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Cycloaddition Chemistry of 2‐Phosphaethynolate Revealed By Angewandte Research Articles Chemie How to cite: Angew. Chem. Int. Ed. 2021, 60, 1197–1202 Cycloaddition Reactions International Edition: doi.org/10.1002/anie.202012506 German Edition: doi.org/10.1002/ange.202012506 The “Hidden” Reductive [2+2+1]-Cycloaddition Chemistry of 2-Phosphaethynolate Revealed by Reduction of a Th-OCP Linkage Jingzhen Du, Gbor Balzs, Ashley J. Wooles, Manfred Scheer,* and Stephen T. Liddle* Abstract: The reduction chemistry of the newly emerging coupling.[2] Furthermore, cycloaddition reactions of (OCP)À 2-phosphaethynolate (OCP)À is not well explored, and many under oxidising or neutral conditions have become well unanswered questions remain about this ligand in this context. established, producing a variety of novel three, four-, five-, or We report that reduction of [Th(TrenTIPS)(OCP)] (2, six-membered phosphorus heterocycles.[1] In contrast, the TIPS i 3À À [1, 3] Tren = [N(CH2CH2NSiPr 3)] ), with RbC8 via [2+2+1] reduction chemistry of (OCP) is in its infancy, but the cycloaddition, produces an unprecedented hexathorium com- clear picture already is that this closed-shell anion resists TIPS plex [{Th(Tren )}6(m-OC2P3)2(m-OC2P3H)2Rb4](5) featur- reduction, to avoid populating antibonding orbitals, inevita- ing four five-membered [C2P3] phosphorus heterocycles, which bly leading, when reduction can be effected, to spontaneous can be converted to a rare oxo complex [{Th(TrenTIPS)- fragmentation of the O-C-P unit in the majority of cases. (m-ORb)}2](6) and the known cyclometallated complex Indeed, this has been observed in many low-valent early i i [1,3] À [Th{N(CH2CH2NSiPr 3)2(CH2CH2SiPr 2CHMeCH2)}] (4)by d-block and f-block cases. Thus, there are no (OCP) thermolysis; thereby, providing an unprecedented example of cycloaddition reactions yet reported under reducing condi- reductive cycloaddition reactivity in the chemistry of tions. 2-phosphaethynolate. This has permitted us to isolate inter- Notwithstanding the proclivity of (OCP)À to fragment on mediates that might normally remain unseen. We have reduction, a few notable examples report divergent reaction debunked an erroneous assumption of a concerted fragmenta- outcomes. Reduction of [Sc{HC(CMeNAr)2}(OAr)(THF)}- À i tion process for (OCP) , rather than cycloaddition products (OCP)] (Ar = 2,6-Pr 2C6H3) with KC8 generates a strongly that then decompose with [Th(TrenTIPS)O]À essentially acting activated transient radical dianion (OCP)2À·, which dimerises 4À [4] as a protecting then leaving group. In contrast, when KC8 or to give (OCPPCO) . In contrast, we reported TIPS TIPS CsC8 were used the phosphinidiide CÀH bond activation that reduction of [U(Tren )(OCP)] (Tren = TIPS i i 3À product [{Th(Tren )}Th{N(CH2CH2NSiPr 3)2[CH2CH2- {N(CH2CH2NSiPr 3)3} ) with KC8/2.2.2-cryptand results in i 2À· SiPr 2CH(Me)CH2C(O)m-P]}] (3) and the oxo complex trapping of the radical dianion [OCP] , formally a product of TIPS III [{Th(Tren )(m-OCs)}2](7) were isolated. reduction by U , in the mixed-valence diuranium(III/IV) TIPS complex [{U(Tren )}2(m-OCP)][K(2.2.2-cryptand)] that Introduction features a strongly activated, highly bent O-C-P unit (126.6(9)8).[5] Seemingly moderate activation of the O-C-P There is burgeoning interest in the emerging, fundamental linkage was found when [Th(OCP){PhC(NSiMe3)2}3] was À chemistry of the 2-phosphaethynolate (OCP) anion, not only reacted with [Ni(COD)2] to afford [Th(m-OCP)Ni(COD)}- because regular investigations of this anion became practi- {PhC(NSiMe3)2}3], which also exhibits a bent O-C-P moiety cable only around a decade ago but also because it is a valence (148.1(3)8).[6] Given these prior results, and since ThIII is isoelectronic, P-analogue of the ubiquitous cyanate (OCN)À known to be more reactive than UIII,[7] this raised the question anion.[1] In terms of the fundamental redox chemistry of of whether there would be different behaviour of activated (OCP)À , it has been found that this anion is readily oxidised, (OCP)À with a Th- rather than U-TrenTIPS system. 2À ostensibly to the heterobicylic dianion, (P4C4O4) , via radical Here, we report the first example of a cycloaddition reaction of (OCP)À under reducing conditions. Specifically, we find a [2+2+1] cycloaddition reaction of (OCP)À , which is [*] Dr. J. Du, Dr. A. J. Wooles, Prof. Dr. S. T. Liddle III Department of Chemistry, The University of Manchester likely mediated by a Th species that results from reduction IV Oxford Road, Manchester, M13 9PL (UK) of a stable Th -OCP linkage by strong reductants MC8 (M = E-mail: [email protected] K, Rb, Cs). This produces an unprecedented hexathorium Dr. G. Balzs, Prof. Dr. M. Scheer cluster containing four five-membered [C2P3] phosphorus Institute of Inorganic Chemistry, University of Regensburg heterocycles. Thermolysis of this cluster produces the ulti- Universittsstr. 