Effect of phosphane ligands in the nucleophilic additions at iridium allenylidene complexes

IF 3.2 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Inorganica Chimica Acta Pub Date : 2025-02-03 DOI:10.1016/j.ica.2025.122577

Nerea Soto-Durán, David Gallego-García, Maria Talavera, Sandra Bolaño

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Abstract

The reactivity of allenylidene complexes towards nucleophilic additions has been deeply investigated in ruthenium complexes, however, studies involving iridium complexes are scarce. Thus, several acetonitrile complexes have been synthesized as precursors for the in situ nucleophilic additions of phosphanes and amines at non-isolated allenylidene complexes of formula [IrCp*Cl(=C=C=CPh₂)(L)]PF₆ (L = PMe₃, P(OMe)_3, PPh₂(OMe), PPh₂Me, PCy₃, P(3,5-C₆H₃(CF₃)₂)₃). Therefore, addition of phosphanes as nucleophiles provided different ratios of the allenyl [IrCp*Cl{C(PR₃)=C=CPh₂}(L)]PF₆ (4·R) and alkynyl complexes [IrCp*Cl{C≡C–CPh₂(PR₃)}(L)]PF₆ (5·R) (R = Ph, OMe, Me) depending on the phosphane used as nucleophile and the one bonded to the metal center. The regioselectivity mainly arose from steric demand instead of the electronic effect of the phosphanes. The addition of amines led, in most cases, to the first substituted aminocarbene complexes [IrCp*Cl{=C(NRR')–CH=CPh₂}(L)]PF₆ (R = H, R' = Et (6); R = R' = Et (7)) with the {IrCp*Cl(PR₃)⁺} fragment; however, using a bulky phosphane such as PCy₃, formation of a second product was observed, probably an iridanaphthalene derivative [IrCp*{κ²C,C-{=C(NRR')–CH=CPh₂}(PCy₃)]PF₆ (R = H, R' = Et (8); R = R' = Et (9)).

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磷配体对烯丙烯铱配合物亲核加成的影响

烯丙二烯配合物对亲核加成物的反应性已经在钌配合物中得到了深入的研究，然而，涉及铱配合物的研究却很少。因此，合成了几种乙腈配合物作为非分离的烯基配合物[IrCp*Cl(=C=C=CPh2)(L)]PF6 (L = PMe3， P(OMe)3, PPh2（OMe), PPh2Me, PCy3， P(3,5- c6h3 (CF3)2)3）的原位亲核添加的前体。因此，磷烷作为亲核试剂的加入提供了不同比例的烯基[IrCp*Cl{C(PR3)=C=CPh2}(L)]PF6（4·R）和炔基配合物[IrCp*Cl{C≡C - CPh2(PR3)}(L)]PF6(5·R) (R = Ph, OMe, Me)，这取决于用作亲核试剂的磷烷和与金属中心键合的磷烷。区域选择性主要是由空间需求引起的，而不是由磷化烷的电子效应引起的。在大多数情况下，胺的加入导致第一取代氨基羰基配合物[IrCp*Cl{=C(NRR') -CH =CPh2}(L)]PF6 (R = H， R' = Et (6)；R = R ' = Et (7)) {IrCp * Cl (PR3) +}片段;然而，使用像PCy3这样的大体积磷化物，可以观察到第二产物的形成，可能是环烯萘的衍生物[IrCp*{κ2C，C-{=C(NRR') - ch =CPh2}(PCy3)]PF6 (R = H， R' = Et (8)；R = R' = Et(9))。

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来源期刊

Inorganica Chimica Acta 化学-无机化学与核化学

CiteScore

6.00

自引率

3.60%

发文量

440

审稿时长

35 days

期刊介绍： Inorganica Chimica Acta is an established international forum for all aspects of advanced Inorganic Chemistry. Original papers of high scientific level and interest are published in the form of Articles and Reviews. Topics covered include: • chemistry of the main group elements and the d- and f-block metals, including the synthesis, characterization and reactivity of coordination, organometallic, biomimetic, supramolecular coordination compounds, including associated computational studies; • synthesis, physico-chemical properties, applications of molecule-based nano-scaled clusters and nanomaterials designed using the principles of coordination chemistry, as well as coordination polymers (CPs), metal-organic frameworks (MOFs), metal-organic polyhedra (MPOs); • reaction mechanisms and physico-chemical investigations computational studies of metalloenzymes and their models; • applications of inorganic compounds, metallodrugs and molecule-based materials. Papers composed primarily of structural reports will typically not be considered for publication.