Mixed metal II-metal IV hybrid fluorides

Jérôme Lhoste; Karim Adil; Armel Le Bail; Marc Leblanc; Annie Hémon-Ribaud; Vincent Maisonneuve

doi:10.1016/j.jfluchem.2011.03.021

Mixed metal ^II-metal ^IV hybrid fluorides

Jérôme Lhoste, Karim Adil, Armel Le Bail, Marc Leblanc, Annie Hémon-Ribaud, Vincent Maisonneuve^*

^*Corresponding author for this work

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

10 Scopus citations

Abstract

Six M ^II-M ^IV type II hybrid fluorides (M ^II = Cu, Ni; M ^IV = Si, Ti, Mo) are compared: (Ni(en) ₃) ·(TiF ₆), [Hpy] ₂·(Cu(py) ₄(MF ₆) ₂) (M ^IV = Ti, Mo), [H ₃O] ₂·(SiF ₆(CuF(py) ₄) ₂) ·(F) ₂ and Cu(en) ₂MF ₆ (M ^IV = Ti, Si). They are obtained at 160 °C under microwave heating and the structures are determined either from single crystal or powder X-ray diffraction data. All phases involve neutral amines that are linked to M ^II cations, a feature of type II hybrids. In (Ni(en) ₃)·(TiF ₆), the cationic (Ni(en) ₃) ²⁺ and anionic (TiF ₆) ^2- entities are isolated. In [Hpy] ₂·(Cu(py) ₄(TiF ₆) ₂) and [Hpy] ₂·(Cu(py) ₄(MoF ₆) ₂), extra non metal bonded amines are protonated to give [Hpy] ⁺ cations that exchange hydrogen bonds with fluoride anions, a feature of type I hybrids. All phases exhibit a fully fluorinated octahedral environment of M ^IV cations, at the opposite from previously reported [H ₃O] ₂·(NbOF ₅(CuF(py) ₄) ₂) ·(F) ₂ or [Hpy] ₂·(Cu(py) ₄) (MoO ₂F ₄) ₂. In [Hpy] ₂·(Cu(py) ₄(MF ₆) ₂) (M ^IV = Ti, Mo) or [H ₃O] ₂·(SiF ₆(CuF(py) ₄) ₂)·(F) ₂, Cu ^II and M ^IV entities are associated by fluoride anions to give anionic or neutral trimetallic clusters, respectively; the results of thermal analysis suggest that the oxidation state is +IV for molybdenum and it is proposed that H ₃O ⁺ and "free" F ^- ion pairs can be replaced locally by H ₂O and HF couples. In Cu(en) ₂MF ₆, the Cu ^II and M ^IV entities alternate and build infinite chains

Original language	English (US)
Pages (from-to)	29-34
Number of pages	6
Journal	Journal of Fluorine Chemistry
Volume	134
DOIs	https://doi.org/10.1016/j.jfluchem.2011.03.021
State	Published - Feb 2012
Externally published	Yes

Keywords

Hybrid fluorides
Hydrothermal synthesis
Microwave heating

ASJC Scopus subject areas

Biochemistry
Environmental Chemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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10.1016/j.jfluchem.2011.03.021

Cite this

@article{146ea69038324ce2bdd2b70d438abf07,

title = "Mixed metal II-metal IV hybrid fluorides",

abstract = "Six M II-M IV type II hybrid fluorides (M II = Cu, Ni; M IV = Si, Ti, Mo) are compared: (Ni(en) 3) ·(TiF 6), [Hpy] 2·(Cu(py) 4(MF 6) 2) (M IV = Ti, Mo), [H 3O] 2·(SiF 6(CuF(py) 4) 2) ·(F) 2 and Cu(en) 2MF 6 (M IV = Ti, Si). They are obtained at 160 °C under microwave heating and the structures are determined either from single crystal or powder X-ray diffraction data. All phases involve neutral amines that are linked to M II cations, a feature of type II hybrids. In (Ni(en) 3)·(TiF 6), the cationic (Ni(en) 3) 2+ and anionic (TiF 6) 2- entities are isolated. In [Hpy] 2·(Cu(py) 4(TiF 6) 2) and [Hpy] 2·(Cu(py) 4(MoF 6) 2), extra non metal bonded amines are protonated to give [Hpy] + cations that exchange hydrogen bonds with fluoride anions, a feature of type I hybrids. All phases exhibit a fully fluorinated octahedral environment of M IV cations, at the opposite from previously reported [H 3O] 2·(NbOF 5(CuF(py) 4) 2) ·(F) 2 or [Hpy] 2·(Cu(py) 4) (MoO 2F 4) 2. In [Hpy] 2·(Cu(py) 4(MF 6) 2) (M IV = Ti, Mo) or [H 3O] 2·(SiF 6(CuF(py) 4) 2)·(F) 2, Cu II and M IV entities are associated by fluoride anions to give anionic or neutral trimetallic clusters, respectively; the results of thermal analysis suggest that the oxidation state is +IV for molybdenum and it is proposed that H 3O + and {"}free{"} F - ion pairs can be replaced locally by H 2O and HF couples. In Cu(en) 2MF 6, the Cu II and M IV entities alternate and build infinite chains",

