一种钌磷杂环庚三烯作为双亲性金属磷烯的合成子。
A Ruthenophosphanorcaradiene as a Synthon for an Ambiphilic Metallophosphinidene.
作者信息
Saint-Denis Tyler G, Wheeler T Alexander, Chen Qingchuan, Balázs Gábor, Settineri Nicholas S, Scheer Manfred, Tilley T Don
机构信息
Department of Chemistry, University of California, Berkeley, Berkeley, California 94720-1460, United States.
Department of Inorganic Chemistry, University of Regensburg, 93040 Regensburg, Germany.
出版信息
J Am Chem Soc. 2024 Feb 21;146(7):4369-4374. doi: 10.1021/jacs.3c14779. Epub 2024 Feb 9.
Reaction of the ruthenium carbene complex Cp*(IPr)RuCl () (IPr = 1,3-bis(Dipp)imidazol-2-ylidene; Dipp = 2,6-diisopropylphenyl) with sodium phosphaethynolate (NaOCP) led to intramolecular dearomatization of one of the Dipp substituents on the Ru-bound carbene to afford a Ru-bound phosphanorcaradiene, . Computations by DFT reveal a transition state characterized by a concerted process whereby CO migrates to the Ru center as the P atom adds to the π system of the aryl group. The phosphanorcaradiene possesses ambiphilic properties and reacts with both nucleophilic and electrophilic substrates, resulting in rearomatization of the ligand aryl group with net P atom transfer to give several unusual metal-bound, P-containing main-group moieties. These new complexes include a metallo-1-phospha-3-azaallene (Ru─P═C═NR), a metalloiminophosphanide (Ru─P═N─R), and a metallophosphaformazan (Ru─P(═N─N═CPh)). Reaction of with the carbene 2,3,4,5-tetramethylimidazol-2-ylidene (IMe) produced the corresponding phosphaalkene DippP═IMe.
钌卡宾配合物Cp*(IPr)RuCl（）（IPr = 1,3-双（二异丙基苯基）咪唑-2-亚基；Dipp = 2,6-二异丙基苯基）与膦乙炔醇钠（NaOCP）反应，导致钌键合卡宾上Dipp取代基之一发生分子内脱芳构化，生成钌键合的磷杂环庚三烯，。密度泛函理论（DFT）计算揭示了一个过渡态，其特征是一个协同过程，即当磷原子加到芳基的π体系时，一氧化碳迁移到钌中心。该磷杂环庚三烯具有双亲性，能与亲核和亲电底物反应，导致配体芳基重新芳构化并伴有净磷原子转移，生成几个不寻常的金属键合含磷主族部分。这些新配合物包括金属-1-磷杂-3-氮杂丙二烯（Ru─P═C═NR）、金属亚氨基磷化物（Ru─P═N─R）和金属磷杂甲脒（Ru─P(═N─N═CPh)）。与卡宾2,3,4,5-四甲基咪唑-2-亚基（IMe）反应生成相应的磷烯DippP═IMe。
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