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Synthesis and Reactivity of [PCCP]-Coordinated Group 5 Alkyl and Alkylidene Complexes Featuring a Metallacyclopropene Backbone
Organometallics ( IF 2.5 ) Pub Date : 2019-10-17 , DOI: 10.1021/acs.organomet.9b00577 Patrick Federmann 1 , Tim Richter 1 , Hubert Wadepohl 1 , Joachim Ballmann 1
Organometallics ( IF 2.5 ) Pub Date : 2019-10-17 , DOI: 10.1021/acs.organomet.9b00577 Patrick Federmann 1 , Tim Richter 1 , Hubert Wadepohl 1 , Joachim Ballmann 1
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The R2P-functionalized tolanes 1a (R = Ph) and 1b (R = iPr) were employed for the synthesis of [PCCP]-coordinated group 5 complexes. In the case of vanadium, the d1-configured dialkyl species [PCCP]V(CH2SiMe3)2 (3a and 3b) were prepared and found to be resistant toward oxidation, i.e., the corresponding alkylidene complexes were not observed upon treatment with various oxidants. For niobium and tantalum, however, the high-valent d0-configured alkyl–alkylidene complexes [PCCP]M(=CHSiMe3)(CH2SiMe3) (M = Nb: 6b, M = Ta: 7b) were obtained for the iPr2P-substituted ligand. Both these alkylidenes, i.e., 6b and 7b, were employed for ring-opening metathesis polymerizations (ROMP) of strained olefins. Although the η2-alkyne motifs in 6b and 7b are best described as metallacyclopropenes, the unsaturated ligand backbone was neither degraded nor copolymerized over the course of these polymerizations. Upon hydrogenolysis of 7b, however, the metallacyclopropene backbone was partially hydrogenated, and the dinuclear (μ-H)3-bridged tantalum(V) complex 8 featuring a metallacyclopropane substructure was formed. An intermediate in this reaction was shown to catalytically hydrogenate one or both arenes in naphthalene, while the isolated dimeric species 8 was found to be inactive under identical reaction conditions.
中文翻译：
具有金属环丙烯骨架的[PCCP]-配位的5族烷基和亚炔基配合物的合成和反应性
将R 2 P-官能二苯乙炔1A（R = PH）和图1b（R =我PR）被用于[PCCP]配位的基团5种配合物的合成。在钒的情况下，制备了d 1构型的二烷基物质[PCCP] V（CH 2 SiMe 3）2（3a和3b），发现具有抗氧化性，即在处理时未观察到相应的亚烷基络合物与各种氧化剂。但是，对于铌和钽，高价d 0构型的烷基-亚烷基络合物[PCCP] M（= CHSiMe 3）（CH 2对于i Pr 2 P-取代的配体，获得了SiMe 3）（M ＝ Nb：6b，M ＝ Ta：7b）。这两个亚烷基，即6b和7b，都用于应变烯烃的开环复分解聚合（ROMP）。虽然η 2点中的基序-alkyne 6B和7B被最好地描述为metallacyclopropenes中，不饱和配体骨架既不降解也没有超过共聚这些聚合的过程中。然而，在7b进行氢解后，金属环丙烯主链被部分氢化，双核（μ-H）3形成了具有金属环丙烷亚结构的桥连的钽（V）配合物8。已显示该反应的中间体催化萘中的一个或两个芳烃催化氢化，而发现分离的二聚体8在相同的反应条件下是无活性的。
更新日期：2019-10-17
中文翻译：
具有金属环丙烯骨架的[PCCP]-配位的5族烷基和亚炔基配合物的合成和反应性
将R 2 P-官能二苯乙炔1A（R = PH）和图1b（R =我PR）被用于[PCCP]配位的基团5种配合物的合成。在钒的情况下，制备了d 1构型的二烷基物质[PCCP] V（CH 2 SiMe 3）2（3a和3b），发现具有抗氧化性，即在处理时未观察到相应的亚烷基络合物与各种氧化剂。但是，对于铌和钽，高价d 0构型的烷基-亚烷基络合物[PCCP] M（= CHSiMe 3）（CH 2对于i Pr 2 P-取代的配体，获得了SiMe 3）（M ＝ Nb：6b，M ＝ Ta：7b）。这两个亚烷基，即6b和7b，都用于应变烯烃的开环复分解聚合（ROMP）。虽然η 2点中的基序-alkyne 6B和7B被最好地描述为metallacyclopropenes中，不饱和配体骨架既不降解也没有超过共聚这些聚合的过程中。然而，在7b进行氢解后，金属环丙烯主链被部分氢化，双核（μ-H）3形成了具有金属环丙烷亚结构的桥连的钽（V）配合物8。已显示该反应的中间体催化萘中的一个或两个芳烃催化氢化，而发现分离的二聚体8在相同的反应条件下是无活性的。
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