Crystal structures and spectroscopic characterization of MBr2(CNXyl)n (M = Fe and Co, n = 4; M = Ni, n = 2; Xyl = 2,6-dimethylphenyl), and of formally zero-valent iron as a cocrystal of Fe(CNXyl)5 and Fe2(CNXyl)9

William W. Brennessel; Benjamin E. Kucera; Victor G. Young; John E. Ellis

doi:10.1107/S205322961900963X

Crystal structures and spectroscopic characterization of MBr2(CNXyl)n (M = Fe and Co, n = 4; M = Ni, n = 2; Xyl = 2,6-dimethylphenyl), and of formally zero-valent iron as a cocrystal of Fe(CNXyl)5 and Fe2(CNXyl)9

William W. Brennessel, Benjamin E. Kucera, Victor G. Young, John E. Ellis

Chemistry (Twin Cities)

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

5 Scopus citations

Abstract

Structures and spectroscopic characterization of the divalent complexes cisdibromidotetrakis( 2,6-dimethylphenyl isocyanide)iron(II) dichloromethane 0.771-solvate, [FeBr2(C9H9N)4]-0.771CH2Cl2 or cis-FeBr2(CNXyl)4-0.771CH2Cl2 (Xyl = 2,6-dimethylphenyl), trans-dibromidotetrakis(2,6-dimethylphenyl isocyanide)-iron(II), [FeBr2(C9H9N)4] or trans-FeBr2(CNXyl)4, trans-dibromidotetrakis(2,6-dimethylphenyl isocyanide)cobalt(II), [CoBr2(C9H9N)4] or trans-CoBr2(CNXyl)4, and trans-dibromidobis(2,6-dimethylphenyl isocyanide)nickel(II), [NiBr2(C9H9N)2] or trans-NiBr2(CNXyl)2, are presented. Additionally, crystals grown from a cold diethyl ether solution of zero-valent Fe(CNXyl)5 produced a structure containing a cocrystallization of mononuclear Fe(CNXyl)5 and the previously unknown dinuclear [Fe(CNXyl)3]2(-2-CNXyl)3, namely pentakis(2,6-dimethylphenyl isocyanide)iron(0) tris(-2-2,6-dimethylphenyl isocyanide)bis[tris(2,6-dimethylphenyl isocyanide)iron(0)], [Fe(C9H9N)5][Fe2(C9H9N)9]. The (M)C- N-C(Xyl) angles of the isocyanide ligand are nearly linear for the metals in the +2 oxidation state, for which the ligands function essentially as pure donors. The -CN stretching frequencies for these divalent metal isocyanides are at or above that of the free ligand. Relative to FeII, in the structure containing iron in the formally zero-valent oxidation state, the Fe-C bond lengths have shortened, the C N bond lengths have elongated, the (M)C-N-C(Xyl) angles of the terminal CNXyl ligands are more bent, and the -CN stretching frequencies have shifted to lower energies, all indicative of substantial M(d-)!- backbonding.

Original language	English (US)
Pages (from-to)	1118-1127
Number of pages	10
Journal	Acta Crystallographica Section C: Structural Chemistry
Volume	75
DOIs	https://doi.org/10.1107/S205322961900963X
State	Published - Aug 1 2019

Bibliographical note

Funding Information:
Funding for the instrument used to analyse 1 was provided by: National Science Foundation (grant No. CHE-1725028).

Funding Information:
The authors acknowledge the US National Science Foundation, and the donors of the Petroleum Research Fund, administered by the American Chemical Society, for funding. The University of Minnesota Chemistry Department is acknowledged for providing and supporting the graduate level course in X-ray crystallography. Students from this course, Kevin J. Erickson, Emily L. Que, Airon Soegianto, Pratik Verma, and Daniel J. Wherritt, are thanked for their assistance with the various crystal structures in this article. Data for the structure of CNXyl were collected on an instrument purchased with funding from the NSF.

Publisher Copyright:
© 2019.

