The synthesis, structure and reactivity of 4-nonafluorobiphenyl complexes

Eddy Martin; David L. Hughes; Michael B. Hursthouse; Louise Male; Simon Lancaster

doi:10.1039/B817252H

The synthesis, structure and reactivity of 4-nonafluorobiphenyl complexes

Eddy Martin, David L. Hughes, Michael B. Hursthouse, Louise Male, Simon Lancaster

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

9 Citations (Scopus)

Abstract

The Grignard reagent Ar_F'MgBr (Ar_F' = 4-(C₆F₅)C₆F₄) reacts with Me₃SiCl, Me₂SiCl₂ and Me₃SnCl to give the 4-nonafluorobiphenyl group 14 complexes Ar_F'Me₃Si, (Ar_F')₂Me₂Si and Ar_F'Me₃Sn respectively. Ar_F'Me₃Sn undergoes only methyl group exchange when treated with BBr₃, yielding Ar_F'Me₂SnBr. The solid state structures of Ar_F'Me₃Sn and Ar_F'Me₂SnBr have been determined and exhibit the expected distorted tetrahedral geometries at tin. The reaction between three equivalents of Ar_F'MgBr and BF₃ was not selective, while one equivalent of Ar_F'MgBr and (Ar_F)₂BF (Ar_F = C₆F₅) reacted cleanly to give (Ar_F)₂Ar_F'B. Treatment of BCl₃ with three equivalents of Ar_F'Li, prepared at low temperature from the reaction between Ar_F'Br and n-BuLi, yielded (Ar_F')₃B. The molecular structures of the acetonitrile adducts of (Ar_F)₂Ar_F'B and (Ar_F')₃B closely resemble that of (Ar_F)₃B·NCMe. During the course of the boron investigations, reaction with adventitious water led to the structural characterization of (Ar_F')₂BOH·OH₂ as a hydrogen-bonded dimer. The Grignard reagent reacts selectively with ZnCl₂ in diethyl ether giving first [(Ar_F')Zn(µ-Cl)(OEt₂)]₂ then (Ar_F')₂Zn(OEt₂)₂, both of which have been characterised by X-ray diffraction. The corresponding reaction with HgCl₂ requires the use of tetrahydrofuran as the solvent and yields (Ar_F')₂Hg(THF)₂.

Original language	English
Pages (from-to)	1593-1601
Number of pages	9
Journal	Dalton Transactions
Issue number	9
DOIs	https://doi.org/10.1039/B817252H
Publication status	Published - 19 Jan 2009

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10.1039/B817252H

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@article{468a1e388a4248bfa985598dd6421469,

title = "The synthesis, structure and reactivity of 4-nonafluorobiphenyl complexes",

abstract = "The Grignard reagent ArF'MgBr (ArF' = 4-(C6F5)C6F4) reacts with Me3SiCl, Me2SiCl2 and Me3SnCl to give the 4-nonafluorobiphenyl group 14 complexes ArF'Me3Si, (ArF')2Me2Si and ArF'Me3Sn respectively. ArF'Me3Sn undergoes only methyl group exchange when treated with BBr3, yielding ArF'Me2SnBr. The solid state structures of ArF'Me3Sn and ArF'Me2SnBr have been determined and exhibit the expected distorted tetrahedral geometries at tin. The reaction between three equivalents of ArF'MgBr and BF3 was not selective, while one equivalent of ArF'MgBr and (ArF)2BF (ArF = C6F5) reacted cleanly to give (ArF)2ArF'B. Treatment of BCl3 with three equivalents of ArF'Li, prepared at low temperature from the reaction between ArF'Br and n-BuLi, yielded (ArF')3B. The molecular structures of the acetonitrile adducts of (ArF)2ArF'B and (ArF')3B closely resemble that of (ArF)3B·NCMe. During the course of the boron investigations, reaction with adventitious water led to the structural characterization of (ArF')2BOH·OH2 as a hydrogen-bonded dimer. The Grignard reagent reacts selectively with ZnCl2 in diethyl ether giving first [(ArF')Zn(µ-Cl)(OEt2)]2 then (ArF')2Zn(OEt2)2, both of which have been characterised by X-ray diffraction. The corresponding reaction with HgCl2 requires the use of tetrahydrofuran as the solvent and yields (ArF')2Hg(THF)2.",

author = "Eddy Martin and Hughes, {David L.} and Hursthouse, {Michael B.} and Louise Male and Simon Lancaster",

year = "2009",

month = jan,

day = "19",

doi = "10.1039/B817252H",

language = "English",

pages = "1593--1601",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "9",

}

TY - JOUR

T1 - The synthesis, structure and reactivity of 4-nonafluorobiphenyl complexes

AU - Martin, Eddy

AU - Hughes, David L.

