Iron(II)-nitrile complexes: Synthesis, structure and property of trans-[FeH(NCR)(dppe)2]+X- (dppe=Ph2PCH2CH2PPh2: R=CH3, CH2CH2OCH3, CH2CH2CH2Cl, C6H5: X=Cl, BPh4, BF4)

Jae Gyung Lee; Beom Sang Yoo; Nam Sun Choi; Keun Il Park; Sung Il Cho; Chongmok Lee; Soon W. Lee

doi:10.1016/S0022-328X(99)00392-7

Iron(II)-nitrile complexes: Synthesis, structure and property of trans-[FeH(NCR)(dppe)₂]⁺X^- (dppe=Ph₂PCH₂CH₂PPh₂: R=CH₃, CH₂CH₂OCH₃, CH₂CH₂CH₂Cl, C₆H₅: X=Cl, BPh₄, BF₄)

Jae Gyung Lee, Beom Sang Yoo, Nam Sun Choi, Keun Il Park, Sung Il Cho, Chongmok Lee, Soon W. Lee

Department of Chemistry & Nanoscience

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

12 Scopus citations

Abstract

Dissolution of trans-FeHCl(dppe)₂, 1, in various nitriles under argon led to the formation of complexes of the type trans-[FeH(NCR)(dppe)₂]Cl (2a (R=CH₃), 3a (R=CH₂CH₂OMe), 4a (R=CH₂CH₂CH₂Cl), 5a (R=Ph)) in several hours. Complexes 2a-4a could be further converted to trans-[FeH(NCR)(dppe)₂][BPh₄] (2b-4b) and trans-[FeH(NCR)(dppe)₂][BF₄] (2c-4c) when they were treated with NaBPh₄ and NaBF₄, respectively. The stability and electrochemical properties of these complexes appeared to depend mainly on their counteranions (Cl^-, BPh₄^-, BF₄^-). Compounds 2b, 2c, 3b, 3c, 4b and 4c reacted with KCN or NaCN to give [FeH(CN)(dppe)₂] (6). Compound 6 underwent electrophilic addition at the cyano nitrogen by RSO₃CF₃ (R=Me, H) to give [FeH(CNR)(dppe)₂][SO₃CF₃] (7a for R=Me, 7b for R=H). Crystallographic data for 2b: monoclinic space group P2₁/c, a=22.508(1) Å, b=16.120(1) Å, c=19.257(1) Å, β=113.86(1)°, Z=4, R(wR₂)=0.0361(0.0882). Crystallographic data for 3b: triclinic space group P1̄, a=13.240(1) Å, b=14.732(2) Å, c=19.807(1) Å, α=75.276(6)°, β=72.466(6)°, γ=82.033(6)°, Z=2, R(wR₂)=0.0368(0.0835). Crystallographic data for 7a: monoclinic space group P2₁/c, a=12.456(1) Å, b=21.880(3) Å, c=19.924(3) Å, β=108.08(1)°, Z=4, R(wR₂)=0.0663 (0.1647).

Original language	English
Pages (from-to)	138-149
Number of pages	12
Journal	Journal of Organometallic Chemistry
Volume	589
Issue number	2
DOIs	https://doi.org/10.1016/S0022-328X(99)00392-7
State	Published - 5 Nov 1999

Bibliographical note

Funding Information:
This work is based on research sponsored by the Korea Ministry of Education under grant BSRI-98-3420.

