Unexpected C−F activation during redox transmetallation with silver N,N′-bis(2,6-difluorophenyl)formamidinate

Zhifang Guo; Glen B. Deacon; Peter C. Junk

doi:10.1002/zaac.202200189

Unexpected C−F activation during redox transmetallation with silver N,N′-bis(2,6-difluorophenyl)formamidinate

Zhifang Guo
, Glen B. Deacon
, Peter C. Junk

School of Chemistry

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

5 Citations (Scopus)

Abstract

The trivalent lanthanoid formamidinates, [Yb₂(DFForm)₄F₂(py)₂] ⋅ CH₃CN (1) (DFForm=N,N′-bis(2,6-difluorophenyl)formamidinate), and [La₆(DFForm)₈F₈O(CH₃CN)₂] ⋅ 6CH₃CN (2) have been prepared from redox transmetallation (RT) reactions employing lanthanoid metals and silver formamidinate (AgDFForm) in CH₃CN. C−F activation was observed in both reactions. The structure of 1 is a fluorine bridged dimer with two seven-coordinate ytterbium metal ions. Surprisingly the lanthanum complex is a trivalent cage with an unexpected central oxygen atom. [La₆(DFForm)₈F₈O(CH₃CN)₂] ⋅ 6CH₃CN (2) formed a 15 membered ring cage of six La atoms, eight F and one O at the centre. There are three different La³⁺ ions in 2 with two different coordination numbers. All the La atoms are coordinated by four bridging fluorides and the central oxygen.

Original language	English
Article number	e202200189
Number of pages	6
Journal	Zeitschrift fuer Anorganische und Allgemeine Chemie
Volume	648
Issue number	19
DOIs	https://doi.org/10.1002/zaac.202200189
Publication status	Published - 14 Oct 2022

Keywords

Crystal structures.
C−F activation reactions
Redox transmetallation (RT) reactions
Silver N,N′-bis(2,6-difluorophenyl)formamidinate (AgDFForm)

Access to Document

10.1002/zaac.202200189Licence: CC BY-NC-ND

Cite this

@article{92bb3593a77a49d5b382eda70c6341c1,

title = "Unexpected C−F activation during redox transmetallation with silver N,N′-bis(2,6-difluorophenyl)formamidinate",

abstract = "The trivalent lanthanoid formamidinates, [Yb2(DFForm)4F2(py)2] ⋅ CH3CN (1) (DFForm=N,N′-bis(2,6-difluorophenyl)formamidinate), and [La6(DFForm)8F8O(CH3CN)2] ⋅ 6CH3CN (2) have been prepared from redox transmetallation (RT) reactions employing lanthanoid metals and silver formamidinate (AgDFForm) in CH3CN. C−F activation was observed in both reactions. The structure of 1 is a fluorine bridged dimer with two seven-coordinate ytterbium metal ions. Surprisingly the lanthanum complex is a trivalent cage with an unexpected central oxygen atom. [La6(DFForm)8F8O(CH3CN)2] ⋅ 6CH3CN (2) formed a 15 membered ring cage of six La atoms, eight F and one O at the centre. There are three different La3+ ions in 2 with two different coordination numbers. All the La atoms are coordinated by four bridging fluorides and the central oxygen.",

keywords = "Crystal structures., C−F activation reactions, Redox transmetallation (RT) reactions, Silver N,N′-bis(2,6-difluorophenyl)formamidinate (AgDFForm)",

author = "Zhifang Guo and Deacon, \{Glen B.\} and Junk, \{Peter C.\}",

note = "Funding Information: GBD and PCJ gratefully acknowledge the ARC for funding (DP190100798). This research was undertaken in part using the MX1 beamline at the Australian Synchrotron, part of ANSTO. Open access publishing facilitated by James Cook University, as part of the Wiley ‐ James Cook University agreement via the Council of Australian University Librarians. [22] Funding Information: GBD and PCJ gratefully acknowledge the ARC for funding (DP190100798). This research was undertaken in part using the MX1 beamline at the Australian Synchrotron, part of ANSTO.[22] Open access publishing facilitated by James Cook University, as part of the Wiley - James Cook University agreement via the Council of Australian University Librarians. Open Access publishing facilitated by James Cook University, as part of the Wiley - James Cook University agreement via the Council of Australian University Librarians. Publisher Copyright: {\textcopyright} 2022 The Authors. Zeitschrift f{\"u}r anorganische und allgemeine Chemie published by Wiley-VCH GmbH.",

year = "2022",

month = oct,

day = "14",

doi = "10.1002/zaac.202200189",

language = "English",

volume = "648",

journal = "Zeitschrift fuer Anorganische und Allgemeine Chemie",

issn = "0044-2313",

publisher = "Wiley-Blackwell",

number = "19",

}

TY - JOUR

T1 - Unexpected C−F activation during redox transmetallation with silver N,N′-bis(2,6-difluorophenyl)formamidinate

AU - Guo, Zhifang

AU - Deacon, Glen B.

