Synthesis and characterization of triply-bonded titanium-iron complexes supported by 2-(diphenylphosphino)pyrrolide ligands

Peter L. Dunn; Rebecca K. Carlson; Ian A. Tonks

doi:10.1016/j.ica.2016.10.002

Synthesis and characterization of triply-bonded titanium-iron complexes supported by 2-(diphenylphosphino)pyrrolide ligands

Peter L. Dunn, Rebecca K. Carlson, Ian A. Tonks

Chemistry (Twin Cities)

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

9 Scopus citations

Abstract

The synthesis of several titanium-iron multiply bonded complexes supported by a 2-(diphenylphosphino)pyrrolide (NP) ligand is reported. Treatment of the homoleptic, 8-coordinate Ti(NP)₄ monometallic precursors with FeCl₂ and KC₈ yielded the tetragonally-symmetric heterobimetallic complex Ti(μ₂-NP)₄Fe, 2. X-ray crystallographic analysis reveals a short metal-metal distance (2.021(2) and 2.028(2) Å for two independent molecules in the asymmetric unit) consistent with a Fe-Ti triple bond. Theoretical calculations also indicate 3 bonding interactions. Further reduction of 2 by 2 electrons with KC₈ results in the isolation of the dianion, [K₂][(κ¹-NP)Ti(μ₂-NP)₃Fe], 3, where one phosphine arm has decoordinated from Fe, and the Fe-Ti triple bond has shortened to 1.9474(7) Å. This shortening results from the local ligand field change about Fe from tetragonal to trigonal, which allows for significantly better orbital overlap with Ti.

Original language	English (US)
Pages (from-to)	43-48
Number of pages	6
Journal	Inorganica Chimica Acta
Volume	460
DOIs	https://doi.org/10.1016/j.ica.2016.10.002
State	Published - 2017

Bibliographical note

Funding Information:
Financial support was provided by the University of Minnesota (start up funds) and the ACS Petroleum Research Fund (ACS-PRF 54225-DNI3). Victor G. Young, Jr. is thanked for assistance with X-ray diffraction data interpretation. The Bruker-AXS D8 Venture diffractometer was purchased through a grant from NSF/MRI (1224900) and the University of Minnesota. Equipment purchases for the NMR facility were supported through a grant from the NIH (S10OD011952) with matching funds from the University of Minnesota. R.K.C. thanks the National Science Foundation for a Graduate Research Fellowship under Grant No. 00039202.

Publisher Copyright:
© 2016 Elsevier B.V.

Keywords

Inorganic synthesis
Iron complexes
Metal-metal multiple bonds
Pyrrolide ligands
Titanium complexes

Access

10.1016/j.ica.2016.10.002

OpenUrl availability

Full text

Cite this

@article{1f668e45e3564bf081a67c9efb6469b2,

title = "Synthesis and characterization of triply-bonded titanium-iron complexes supported by 2-(diphenylphosphino)pyrrolide ligands",

abstract = "The synthesis of several titanium-iron multiply bonded complexes supported by a 2-(diphenylphosphino)pyrrolide (NP) ligand is reported. Treatment of the homoleptic, 8-coordinate Ti(NP)4 monometallic precursors with FeCl2 and KC8 yielded the tetragonally-symmetric heterobimetallic complex Ti(μ2-NP)4Fe, 2. X-ray crystallographic analysis reveals a short metal-metal distance (2.021(2) and 2.028(2) {\AA} for two independent molecules in the asymmetric unit) consistent with a Fe-Ti triple bond. Theoretical calculations also indicate 3 bonding interactions. Further reduction of 2 by 2 electrons with KC8 results in the isolation of the dianion, [K2][(κ1-NP)Ti(μ2-NP)3Fe], 3, where one phosphine arm has decoordinated from Fe, and the Fe-Ti triple bond has shortened to 1.9474(7) {\AA}. This shortening results from the local ligand field change about Fe from tetragonal to trigonal, which allows for significantly better orbital overlap with Ti.",

keywords = "Inorganic synthesis, Iron complexes, Metal-metal multiple bonds, Pyrrolide ligands, Titanium complexes",