Keywords

Counteranions
Crystallographic data
Electrophilic addition
Iron nitrile

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10.1016/S0022-328X(99)00392-7

Cite this

@article{d9fb5ae4357646549a288e3355d2548c,

title = "Iron(II)-nitrile complexes: Synthesis, structure and property of trans-[FeH(NCR)(dppe)2]+X- (dppe=Ph2PCH2CH2PPh2: R=CH3, CH2CH2OCH3, CH2CH2CH2Cl, C6H5: X=Cl, BPh4, BF4)",

abstract = "Dissolution of trans-FeHCl(dppe)2, 1, in various nitriles under argon led to the formation of complexes of the type trans-[FeH(NCR)(dppe)2]Cl (2a (R=CH3), 3a (R=CH2CH2OMe), 4a (R=CH2CH2CH2Cl), 5a (R=Ph)) in several hours. Complexes 2a-4a could be further converted to trans-[FeH(NCR)(dppe)2][BPh4] (2b-4b) and trans-[FeH(NCR)(dppe)2][BF4] (2c-4c) when they were treated with NaBPh4 and NaBF4, respectively. The stability and electrochemical properties of these complexes appeared to depend mainly on their counteranions (Cl-, BPh4-, BF4-). Compounds 2b, 2c, 3b, 3c, 4b and 4c reacted with KCN or NaCN to give [FeH(CN)(dppe)2] (6). Compound 6 underwent electrophilic addition at the cyano nitrogen by RSO3CF3 (R=Me, H) to give [FeH(CNR)(dppe)2][SO3CF3] (7a for R=Me, 7b for R=H). Crystallographic data for 2b: monoclinic space group P21/c, a=22.508(1) {\AA}, b=16.120(1) {\AA}, c=19.257(1) {\AA}, β=113.86(1)°, Z=4, R(wR2)=0.0361(0.0882). Crystallographic data for 3b: triclinic space group P{\=1}, a=13.240(1) {\AA}, b=14.732(2) {\AA}, c=19.807(1) {\AA}, α=75.276(6)°, β=72.466(6)°, γ=82.033(6)°, Z=2, R(wR2)=0.0368(0.0835). Crystallographic data for 7a: monoclinic space group P21/c, a=12.456(1) {\AA}, b=21.880(3) {\AA}, c=19.924(3) {\AA}, β=108.08(1)°, Z=4, R(wR2)=0.0663 (0.1647).",

keywords = "Counteranions, Crystallographic data, Electrophilic addition, Iron nitrile",

author = "Lee, {Jae Gyung} and Yoo, {Beom Sang} and Choi, {Nam Sun} and Park, {Keun Il} and Cho, {Sung Il} and Chongmok Lee and Lee, {Soon W.}",

note = "Funding Information: This work is based on research sponsored by the Korea Ministry of Education under grant BSRI-98-3420.",

year = "1999",

month = nov,

day = "5",

doi = "10.1016/S0022-328X(99)00392-7",

language = "English",

volume = "589",

pages = "138--149",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier",

number = "2",

}

Iron(II)-nitrile complexes: Synthesis, structure and property of trans-[FeH(NCR)(dppe)₂]⁺X^- (dppe=Ph₂PCH₂CH₂PPh₂: R=CH₃, CH₂CH₂OCH₃, CH₂CH₂CH₂Cl, C₆H₅: X=Cl, BPh₄, BF₄). / Lee, Jae Gyung; Yoo, Beom Sang; Choi, Nam Sun et al.
In: Journal of Organometallic Chemistry, Vol. 589, No. 2, 05.11.1999, p. 138-149.

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

TY - JOUR

T1 - Iron(II)-nitrile complexes

T2 - Synthesis, structure and property of trans-[FeH(NCR)(dppe)2]+X- (dppe=Ph2PCH2CH2PPh2: R=CH3, CH2CH2OCH3, CH2CH2CH2Cl, C6H5: X=Cl, BPh4, BF4)

AU - Lee, Jae Gyung

AU - Yoo, Beom Sang

AU - Choi, Nam Sun

AU - Park, Keun Il

AU - Cho, Sung Il

AU - Lee, Chongmok

AU - Lee, Soon W.

N1 - Funding Information: This work is based on research sponsored by the Korea Ministry of Education under grant BSRI-98-3420.

