Research output: Contribution to journal › Article › peer-review
Cationic polypnictogen complexes as building blocks for novel ferrocenes. / Widmann, M; Zhang, ZH; Rehse, A; Balázs, G; Timoshkin, AY; Meyer, K; Winter, R; Scheer, M.
In: Inorganic Chemistry Frontiers, Vol. 13, No. 7, 2026, p. 3112-3119.Research output: Contribution to journal › Article › peer-review
}
TY - JOUR
T1 - Cationic polypnictogen complexes as building blocks for novel ferrocenes
AU - Widmann, M
AU - Zhang, ZH
AU - Rehse, A
AU - Balázs, G
AU - Timoshkin, AY
AU - Meyer, K
AU - Winter, R
AU - Scheer, M
N1 - Times Cited in Web of Science Core Collection: 0 Total Times Cited: 0 Cited Reference Count: 60
PY - 2026
Y1 - 2026
N2 - The systematic nucleophilic functionalisation of the cationic pentaphosphole ligand complex [Cp*Fe(eta 4-P5Me)][OTf] ([OTf]- = [SO3CF3]-) (A) with sterically demanding CpR derivatives is reported. This newly developed protocol turned out to be a highly reliable method for the synthesis of end-deck cyclo-P5 ligand complexes bearing bulky CpR substituents. By the reaction of A with anionic CpR salts, complexes of the type [Cp*Fe(eta 4-P5MeCpR)] (Cp* = eta 5-C5Me5; CpR = Cp ' (1), Cp '' (2), Cp & tprime; (3), CpMe (4); Cp ' = eta 5-C5H4tBu, Cp '' = eta 5-1,3-tBu2C5H3, Cp & tprime; = eta 5-1,3,4-tBu3C5H2, CpMe = eta 5-C5Me4H) are obtained. All products feature a selective 1,1 '-disubstitution at the cyclo-P5 ligand. Further reactivity studies of these complexes with FeBr2 enabled the formation of novel, sterically demanding ferrocene derivatives [{Cp*Fe(eta 4-P5Me(eta 5-Cp ''))}2Fe] (5) and [Cp*Fe(eta 4-P5Me(eta 5-Cp ''))FeCp ''] (6), featuring three different Fe atoms in a ferrocene-like environment. Oxidation of 5 yielded the dicationic complex [{Cp*Fe(eta 4-P5Me(eta 5-Cp ''))}2Fe][FAl]2 (7). EPR, zero-field 57Fe M & ouml;ssbauer, as well as DFT investigations on 7 showed a symmetric distribution of the positive charges on the outer Fe atoms.
AB - The systematic nucleophilic functionalisation of the cationic pentaphosphole ligand complex [Cp*Fe(eta 4-P5Me)][OTf] ([OTf]- = [SO3CF3]-) (A) with sterically demanding CpR derivatives is reported. This newly developed protocol turned out to be a highly reliable method for the synthesis of end-deck cyclo-P5 ligand complexes bearing bulky CpR substituents. By the reaction of A with anionic CpR salts, complexes of the type [Cp*Fe(eta 4-P5MeCpR)] (Cp* = eta 5-C5Me5; CpR = Cp ' (1), Cp '' (2), Cp & tprime; (3), CpMe (4); Cp ' = eta 5-C5H4tBu, Cp '' = eta 5-1,3-tBu2C5H3, Cp & tprime; = eta 5-1,3,4-tBu3C5H2, CpMe = eta 5-C5Me4H) are obtained. All products feature a selective 1,1 '-disubstitution at the cyclo-P5 ligand. Further reactivity studies of these complexes with FeBr2 enabled the formation of novel, sterically demanding ferrocene derivatives [{Cp*Fe(eta 4-P5Me(eta 5-Cp ''))}2Fe] (5) and [Cp*Fe(eta 4-P5Me(eta 5-Cp ''))FeCp ''] (6), featuring three different Fe atoms in a ferrocene-like environment. Oxidation of 5 yielded the dicationic complex [{Cp*Fe(eta 4-P5Me(eta 5-Cp ''))}2Fe][FAl]2 (7). EPR, zero-field 57Fe M & ouml;ssbauer, as well as DFT investigations on 7 showed a symmetric distribution of the positive charges on the outer Fe atoms.
KW - BOND COVALENT RADII
KW - BASIS-SETS
KW - CHEMISTRY
KW - MECHANISM
KW - SINGLE
KW - LIGAND
UR - https://www.mendeley.com/catalogue/114914c9-5b54-33ac-a227-798769e5893e/
U2 - 10.1039/d5qi02477c
DO - 10.1039/d5qi02477c
M3 - статья
VL - 13
SP - 3112
EP - 3119
JO - Inorganic Chemistry Frontiers
JF - Inorganic Chemistry Frontiers
SN - 2052-1545
IS - 7
ER -
ID: 151955165