Tailoring the Fe → Pd interaction in cationic Pd(<scp>ii</scp>) complexes<i>via</i>structural variation of the ligand scaffold of sterically demanding dppf-analogs and their P,N-counterparts

Dey, Subhayan; Roesler, Fabian; Bruhn, Clemens; Kelemen, Zsolt; Pietschnig, Rudolf

doi:10.1039/d3qi00576c

Cited by 2 publications

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References 98 publications

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“…For comparison, the thermodynamic driving force of the related transformation is lower in case of diphospha[2]ferrocenophane (ΔG = À 2.1 kcal/mol), but the corresponding reaction barrier is lower (34.4 kcal/mol) as well (for better comparison values were recomputed at ωB97X-D/def2-TZVP). [29] The question arises why only 4 is formed exclusively and no other selenium containing species could be detected. Different possible products were investigated (Scheme S1, ESI) and based on our computational results it can be established that introducing a second selenium atom is less favoured thermodynamically, with the transfer reactions being endergonic.…”

Section: Resultsmentioning

confidence: 99%

Controlled Ring Opening of a Tetracyclic Tetraphosphane with Twofold Metallocene Bridging

Dey,

Szathmári,

Franz

et al. 2024

Chemistry A European J

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A direct route to a doubly ferrocene bridged tetracyclic tetraphosphane 1 was developed via reductive coupling of Fe(CpPCl2)2 (2a), where a chlorine terminated linear P4‐compound 3 could be identified as an intermediate. Selective P‐P bond activation was further achieved by reacting 1 with elemental selenium or [Cp*Al]4, where regioselective insertion of Se or Al atoms resulted in ferrocenylene bridged [P4Se] (4) or [P4Al] (7) moieties. Compound 7 can be transformed to a hydrogen terminated linear P4 species, 8, with protic solvents. Methylation of compound 1 with MeOTf, proceeds via intermediate formation of monomethylated species 5, which gradually produced Me2‐terminated dicationic 6, again containing a linear P4‐unit. Besides spectroscopic characterization, the structural details of compounds 1, 4, 6, and 8 could be determined by SC‐XRD. Moreover, DFT calculations were used to rationalize the reactivity of 1, derived compounds and intermediates. As a key feature, 1 undergoes ring opening polymerization to a linear polyphosphane 9.

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Section: Resultsmentioning

confidence: 99%

Controlled Ring Opening of a Tetracyclic Tetraphosphane with Twofold Metallocene Bridging

Dey,

Szathmári,

Franz

et al. 2024

Chemistry A European J

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Synthesis and Coordination Behavior of a Hybrid Phosphanylferrocene Amidine Ligand

Binnani,

Leitner,

Císařová

et al. 2023

Eur J Inorg Chem

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The combination of different donor moieties often results in unconventional coordination behavior. This contribution describes the synthesis of a new hybrid ligand, phosphanylferrocene amidine Ph2PfcN=CHNMe2 (1; fc = ferrocene‐1,1¢‐diyl), and its coordination behavior toward the light platinum metals. Reacting compound 1 with [PdCl2(MeCN)2] produced the chelate complex [PdCl2(1‐κ2P,N)] and the bis(phosphane) complex trans‐[PdCl2(1‐κP)2], depending on the ligand‐to‐metal stoichiometry. Halide removal from [PdCl2(1‐κ2P,N)] with Na[BARF] afforded the chloride‐bridged dimer [Pd2(μ‐Cl)2(1‐κ2P,N)2][BARF]2, which was presumably in equilibrium with the mononuclear κ3‐complex [PdCl(1‐κ3Fe,P,N)][BARF] in solution (BARF = tetrakis[3,5‐bis(trifluoromethyl)phenyl]borate). The reactions of 1 with the isoelectronic precursors [(arene)MCl(μ‐Cl)]2 (M/arene = Ru(II)/p‐cymene, and Rh(III)/C5Me5) generated the respective bridge‐cleavage products [(arene)MCl2(1‐κP)], which transformed into the P,N‐chelate complexes [(arene)MCl(1‐κ2P,N)][BARF] when treated with Na[BARF] as a chloride scavenger. All this suggests preferential coordination the phosphane moiety to soft metal ions, while the coordination of the amidine moiety can be induced through changing the reaction stoichiometry or by generating a vacant coordination site at the metal ion. The compounds were characterized using a combination of standard spectroscopic methods (multinuclear NMR, IR, and ESI MS) and single‐crystal X‐ray crystallography, and compounds 1 and 3 were further studied by cyclic voltammetry.

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Tailoring the Fe → Pd interaction in cationic Pd(ii) complexesviastructural variation of the ligand scaffold of sterically demanding dppf-analogs and their P,N-counterparts

Abstract: Two 1,1’-azaphospha substituted dppf-analogues Fc'(NMe2)(PPh2) (Ph = C6H5, Fc' = 1,1'-ferrocenediyl, 3a) and Fc'(NMe2)(PMes2) (Mes = 2,4,6-Me3C6H2, 3b) have been prepared, via reductive amination, followed by salt-metathesis (of 2), starting...

Cited by 2 publications

References 98 publications

Controlled Ring Opening of a Tetracyclic Tetraphosphane with Twofold Metallocene Bridging

Controlled Ring Opening of a Tetracyclic Tetraphosphane with Twofold Metallocene Bridging

Synthesis and Coordination Behavior of a Hybrid Phosphanylferrocene Amidine Ligand

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