Keywords

2 6-dimethylphenyl isocyanide
IR spectroscopy
NMR.
cobalt
crystal structure
iron
nickel
xylyl isocyanide

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Brennessel, W. W., Kucera, B. E., Young, V. G., & Ellis, J. E. (2019). Crystal structures and spectroscopic characterization of MBr2(CNXyl)n (M = Fe and Co, n = 4; M = Ni, n = 2; Xyl = 2,6-dimethylphenyl), and of formally zero-valent iron as a cocrystal of Fe(CNXyl)5 and Fe2(CNXyl)9. Acta Crystallographica Section C: Structural Chemistry, 75, 1118-1127. https://doi.org/10.1107/S205322961900963X

Crystal structures and spectroscopic characterization of MBr2(CNXyl)n (M = Fe and Co, n = 4; M = Ni, n = 2; Xyl = 2,6-dimethylphenyl), and of formally zero-valent iron as a cocrystal of Fe(CNXyl)5 and Fe2(CNXyl)9. / Brennessel, William W.; Kucera, Benjamin E.; Young, Victor G. et al.
In: Acta Crystallographica Section C: Structural Chemistry, Vol. 75, 01.08.2019, p. 1118-1127.

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

Brennessel, WW, Kucera, BE, Young, VG & Ellis, JE 2019, 'Crystal structures and spectroscopic characterization of MBr2(CNXyl)n (M = Fe and Co, n = 4; M = Ni, n = 2; Xyl = 2,6-dimethylphenyl), and of formally zero-valent iron as a cocrystal of Fe(CNXyl)5 and Fe2(CNXyl)9', Acta Crystallographica Section C: Structural Chemistry, vol. 75, pp. 1118-1127. https://doi.org/10.1107/S205322961900963X

Brennessel WW, Kucera BE, Young VG, Ellis JE. Crystal structures and spectroscopic characterization of MBr2(CNXyl)n (M = Fe and Co, n = 4; M = Ni, n = 2; Xyl = 2,6-dimethylphenyl), and of formally zero-valent iron as a cocrystal of Fe(CNXyl)5 and Fe2(CNXyl)9. Acta Crystallographica Section C: Structural Chemistry. 2019 Aug 1;75:1118-1127. doi: 10.1107/S205322961900963X

Brennessel, William W. ; Kucera, Benjamin E. ; Young, Victor G. et al. / Crystal structures and spectroscopic characterization of MBr2(CNXyl)n (M = Fe and Co, n = 4; M = Ni, n = 2; Xyl = 2,6-dimethylphenyl), and of formally zero-valent iron as a cocrystal of Fe(CNXyl)5 and Fe2(CNXyl)9. In: Acta Crystallographica Section C: Structural Chemistry. 2019 ; Vol. 75. pp. 1118-1127.

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title = "Crystal structures and spectroscopic characterization of MBr2(CNXyl)n (M = Fe and Co, n = 4; M = Ni, n = 2; Xyl = 2,6-dimethylphenyl), and of formally zero-valent iron as a cocrystal of Fe(CNXyl)5 and Fe2(CNXyl)9",

abstract = "Structures and spectroscopic characterization of the divalent complexes cisdibromidotetrakis( 2,6-dimethylphenyl isocyanide)iron(II) dichloromethane 0.771-solvate, [FeBr2(C9H9N)4]-0.771CH2Cl2 or cis-FeBr2(CNXyl)4-0.771CH2Cl2 (Xyl = 2,6-dimethylphenyl), trans-dibromidotetrakis(2,6-dimethylphenyl isocyanide)-iron(II), [FeBr2(C9H9N)4] or trans-FeBr2(CNXyl)4, trans-dibromidotetrakis(2,6-dimethylphenyl isocyanide)cobalt(II), [CoBr2(C9H9N)4] or trans-CoBr2(CNXyl)4, and trans-dibromidobis(2,6-dimethylphenyl isocyanide)nickel(II), [NiBr2(C9H9N)2] or trans-NiBr2(CNXyl)2, are presented. Additionally, crystals grown from a cold diethyl ether solution of zero-valent Fe(CNXyl)5 produced a structure containing a cocrystallization of mononuclear Fe(CNXyl)5 and the previously unknown dinuclear [Fe(CNXyl)3]2(-2-CNXyl)3, namely pentakis(2,6-dimethylphenyl isocyanide)iron(0) tris(-2-2,6-dimethylphenyl isocyanide)bis[tris(2,6-dimethylphenyl isocyanide)iron(0)], [Fe(C9H9N)5][Fe2(C9H9N)9]. The (M)C- N-C(Xyl) angles of the isocyanide ligand are nearly linear for the metals in the +2 oxidation state, for which the ligands function essentially as pure donors. The -CN stretching frequencies for these divalent metal isocyanides are at or above that of the free ligand. Relative to FeII, in the structure containing iron in the formally zero-valent oxidation state, the Fe-C bond lengths have shortened, the C N bond lengths have elongated, the (M)C-N-C(Xyl) angles of the terminal CNXyl ligands are more bent, and the -CN stretching frequencies have shifted to lower energies, all indicative of substantial M(d-)!- backbonding.",

