Heteroleptic, two-coordinate [M(NHC){N(SiMe3)2}] (M = Co, Fe) complexes: Synthesis, reactivity and magnetism rationalized by an unexpected metal oxidation state

Andreas A. Danopoulos; Pierre Braunstein; Kirill Yu Monakhov; Jan Van Leusen; Paul Kögerler; Martin Clémancey; Jean Marc Latour; Anass Benayad; Moniek Tromp; Elixabete Rezabal; Gilles Frison

doi:10.1039/c6dt03565e

Heteroleptic, two-coordinate [M(NHC){N(SiMe₃)₂}] (M = Co, Fe) complexes: Synthesis, reactivity and magnetism rationalized by an unexpected metal oxidation state

Andreas A. Danopoulos
, Pierre Braunstein
, Kirill Yu Monakhov
, Jan Van Leusen
, Paul Kögerler
, Martin Clémancey
, Jean Marc Latour
, Anass Benayad
, Moniek Tromp
, Elixabete Rezabal
, Gilles Frison

Research output: Contribution to journal › Article › peer-review

Abstract

The linear, two-coordinate and isostructural heteroleptic [M(IPr){N(SiMe₃)₂}] (IPr = 1,3-bis(diisopropylphenyl)-imidazol-2-ylidene), formally M^I complexes (M = Co, 3; Fe, 4) were obtained by the reduction of [M(IPr)Cl{N(SiMe₃)₂}] with KC₈, or [Co(IPr){N(SiMe₃)₂}₂] with mes∗PH₂, mes∗ = 2,4,6-tBu₃C₆H₂. The magnetism of 3 and 4 implies Co^II and Fe^II centres coupled to one ligand-delocalized electron, in line with XPS and XANES data; the ac susceptibility of 4 detected a pronounced frequency dependence due to slow magnetization relaxation. Reduction of [Fe(IPr)Cl{N(SiMe₃)₂}] with excess KC₈ in toluene gave the heteronuclear 'inverse-sandwich' Fe-K complex 7, featuring η⁶-toluene sandwiched between one Fe⁰ and one K⁺ centre.

Original language	English
Pages (from-to)	1163-1171
Number of pages	9
Journal	Dalton Transactions
Volume	46
Issue number	4
DOIs	https://doi.org/10.1039/c6dt03565e
Publication status	Published - 1 Jan 2017
Externally published	Yes

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Danopoulos, A. A., Braunstein, P., Monakhov, K. Y., Van Leusen, J., Kögerler, P., Clémancey, M., Latour, J. M., Benayad, A., Tromp, M., Rezabal, E., & Frison, G. (2017). Heteroleptic, two-coordinate [M(NHC){N(SiMe₃)₂}] (M = Co, Fe) complexes: Synthesis, reactivity and magnetism rationalized by an unexpected metal oxidation state. Dalton Transactions, 46(4), 1163-1171. https://doi.org/10.1039/c6dt03565e

@article{685d0fc451804271af6145e521b28c51,

title = "Heteroleptic, two-coordinate [M(NHC)\{N(SiMe3)2\}] (M = Co, Fe) complexes: Synthesis, reactivity and magnetism rationalized by an unexpected metal oxidation state",

abstract = "The linear, two-coordinate and isostructural heteroleptic [M(IPr)\{N(SiMe3)2\}] (IPr = 1,3-bis(diisopropylphenyl)-imidazol-2-ylidene), formally MI complexes (M = Co, 3; Fe, 4) were obtained by the reduction of [M(IPr)Cl\{N(SiMe3)2\}] with KC8, or [Co(IPr)\{N(SiMe3)2\}2] with mes∗PH2, mes∗ = 2,4,6-tBu3C6H2. The magnetism of 3 and 4 implies CoII and FeII centres coupled to one ligand-delocalized electron, in line with XPS and XANES data; the ac susceptibility of 4 detected a pronounced frequency dependence due to slow magnetization relaxation. Reduction of [Fe(IPr)Cl\{N(SiMe3)2\}] with excess KC8 in toluene gave the heteronuclear 'inverse-sandwich' Fe-K complex 7, featuring η6-toluene sandwiched between one Fe0 and one K+ centre.",

author = "Danopoulos, \{Andreas A.\} and Pierre Braunstein and Monakhov, \{Kirill Yu\} and \{Van Leusen\}, Jan and Paul K{\"o}gerler and Martin Cl{\'e}mancey and Latour, \{Jean Marc\} and Anass Benayad and Moniek Tromp and Elixabete Rezabal and Gilles Frison",