AU - Junk, Peter C.

N1 - Funding Information: GBD and PCJ gratefully acknowledge the ARC for funding (DP190100798). This research was undertaken in part using the MX1 beamline at the Australian Synchrotron, part of ANSTO. Open access publishing facilitated by James Cook University, as part of the Wiley ‐ James Cook University agreement via the Council of Australian University Librarians. [22] Funding Information: GBD and PCJ gratefully acknowledge the ARC for funding (DP190100798). This research was undertaken in part using the MX1 beamline at the Australian Synchrotron, part of ANSTO.[22] Open access publishing facilitated by James Cook University, as part of the Wiley - James Cook University agreement via the Council of Australian University Librarians. Open Access publishing facilitated by James Cook University, as part of the Wiley - James Cook University agreement via the Council of Australian University Librarians. Publisher Copyright: © 2022 The Authors. Zeitschrift für anorganische und allgemeine Chemie published by Wiley-VCH GmbH.

PY - 2022/10/14

Y1 - 2022/10/14

N2 - The trivalent lanthanoid formamidinates, [Yb2(DFForm)4F2(py)2] ⋅ CH3CN (1) (DFForm=N,N′-bis(2,6-difluorophenyl)formamidinate), and [La6(DFForm)8F8O(CH3CN)2] ⋅ 6CH3CN (2) have been prepared from redox transmetallation (RT) reactions employing lanthanoid metals and silver formamidinate (AgDFForm) in CH3CN. C−F activation was observed in both reactions. The structure of 1 is a fluorine bridged dimer with two seven-coordinate ytterbium metal ions. Surprisingly the lanthanum complex is a trivalent cage with an unexpected central oxygen atom. [La6(DFForm)8F8O(CH3CN)2] ⋅ 6CH3CN (2) formed a 15 membered ring cage of six La atoms, eight F and one O at the centre. There are three different La3+ ions in 2 with two different coordination numbers. All the La atoms are coordinated by four bridging fluorides and the central oxygen.

AB - The trivalent lanthanoid formamidinates, [Yb2(DFForm)4F2(py)2] ⋅ CH3CN (1) (DFForm=N,N′-bis(2,6-difluorophenyl)formamidinate), and [La6(DFForm)8F8O(CH3CN)2] ⋅ 6CH3CN (2) have been prepared from redox transmetallation (RT) reactions employing lanthanoid metals and silver formamidinate (AgDFForm) in CH3CN. C−F activation was observed in both reactions. The structure of 1 is a fluorine bridged dimer with two seven-coordinate ytterbium metal ions. Surprisingly the lanthanum complex is a trivalent cage with an unexpected central oxygen atom. [La6(DFForm)8F8O(CH3CN)2] ⋅ 6CH3CN (2) formed a 15 membered ring cage of six La atoms, eight F and one O at the centre. There are three different La3+ ions in 2 with two different coordination numbers. All the La atoms are coordinated by four bridging fluorides and the central oxygen.

KW - Crystal structures.

KW - C−F activation reactions

KW - Redox transmetallation (RT) reactions

KW - Silver N,N′-bis(2,6-difluorophenyl)formamidinate (AgDFForm)

UR - https://www.scopus.com/pages/publications/85136457833

U2 - 10.1002/zaac.202200189

DO - 10.1002/zaac.202200189

M3 - Article

AN - SCOPUS:85136457833

SN - 0044-2313

VL - 648

JO - Zeitschrift fuer Anorganische und Allgemeine Chemie

JF - Zeitschrift fuer Anorganische und Allgemeine Chemie

IS - 19

M1 - e202200189

ER -

Unexpected C−F activation during redox transmetallation with silver N,N′-bis(2,6-difluorophenyl)formamidinate

Abstract

Keywords

Access to Document

Other files and links

CTREC: Challenging targets in rare earth metal-organic chemistry

Australian Synchrotron

Cite this

Unexpected C−F activation during redox transmetallation with silver N,N′-bis(2,6-difluorophenyl)formamidinate

Abstract

Keywords

Access to Document

Other files and links

Projects

CTREC: Challenging targets in rare earth metal-organic chemistry

Equipment

Australian Synchrotron

Cite this