TY - JOUR

T1 - Nucleophilic Functionalization of a Cationic Pentaphosphole Complex–A Systematic Study of Reactivity

AU - Widmann, Maximilian

AU - Riesinger, Christoph

AU - Тимошкин, Алексей Юрьевич

AU - Blank, Philip

AU - Scheer, M.

PY - 2025/3/12

Y1 - 2025/3/12

N2 - The systematic nucleophilic functionalization of the cationic pentaphosphole ligand complex [Cp*Fe(η4-P5Me)][OTf] (A) with group 16/17 nucleophiles is reported. This method represents a highly reliable and versatile strategy for the design of novel transition-metal complexes featuring twofold substituted end-deck cyclo-P5 ligands, bearing unprecedented hetero-element substituents. By the reaction of A with classical group 16 nucleophiles, complexes of the type [Cp*Fe(η4-P5MeE)] (E=OEt (1), OtBu (2), SPh (3), SePh (4)) are obtained. By transferring this protocol to group 17 nucleophiles, the highly sensitive complexes [Cp*FeP5(η4-P5MeX)] (X=F (5), Cl (6), Br (7), I (8)) could be isolated. All products show exclusively 1,1'-substitution at the cyclo-P5 ring. Interestingly, further studies on the reactivity of the halogenated species revealed their ability to undergo ring-opening reactions with cyclic ethers such as THF and ethylene oxide yielding [Cp*FeP5(η4-P5MeOC4H8X)] (X=Br (9), I (10)) or [Cp*FeP5(η4-P5MeOC2H4X)] (X=Br (11), I (12)), respectively. Furthermore, the use of acyclic ethers such as dimethoxyethane led to the formation of [Cp*FeP5(η4-P5MeOC2H4OCH3)] (13) mediated by C−O bond cleavage, followed by subsequent P−O bond formation, as further enlightened by DFT calculations.

AB - The systematic nucleophilic functionalization of the cationic pentaphosphole ligand complex [Cp*Fe(η4-P5Me)][OTf] (A) with group 16/17 nucleophiles is reported. This method represents a highly reliable and versatile strategy for the design of novel transition-metal complexes featuring twofold substituted end-deck cyclo-P5 ligands, bearing unprecedented hetero-element substituents. By the reaction of A with classical group 16 nucleophiles, complexes of the type [Cp*Fe(η4-P5MeE)] (E=OEt (1), OtBu (2), SPh (3), SePh (4)) are obtained. By transferring this protocol to group 17 nucleophiles, the highly sensitive complexes [Cp*FeP5(η4-P5MeX)] (X=F (5), Cl (6), Br (7), I (8)) could be isolated. All products show exclusively 1,1'-substitution at the cyclo-P5 ring. Interestingly, further studies on the reactivity of the halogenated species revealed their ability to undergo ring-opening reactions with cyclic ethers such as THF and ethylene oxide yielding [Cp*FeP5(η4-P5MeOC4H8X)] (X=Br (9), I (10)) or [Cp*FeP5(η4-P5MeOC2H4X)] (X=Br (11), I (12)), respectively. Furthermore, the use of acyclic ethers such as dimethoxyethane led to the formation of [Cp*FeP5(η4-P5MeOC2H4OCH3)] (13) mediated by C−O bond cleavage, followed by subsequent P−O bond formation, as further enlightened by DFT calculations.

KW - iron

KW - nucleophilic functionalization

KW - main group chemistry

KW - phosphorus

KW - iron

KW - main group chemistry

KW - nucleophilic functionalization

KW - phosphorus

UR - https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/chem.202404494

UR - https://www.mendeley.com/catalogue/d658f878-9482-3ee7-a0cd-2b28fbb3d188/

U2 - 10.1002/chem.202404494

DO - 10.1002/chem.202404494

M3 - Article

VL - 31

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

IS - 15

M1 - e202404494

ER -