note = "Publisher Copyright: {\textcopyright} 2017 The Royal Society of Chemistry.",

year = "2017",

month = jan,

day = "1",

doi = "10.1039/c6dt03565e",

language = "English",

volume = "46",

pages = "1163--1171",

journal = "Dalton Transactions",

issn = "1477-9226",

number = "4",

}

Danopoulos, AA, Braunstein, P, Monakhov, KY, Van Leusen, J, Kögerler, P, Clémancey, M, Latour, JM, Benayad, A, Tromp, M, Rezabal, E & Frison, G 2017, 'Heteroleptic, two-coordinate [M(NHC){N(SiMe₃)₂}] (M = Co, Fe) complexes: Synthesis, reactivity and magnetism rationalized by an unexpected metal oxidation state', Dalton Transactions, vol. 46, no. 4, pp. 1163-1171. https://doi.org/10.1039/c6dt03565e

TY - JOUR

T1 - Heteroleptic, two-coordinate [M(NHC){N(SiMe3)2}] (M = Co, Fe) complexes

T2 - Synthesis, reactivity and magnetism rationalized by an unexpected metal oxidation state

AU - Danopoulos, Andreas A.

AU - Braunstein, Pierre

AU - Monakhov, Kirill Yu

AU - Van Leusen, Jan

AU - Kögerler, Paul

AU - Clémancey, Martin

AU - Latour, Jean Marc

AU - Benayad, Anass

AU - Tromp, Moniek

AU - Rezabal, Elixabete

AU - Frison, Gilles

PY - 2017/1/1

Y1 - 2017/1/1

N2 - The linear, two-coordinate and isostructural heteroleptic [M(IPr){N(SiMe3)2}] (IPr = 1,3-bis(diisopropylphenyl)-imidazol-2-ylidene), formally MI complexes (M = Co, 3; Fe, 4) were obtained by the reduction of [M(IPr)Cl{N(SiMe3)2}] with KC8, or [Co(IPr){N(SiMe3)2}2] with mes∗PH2, mes∗ = 2,4,6-tBu3C6H2. The magnetism of 3 and 4 implies CoII and FeII centres coupled to one ligand-delocalized electron, in line with XPS and XANES data; the ac susceptibility of 4 detected a pronounced frequency dependence due to slow magnetization relaxation. Reduction of [Fe(IPr)Cl{N(SiMe3)2}] with excess KC8 in toluene gave the heteronuclear 'inverse-sandwich' Fe-K complex 7, featuring η6-toluene sandwiched between one Fe0 and one K+ centre.

AB - The linear, two-coordinate and isostructural heteroleptic [M(IPr){N(SiMe3)2}] (IPr = 1,3-bis(diisopropylphenyl)-imidazol-2-ylidene), formally MI complexes (M = Co, 3; Fe, 4) were obtained by the reduction of [M(IPr)Cl{N(SiMe3)2}] with KC8, or [Co(IPr){N(SiMe3)2}2] with mes∗PH2, mes∗ = 2,4,6-tBu3C6H2. The magnetism of 3 and 4 implies CoII and FeII centres coupled to one ligand-delocalized electron, in line with XPS and XANES data; the ac susceptibility of 4 detected a pronounced frequency dependence due to slow magnetization relaxation. Reduction of [Fe(IPr)Cl{N(SiMe3)2}] with excess KC8 in toluene gave the heteronuclear 'inverse-sandwich' Fe-K complex 7, featuring η6-toluene sandwiched between one Fe0 and one K+ centre.

U2 - 10.1039/c6dt03565e

DO - 10.1039/c6dt03565e

M3 - Article

C2 - 28054058

AN - SCOPUS:85010382717

SN - 1477-9226

VL - 46

SP - 1163

EP - 1171

JO - Dalton Transactions

JF - Dalton Transactions

IS - 4

ER -

Heteroleptic, two-coordinate [M(NHC){N(SiMe3)2}] (M = Co, Fe) complexes: Synthesis, reactivity and magnetism rationalized by an unexpected metal oxidation state

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Heteroleptic, two-coordinate [M(NHC){N(SiMe₃)₂}] (M = Co, Fe) complexes: Synthesis, reactivity and magnetism rationalized by an unexpected metal oxidation state