Riesinger, Christoph and Zimmermann, Lisa and Szlosek, Robert and Balazs, Gabor and Wieneke, Jan and Orel, Lisa-Marie and Dütsch, Luis and Scheer, Manfred (2025) Functionalization, Fragmentation, and Expansion of cyclo-P4R2 Ligands. CHEMISTRY-A EUROPEAN JOURNAL, 31 (36): e202501305. ISSN 0947-6539, 1521-3765
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In this study, three isolobal complexes of the form [{LnM}(eta 3-P4R2)]+ ({LnM} = {CpMo(CO)2} (A), {Cp'''Ni} (B), {Cp'''Co}- (C), R = Ph, iPr; Cp''' = 1,2,4-tBu3C5H2) are reacted with nucleophilic carbenes (L). While C does not show any reactivity, the cationic complexes A and B undergo addition reactions. The respective products [CpMo(CO)2(eta 3-P4R2L)]+ (1a - d) and [Cp'''Ni(eta 1:1-P4R2L)]+ (3a - d) show different geometries for the L-P3PR2 ligands. Their reactivity towards EtO- results in either a simple addition (for 1) or a complex addition, ring-opening, rearrangement sequence (for 3). Moreover, [Cp'''Ni(eta 2-IDippPP(OEt)PPiPr2)] (4) could be methylated by the reaction with MeOTf, which affords an iso-tetraphosphine ligand, marking the first example of complete functionalization of a polyphosphorus ligand to a complexed phosphine. Mechanistic studies shed light upon the fundamental principles, which differentiate the influence of the isolobal {CpMo(CO)2}, {Cp'''Ni}, and {Cp'''Co}- transition metal units. Lastly, 3a-d were chosen as model substrates for further nucleophilic functionalization. In this regard, 3 reacts with [CN]- in a [3+1] fragmentation reaction affording the dimerized species [{Cp'''Ni}2(mu,eta 1:1:1:1-cyclo-P4(PR2)2)] (6a: R = Ph, 6b: R = iPr) together with IDippP-CN. In contrast, the reaction with [ECO]- (E = P, As) led to an extension of the pnictogen framework yielding [Cp'''Ni(eta 1:1-EP4Ph2IDipp)] (8a: E = P, 8b: E = As).
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | HYBRID DENSITY FUNCTIONALS; METAL-MEDIATED ACTIVATION; ORGANIC-CHEMISTRY; BASIS-SETS; PHOSPHORUS; COMPLEXES; COORDINATION; REACTIVITY; CARBON; BONDS; isolobal; P-4 activation; phosphorus; reaction mechanism; transition metal |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie > Chair Prof. Dr. Manfred Scheer |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 07 May 2026 04:18 |
| Last Modified: | 07 May 2026 04:18 |
| URI: | https://pred.uni-regensburg.de/id/eprint/66174 |
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