keywords = "Hybrid fluorides, Hydrothermal synthesis, Microwave heating",

author = "J{\'e}r{\^o}me Lhoste and Karim Adil and {Le Bail}, Armel and Marc Leblanc and Annie H{\'e}mon-Ribaud and Vincent Maisonneuve",

year = "2012",

month = feb,

doi = "10.1016/j.jfluchem.2011.03.021",

language = "English (US)",

volume = "134",

pages = "29--34",

journal = "Journal of Fluorine Chemistry",

issn = "0022-1139",

publisher = "Elsevier",

}

TY - JOUR

T1 - Mixed metal II-metal IV hybrid fluorides

AU - Lhoste, Jérôme

AU - Adil, Karim

AU - Le Bail, Armel

AU - Leblanc, Marc

AU - Hémon-Ribaud, Annie

AU - Maisonneuve, Vincent

PY - 2012/2

Y1 - 2012/2

N2 - Six M II-M IV type II hybrid fluorides (M II = Cu, Ni; M IV = Si, Ti, Mo) are compared: (Ni(en) 3) ·(TiF 6), [Hpy] 2·(Cu(py) 4(MF 6) 2) (M IV = Ti, Mo), [H 3O] 2·(SiF 6(CuF(py) 4) 2) ·(F) 2 and Cu(en) 2MF 6 (M IV = Ti, Si). They are obtained at 160 °C under microwave heating and the structures are determined either from single crystal or powder X-ray diffraction data. All phases involve neutral amines that are linked to M II cations, a feature of type II hybrids. In (Ni(en) 3)·(TiF 6), the cationic (Ni(en) 3) 2+ and anionic (TiF 6) 2- entities are isolated. In [Hpy] 2·(Cu(py) 4(TiF 6) 2) and [Hpy] 2·(Cu(py) 4(MoF 6) 2), extra non metal bonded amines are protonated to give [Hpy] + cations that exchange hydrogen bonds with fluoride anions, a feature of type I hybrids. All phases exhibit a fully fluorinated octahedral environment of M IV cations, at the opposite from previously reported [H 3O] 2·(NbOF 5(CuF(py) 4) 2) ·(F) 2 or [Hpy] 2·(Cu(py) 4) (MoO 2F 4) 2. In [Hpy] 2·(Cu(py) 4(MF 6) 2) (M IV = Ti, Mo) or [H 3O] 2·(SiF 6(CuF(py) 4) 2)·(F) 2, Cu II and M IV entities are associated by fluoride anions to give anionic or neutral trimetallic clusters, respectively; the results of thermal analysis suggest that the oxidation state is +IV for molybdenum and it is proposed that H 3O + and "free" F - ion pairs can be replaced locally by H 2O and HF couples. In Cu(en) 2MF 6, the Cu II and M IV entities alternate and build infinite chains

AB - Six M II-M IV type II hybrid fluorides (M II = Cu, Ni; M IV = Si, Ti, Mo) are compared: (Ni(en) 3) ·(TiF 6), [Hpy] 2·(Cu(py) 4(MF 6) 2) (M IV = Ti, Mo), [H 3O] 2·(SiF 6(CuF(py) 4) 2) ·(F) 2 and Cu(en) 2MF 6 (M IV = Ti, Si). They are obtained at 160 °C under microwave heating and the structures are determined either from single crystal or powder X-ray diffraction data. All phases involve neutral amines that are linked to M II cations, a feature of type II hybrids. In (Ni(en) 3)·(TiF 6), the cationic (Ni(en) 3) 2+ and anionic (TiF 6) 2- entities are isolated. In [Hpy] 2·(Cu(py) 4(TiF 6) 2) and [Hpy] 2·(Cu(py) 4(MoF 6) 2), extra non metal bonded amines are protonated to give [Hpy] + cations that exchange hydrogen bonds with fluoride anions, a feature of type I hybrids. All phases exhibit a fully fluorinated octahedral environment of M IV cations, at the opposite from previously reported [H 3O] 2·(NbOF 5(CuF(py) 4) 2) ·(F) 2 or [Hpy] 2·(Cu(py) 4) (MoO 2F 4) 2. In [Hpy] 2·(Cu(py) 4(MF 6) 2) (M IV = Ti, Mo) or [H 3O] 2·(SiF 6(CuF(py) 4) 2)·(F) 2, Cu II and M IV entities are associated by fluoride anions to give anionic or neutral trimetallic clusters, respectively; the results of thermal analysis suggest that the oxidation state is +IV for molybdenum and it is proposed that H 3O + and "free" F - ion pairs can be replaced locally by H 2O and HF couples. In Cu(en) 2MF 6, the Cu II and M IV entities alternate and build infinite chains

KW - Hybrid fluorides

KW - Hydrothermal synthesis

KW - Microwave heating

UR - http://www.scopus.com/inward/record.url?scp=84856085233&partnerID=8YFLogxK

U2 - 10.1016/j.jfluchem.2011.03.021

DO - 10.1016/j.jfluchem.2011.03.021

M3 - Article

AN - SCOPUS:84856085233

SN - 0022-1139

VL - 134

SP - 29

EP - 34

JO - Journal of Fluorine Chemistry

JF - Journal of Fluorine Chemistry

ER -