author = "Dunn, {Peter L.} and Carlson, {Rebecca K.} and Tonks, {Ian A.}",

note = "Funding Information: Financial support was provided by the University of Minnesota (start up funds) and the ACS Petroleum Research Fund (ACS-PRF 54225-DNI3). Victor G. Young, Jr. is thanked for assistance with X-ray diffraction data interpretation. The Bruker-AXS D8 Venture diffractometer was purchased through a grant from NSF/MRI (1224900) and the University of Minnesota. Equipment purchases for the NMR facility were supported through a grant from the NIH (S10OD011952) with matching funds from the University of Minnesota. R.K.C. thanks the National Science Foundation for a Graduate Research Fellowship under Grant No. 00039202. Publisher Copyright: {\textcopyright} 2016 Elsevier B.V.",

year = "2017",

doi = "10.1016/j.ica.2016.10.002",

language = "English (US)",

volume = "460",

pages = "43--48",

journal = "Inorganica Chimica Acta",

issn = "0020-1693",

publisher = "Elsevier BV",

}

TY - JOUR

T1 - Synthesis and characterization of triply-bonded titanium-iron complexes supported by 2-(diphenylphosphino)pyrrolide ligands

AU - Dunn, Peter L.

AU - Carlson, Rebecca K.

AU - Tonks, Ian A.

N1 - Funding Information: Financial support was provided by the University of Minnesota (start up funds) and the ACS Petroleum Research Fund (ACS-PRF 54225-DNI3). Victor G. Young, Jr. is thanked for assistance with X-ray diffraction data interpretation. The Bruker-AXS D8 Venture diffractometer was purchased through a grant from NSF/MRI (1224900) and the University of Minnesota. Equipment purchases for the NMR facility were supported through a grant from the NIH (S10OD011952) with matching funds from the University of Minnesota. R.K.C. thanks the National Science Foundation for a Graduate Research Fellowship under Grant No. 00039202. Publisher Copyright: © 2016 Elsevier B.V.

PY - 2017

Y1 - 2017

N2 - The synthesis of several titanium-iron multiply bonded complexes supported by a 2-(diphenylphosphino)pyrrolide (NP) ligand is reported. Treatment of the homoleptic, 8-coordinate Ti(NP)4 monometallic precursors with FeCl2 and KC8 yielded the tetragonally-symmetric heterobimetallic complex Ti(μ2-NP)4Fe, 2. X-ray crystallographic analysis reveals a short metal-metal distance (2.021(2) and 2.028(2) Å for two independent molecules in the asymmetric unit) consistent with a Fe-Ti triple bond. Theoretical calculations also indicate 3 bonding interactions. Further reduction of 2 by 2 electrons with KC8 results in the isolation of the dianion, [K2][(κ1-NP)Ti(μ2-NP)3Fe], 3, where one phosphine arm has decoordinated from Fe, and the Fe-Ti triple bond has shortened to 1.9474(7) Å. This shortening results from the local ligand field change about Fe from tetragonal to trigonal, which allows for significantly better orbital overlap with Ti.

AB - The synthesis of several titanium-iron multiply bonded complexes supported by a 2-(diphenylphosphino)pyrrolide (NP) ligand is reported. Treatment of the homoleptic, 8-coordinate Ti(NP)4 monometallic precursors with FeCl2 and KC8 yielded the tetragonally-symmetric heterobimetallic complex Ti(μ2-NP)4Fe, 2. X-ray crystallographic analysis reveals a short metal-metal distance (2.021(2) and 2.028(2) Å for two independent molecules in the asymmetric unit) consistent with a Fe-Ti triple bond. Theoretical calculations also indicate 3 bonding interactions. Further reduction of 2 by 2 electrons with KC8 results in the isolation of the dianion, [K2][(κ1-NP)Ti(μ2-NP)3Fe], 3, where one phosphine arm has decoordinated from Fe, and the Fe-Ti triple bond has shortened to 1.9474(7) Å. This shortening results from the local ligand field change about Fe from tetragonal to trigonal, which allows for significantly better orbital overlap with Ti.

KW - Inorganic synthesis

KW - Iron complexes

KW - Metal-metal multiple bonds

KW - Pyrrolide ligands

KW - Titanium complexes

UR - http://www.scopus.com/inward/record.url?scp=84992411184&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84992411184&partnerID=8YFLogxK

U2 - 10.1016/j.ica.2016.10.002

DO - 10.1016/j.ica.2016.10.002

M3 - Article

AN - SCOPUS:84992411184

SN - 0020-1693

VL - 460

SP - 43

EP - 48

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

ER -

Synthesis and characterization of triply-bonded titanium-iron complexes supported by 2-(diphenylphosphino)pyrrolide ligands

Abstract

Bibliographical note

Keywords

Access

OpenUrl availability

Other files and links

Fingerprint

Cite this