合物（NHC）M[N(SiMe)]（M = Yb(II)、Sm(II)、Ca(II)； = 1, 2）在温和条件和低催化剂负载量下，对PhPH和PH与烯烃的加成反应显示出显著的催化效率。揭示了NHC的σ供体能力对苯乙烯与PhPH和PH进行氢膦化反应催化活性的影响。对于这一系列三配位配合物，清楚地证明了随着卡宾配体σ供电子强度的增加，催化活性有增加的趋势。配合物（NHC）Sm[N(SiMe)]（NHC = 1,3 - 二异丙基 - 2 - 咪唑 - 2 - 亚基）（）被证明是最有效的催化剂，它能实现难以实现的转化，如PhPH加成到降冰片烯以及反式 - 和顺式 - 二苯乙烯的内部C═C键上，对PH加成到苯乙烯提供最高的反应速率。PH与苯乙烯烷基化反应具有优异的区域选择性和化学选择性，可用于选择性地高产率合成所需的有机膦——伯、仲或叔膦。PH与各种取代苯乙烯的逐步烷基化可有效地用作合成不对称仲膦的方法。发现了由促进的苯乙烯与PH加成反应的速率方程：速率 = [苯乙烯][5Sm] 。