AU - Hursthouse, Michael B.

AU - Male, Louise

AU - Lancaster, Simon

PY - 2009/1/19

Y1 - 2009/1/19

N2 - The Grignard reagent ArF'MgBr (ArF' = 4-(C6F5)C6F4) reacts with Me3SiCl, Me2SiCl2 and Me3SnCl to give the 4-nonafluorobiphenyl group 14 complexes ArF'Me3Si, (ArF')2Me2Si and ArF'Me3Sn respectively. ArF'Me3Sn undergoes only methyl group exchange when treated with BBr3, yielding ArF'Me2SnBr. The solid state structures of ArF'Me3Sn and ArF'Me2SnBr have been determined and exhibit the expected distorted tetrahedral geometries at tin. The reaction between three equivalents of ArF'MgBr and BF3 was not selective, while one equivalent of ArF'MgBr and (ArF)2BF (ArF = C6F5) reacted cleanly to give (ArF)2ArF'B. Treatment of BCl3 with three equivalents of ArF'Li, prepared at low temperature from the reaction between ArF'Br and n-BuLi, yielded (ArF')3B. The molecular structures of the acetonitrile adducts of (ArF)2ArF'B and (ArF')3B closely resemble that of (ArF)3B·NCMe. During the course of the boron investigations, reaction with adventitious water led to the structural characterization of (ArF')2BOH·OH2 as a hydrogen-bonded dimer. The Grignard reagent reacts selectively with ZnCl2 in diethyl ether giving first [(ArF')Zn(µ-Cl)(OEt2)]2 then (ArF')2Zn(OEt2)2, both of which have been characterised by X-ray diffraction. The corresponding reaction with HgCl2 requires the use of tetrahydrofuran as the solvent and yields (ArF')2Hg(THF)2.

AB - The Grignard reagent ArF'MgBr (ArF' = 4-(C6F5)C6F4) reacts with Me3SiCl, Me2SiCl2 and Me3SnCl to give the 4-nonafluorobiphenyl group 14 complexes ArF'Me3Si, (ArF')2Me2Si and ArF'Me3Sn respectively. ArF'Me3Sn undergoes only methyl group exchange when treated with BBr3, yielding ArF'Me2SnBr. The solid state structures of ArF'Me3Sn and ArF'Me2SnBr have been determined and exhibit the expected distorted tetrahedral geometries at tin. The reaction between three equivalents of ArF'MgBr and BF3 was not selective, while one equivalent of ArF'MgBr and (ArF)2BF (ArF = C6F5) reacted cleanly to give (ArF)2ArF'B. Treatment of BCl3 with three equivalents of ArF'Li, prepared at low temperature from the reaction between ArF'Br and n-BuLi, yielded (ArF')3B. The molecular structures of the acetonitrile adducts of (ArF)2ArF'B and (ArF')3B closely resemble that of (ArF)3B·NCMe. During the course of the boron investigations, reaction with adventitious water led to the structural characterization of (ArF')2BOH·OH2 as a hydrogen-bonded dimer. The Grignard reagent reacts selectively with ZnCl2 in diethyl ether giving first [(ArF')Zn(µ-Cl)(OEt2)]2 then (ArF')2Zn(OEt2)2, both of which have been characterised by X-ray diffraction. The corresponding reaction with HgCl2 requires the use of tetrahydrofuran as the solvent and yields (ArF')2Hg(THF)2.

U2 - 10.1039/B817252H

DO - 10.1039/B817252H

M3 - Article

SP - 1593

EP - 1601

JO - Dalton Transactions

JF - Dalton Transactions

SN - 1477-9226

IS - 9

ER -