31, 93053 Regensburg (Germany) mate products of this reaction, a rare example of a thorium- E-mail: [email protected] oxo species and a cyclometallated complex via OÀC and Supporting information and the ORCID identification number(s) for ThÀC bond cleavage. The isolation of the cluster intermedi- the author(s) of this article can be found under: ate, which might normally have remained unseen, as well as https://doi.org/10.1002/anie.202012506. the final oxo product permits us to realise that a reaction that 2020 The Authors. Angewandte Chemie International Edition has the superficial overall appearance of a concerted cleavage published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution License, which of the OÀC bond of the O-C-P unit is in fact far more permits use, distribution and reproduction in any medium, provided complicated than previously thought. The sterically demand- the original work is properly cited. ing [Th(TrenTIPS)O]À unit has essentially performed the role of Angew. Chem. Int. Ed. 2021, 60, 1197 – 1202 2020 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH 1197 Angewandte Research Articles Chemie protecting then leaving group, allowing the presence of an of the fingerprint region (Figure S2). The solid structure of 2 otherwise “hidden” [2+2+1] cycloaddition reaction to be (Figure 1) reveals ThÀO, OÀC, and CÀP distances of 2.334(3), recognised. These observations, together with the isolation of 1.246(5), and 1.544(5) , and Th-O-C and O-C-P angles of phosphinidiide and CÀH activation by-products when M = K, 173.1(3) and 178.8(5)8, respectively, suggesting overall[11] the suggest that reductive (OCP)À fragmentation reactions more dominance of PC-OÀ , rather than ÀP=C=O, resonance widely are likely more elaborate than previously thought. forms, as commonly observed when this anion is coordinated [3] to electropositive metal ions. The ThÀNamide and ThÀNamine distances are unremarkable. These data compare well to other Results and Discussion actinide-OCP complexes.[5,6,12] In order to ascertain the likely reducibility of 2,we Synthesis, characterisation, and solid-state structure of 2. computed the DFT geometry optimised structure of 2 and its TIPS [8] III À [9] Treatment of [Th(Tren )(DME)][BPh4] (1) with reduced Th form 2 . Interestingly, the LUMO of 2 is TIPS [Na(OCP)(1,4-diox)2.2] in DME gives [Th(Tren )(OCP)] computed to be mainly a 7s/5f hybrid with only minor [9] 1 (2) in 52% crystalline yield (Scheme 1). The H NMR (< 10%) 6d character and it has the appearance of a ml = 3 spectrum of 2 exhibits three resonances spanning the range orbital (f-type) with three of the six lobes diminished due to from 1.0 to 4.0 ppm, with the protons of the isopropyl groups destructive interference from the 7s component (Figure S18). being overlapped, which was previously observed in the In 2À (Figure S19), the HOMO is still Th-centred, though now TIPS [10] 13 closely related compound [Th(Tren )(N3)]. The C- this orbital is roughly composed of equal 7s, 6d, and 5f {1H} NMR spectrum of 2 shows five resonances within the contributions; the quasi-degenerate LUMO and LUMO + 1 range 10.0 to 160.0 ppm, with the (OCP)À carbon resonance of 2À , which are p* orbitals of (OCP)À lie 0.5 eV above the identified at 157.6 ppm. Single resonances at 3.4 and HOMO, and there is clear overlap of the Th-coefficient with À339.9 ppm in the 29Si{1H} and 31P{1H} NMR spectra of 2, the O-C-P components, and so MLCTresulting in spin density respectively, support the C3v symmetric formulation (Sup- transfer to the O-C-P unit with concomitant radical couplings porting Information, Figures S7–S10). In the ATR-IR spec- is easily energetically feasible. trum of 2, the antisymmetric stretch of (OCP)À is clearly Reduction chemistry of 2. With 2 in-hand, and a theoret- identified as a strong absorption at 1678 cmÀ1, but the ical basis for its likely reduction chemistry established, we [9] symmetric stretch could not be assigned due to the complexity examined its reduction with MC8 (M = K, Rb, Cs). Un- Scheme 1. Synthesis of the thorium(IV)-OCP complex 2, and reduction of 2 to prepare 3 and 5–7 using MC8 (M =K, Rb, Cs) reagents. The proposed structure of the eliminated H6C4P6 from 5 is one of several possible isomers. However, if polymeric species do not form, it seems most likely on the basis of Ref. [24]. 1198 www.angewandte.org 2020 The Authors.
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