Square planar vs tetrahedral geometry in four coordinate iron(II) complexes

Eric J. Hawrelak; Wesley H. Bernskoetter; Emil Lobkovsky; Gordon T. Yee; Eckhard Bill; Paul J. Chirik

doi:10.1021/ic048202+

Square planar vs tetrahedral geometry in four coordinate iron(II) complexes

Eric J. Hawrelak, Wesley H. Bernskoetter, Emil Lobkovsky, Gordon T. Yee, Eckhard Bill, Paul J. Chirik

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

118 Scopus citations

Abstract

The geometric preferences of a family of four coordinate, iron(II) d ⁶ complexes of the general form L ₂FeX ₂ have been systematically evaluated. Treatment of Fe ₂(Mes) ₄ (Mes = 2,4,6-Me ₃C ₆H ₂) with monodentate phosphine and phosphite ligands furnished square planar trans-P ₂Fe(Mes) ₂ derivatives. Identification of the geometry has been accomplished by a combination of solution and solid-state magnetometry and, in two cases (P = PMe ₃, PEt ₂Ph), X-ray diffraction. In contrast, both tetrahedral and square planar coordination has been observed upon complexation of chelating phosphine ligands. A combination of crystallographic and magnetic susceptibility data for (depe)Fe-(Mes) ₂ (depe = 1,2- bis(diethylphosphino)ethane) established a tetrahedral molecular geometry whereas SQUID magnetometry and Mössbauer spectroscopy on samples of (dppe)Fe(Mes) ₂ (dppe = 1,2-bis(diphenylphosphino)-ethane) indicated a planar molecule. When dissolved in chlorinated solvents, the latter compound promotes chlorine atom abstraction, forming tetrahedral (dppe)Fe(Mes)Cl and (dppe)FeCl ₂. Ligand substitution reactions have been studied for both structural types and are rapid on the NMR time scale at ambient temperature.

Original language	English (US)
Pages (from-to)	3103-3111
Number of pages	9
Journal	Inorganic Chemistry
Volume	44
Issue number	9
DOIs	https://doi.org/10.1021/ic048202+
State	Published - May 2 2005
Externally published	Yes

All Science Journal Classification (ASJC) codes

Inorganic Chemistry
Physical and Theoretical Chemistry

Access to Document

10.1021/ic048202+

Cite this

@article{0e926a77cb1b4cd2b0a6539c8adf9f1c,

title = "Square planar vs tetrahedral geometry in four coordinate iron(II) complexes",

abstract = "The geometric preferences of a family of four coordinate, iron(II) d 6 complexes of the general form L 2FeX 2 have been systematically evaluated. Treatment of Fe 2(Mes) 4 (Mes = 2,4,6-Me 3C 6H 2) with monodentate phosphine and phosphite ligands furnished square planar trans-P 2Fe(Mes) 2 derivatives. Identification of the geometry has been accomplished by a combination of solution and solid-state magnetometry and, in two cases (P = PMe 3, PEt 2Ph), X-ray diffraction. In contrast, both tetrahedral and square planar coordination has been observed upon complexation of chelating phosphine ligands. A combination of crystallographic and magnetic susceptibility data for (depe)Fe-(Mes) 2 (depe = 1,2- bis(diethylphosphino)ethane) established a tetrahedral molecular geometry whereas SQUID magnetometry and M{\"o}ssbauer spectroscopy on samples of (dppe)Fe(Mes) 2 (dppe = 1,2-bis(diphenylphosphino)-ethane) indicated a planar molecule. When dissolved in chlorinated solvents, the latter compound promotes chlorine atom abstraction, forming tetrahedral (dppe)Fe(Mes)Cl and (dppe)FeCl 2. Ligand substitution reactions have been studied for both structural types and are rapid on the NMR time scale at ambient temperature.",

author = "Hawrelak, {Eric J.} and Bernskoetter, {Wesley H.} and Emil Lobkovsky and Yee, {Gordon T.} and Eckhard Bill and Chirik, {Paul J.}",

year = "2005",

month = may,

day = "2",

doi = "10.1021/ic048202+",

language = "English (US)",

volume = "44",

pages = "3103--3111",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "9",

}

TY - JOUR

T1 - Square planar vs tetrahedral geometry in four coordinate iron(II) complexes

AU - Hawrelak, Eric J.

AU - Bernskoetter, Wesley H.

AU - Lobkovsky, Emil

AU - Yee, Gordon T.

AU - Bill, Eckhard

AU - Chirik, Paul J.

PY - 2005/5/2

Y1 - 2005/5/2

N2 - The geometric preferences of a family of four coordinate, iron(II) d 6 complexes of the general form L 2FeX 2 have been systematically evaluated. Treatment of Fe 2(Mes) 4 (Mes = 2,4,6-Me 3C 6H 2) with monodentate phosphine and phosphite ligands furnished square planar trans-P 2Fe(Mes) 2 derivatives. Identification of the geometry has been accomplished by a combination of solution and solid-state magnetometry and, in two cases (P = PMe 3, PEt 2Ph), X-ray diffraction. In contrast, both tetrahedral and square planar coordination has been observed upon complexation of chelating phosphine ligands. A combination of crystallographic and magnetic susceptibility data for (depe)Fe-(Mes) 2 (depe = 1,2- bis(diethylphosphino)ethane) established a tetrahedral molecular geometry whereas SQUID magnetometry and Mössbauer spectroscopy on samples of (dppe)Fe(Mes) 2 (dppe = 1,2-bis(diphenylphosphino)-ethane) indicated a planar molecule. When dissolved in chlorinated solvents, the latter compound promotes chlorine atom abstraction, forming tetrahedral (dppe)Fe(Mes)Cl and (dppe)FeCl 2. Ligand substitution reactions have been studied for both structural types and are rapid on the NMR time scale at ambient temperature.

AB - The geometric preferences of a family of four coordinate, iron(II) d 6 complexes of the general form L 2FeX 2 have been systematically evaluated. Treatment of Fe 2(Mes) 4 (Mes = 2,4,6-Me 3C 6H 2) with monodentate phosphine and phosphite ligands furnished square planar trans-P 2Fe(Mes) 2 derivatives. Identification of the geometry has been accomplished by a combination of solution and solid-state magnetometry and, in two cases (P = PMe 3, PEt 2Ph), X-ray diffraction. In contrast, both tetrahedral and square planar coordination has been observed upon complexation of chelating phosphine ligands. A combination of crystallographic and magnetic susceptibility data for (depe)Fe-(Mes) 2 (depe = 1,2- bis(diethylphosphino)ethane) established a tetrahedral molecular geometry whereas SQUID magnetometry and Mössbauer spectroscopy on samples of (dppe)Fe(Mes) 2 (dppe = 1,2-bis(diphenylphosphino)-ethane) indicated a planar molecule. When dissolved in chlorinated solvents, the latter compound promotes chlorine atom abstraction, forming tetrahedral (dppe)Fe(Mes)Cl and (dppe)FeCl 2. Ligand substitution reactions have been studied for both structural types and are rapid on the NMR time scale at ambient temperature.

UR - http://www.scopus.com/inward/record.url?scp=19944385273&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=19944385273&partnerID=8YFLogxK

U2 - 10.1021/ic048202+

DO - 10.1021/ic048202+

M3 - Article

C2 - 15847415

AN - SCOPUS:19944385273

SN - 0020-1669

VL - 44

SP - 3103

EP - 3111

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 9

ER -

Square planar vs tetrahedral geometry in four coordinate iron(II) complexes

Abstract

All Science Journal Classification (ASJC) codes

Access to Document

Other files and links

Fingerprint

Cite this