PY - 1999/11/5

Y1 - 1999/11/5

N2 - Dissolution of trans-FeHCl(dppe)2, 1, in various nitriles under argon led to the formation of complexes of the type trans-[FeH(NCR)(dppe)2]Cl (2a (R=CH3), 3a (R=CH2CH2OMe), 4a (R=CH2CH2CH2Cl), 5a (R=Ph)) in several hours. Complexes 2a-4a could be further converted to trans-[FeH(NCR)(dppe)2][BPh4] (2b-4b) and trans-[FeH(NCR)(dppe)2][BF4] (2c-4c) when they were treated with NaBPh4 and NaBF4, respectively. The stability and electrochemical properties of these complexes appeared to depend mainly on their counteranions (Cl-, BPh4-, BF4-). Compounds 2b, 2c, 3b, 3c, 4b and 4c reacted with KCN or NaCN to give [FeH(CN)(dppe)2] (6). Compound 6 underwent electrophilic addition at the cyano nitrogen by RSO3CF3 (R=Me, H) to give [FeH(CNR)(dppe)2][SO3CF3] (7a for R=Me, 7b for R=H). Crystallographic data for 2b: monoclinic space group P21/c, a=22.508(1) Å, b=16.120(1) Å, c=19.257(1) Å, β=113.86(1)°, Z=4, R(wR2)=0.0361(0.0882). Crystallographic data for 3b: triclinic space group P1̄, a=13.240(1) Å, b=14.732(2) Å, c=19.807(1) Å, α=75.276(6)°, β=72.466(6)°, γ=82.033(6)°, Z=2, R(wR2)=0.0368(0.0835). Crystallographic data for 7a: monoclinic space group P21/c, a=12.456(1) Å, b=21.880(3) Å, c=19.924(3) Å, β=108.08(1)°, Z=4, R(wR2)=0.0663 (0.1647).

AB - Dissolution of trans-FeHCl(dppe)2, 1, in various nitriles under argon led to the formation of complexes of the type trans-[FeH(NCR)(dppe)2]Cl (2a (R=CH3), 3a (R=CH2CH2OMe), 4a (R=CH2CH2CH2Cl), 5a (R=Ph)) in several hours. Complexes 2a-4a could be further converted to trans-[FeH(NCR)(dppe)2][BPh4] (2b-4b) and trans-[FeH(NCR)(dppe)2][BF4] (2c-4c) when they were treated with NaBPh4 and NaBF4, respectively. The stability and electrochemical properties of these complexes appeared to depend mainly on their counteranions (Cl-, BPh4-, BF4-). Compounds 2b, 2c, 3b, 3c, 4b and 4c reacted with KCN or NaCN to give [FeH(CN)(dppe)2] (6). Compound 6 underwent electrophilic addition at the cyano nitrogen by RSO3CF3 (R=Me, H) to give [FeH(CNR)(dppe)2][SO3CF3] (7a for R=Me, 7b for R=H). Crystallographic data for 2b: monoclinic space group P21/c, a=22.508(1) Å, b=16.120(1) Å, c=19.257(1) Å, β=113.86(1)°, Z=4, R(wR2)=0.0361(0.0882). Crystallographic data for 3b: triclinic space group P1̄, a=13.240(1) Å, b=14.732(2) Å, c=19.807(1) Å, α=75.276(6)°, β=72.466(6)°, γ=82.033(6)°, Z=2, R(wR2)=0.0368(0.0835). Crystallographic data for 7a: monoclinic space group P21/c, a=12.456(1) Å, b=21.880(3) Å, c=19.924(3) Å, β=108.08(1)°, Z=4, R(wR2)=0.0663 (0.1647).

KW - Counteranions

KW - Crystallographic data

KW - Electrophilic addition

KW - Iron nitrile

UR - http://www.scopus.com/inward/record.url?scp=0006936743&partnerID=8YFLogxK

U2 - 10.1016/S0022-328X(99)00392-7

DO - 10.1016/S0022-328X(99)00392-7

M3 - Article

AN - SCOPUS:0006936743

SN - 0022-328X

VL - 589

SP - 138

EP - 149

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 2

ER -