keywords = "2 6-dimethylphenyl isocyanide, IR spectroscopy, NMR., cobalt, crystal structure, iron, nickel, xylyl isocyanide",

author = "Brennessel, {William W.} and Kucera, {Benjamin E.} and Young, {Victor G.} and Ellis, {John E.}",

note = "Funding Information: Funding for the instrument used to analyse 1 was provided by: National Science Foundation (grant No. CHE-1725028). Funding Information: The authors acknowledge the US National Science Foundation, and the donors of the Petroleum Research Fund, administered by the American Chemical Society, for funding. The University of Minnesota Chemistry Department is acknowledged for providing and supporting the graduate level course in X-ray crystallography. Students from this course, Kevin J. Erickson, Emily L. Que, Airon Soegianto, Pratik Verma, and Daniel J. Wherritt, are thanked for their assistance with the various crystal structures in this article. Data for the structure of CNXyl were collected on an instrument purchased with funding from the NSF. Publisher Copyright: {\textcopyright} 2019.",

year = "2019",

month = aug,

day = "1",

doi = "10.1107/S205322961900963X",

language = "English (US)",

volume = "75",

pages = "1118--1127",

journal = "Acta Crystallographica Section C: Structural Chemistry",

issn = "2053-2296",

publisher = "John Wiley and Sons Inc.",

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TY - JOUR

T1 - Crystal structures and spectroscopic characterization of MBr2(CNXyl)n (M = Fe and Co, n = 4; M = Ni, n = 2; Xyl = 2,6-dimethylphenyl), and of formally zero-valent iron as a cocrystal of Fe(CNXyl)5 and Fe2(CNXyl)9

AU - Brennessel, William W.

AU - Kucera, Benjamin E.

AU - Young, Victor G.

AU - Ellis, John E.

N1 - Funding Information: Funding for the instrument used to analyse 1 was provided by: National Science Foundation (grant No. CHE-1725028). Funding Information: The authors acknowledge the US National Science Foundation, and the donors of the Petroleum Research Fund, administered by the American Chemical Society, for funding. The University of Minnesota Chemistry Department is acknowledged for providing and supporting the graduate level course in X-ray crystallography. Students from this course, Kevin J. Erickson, Emily L. Que, Airon Soegianto, Pratik Verma, and Daniel J. Wherritt, are thanked for their assistance with the various crystal structures in this article. Data for the structure of CNXyl were collected on an instrument purchased with funding from the NSF. Publisher Copyright: © 2019.

PY - 2019/8/1

Y1 - 2019/8/1

N2 - Structures and spectroscopic characterization of the divalent complexes cisdibromidotetrakis( 2,6-dimethylphenyl isocyanide)iron(II) dichloromethane 0.771-solvate, [FeBr2(C9H9N)4]-0.771CH2Cl2 or cis-FeBr2(CNXyl)4-0.771CH2Cl2 (Xyl = 2,6-dimethylphenyl), trans-dibromidotetrakis(2,6-dimethylphenyl isocyanide)-iron(II), [FeBr2(C9H9N)4] or trans-FeBr2(CNXyl)4, trans-dibromidotetrakis(2,6-dimethylphenyl isocyanide)cobalt(II), [CoBr2(C9H9N)4] or trans-CoBr2(CNXyl)4, and trans-dibromidobis(2,6-dimethylphenyl isocyanide)nickel(II), [NiBr2(C9H9N)2] or trans-NiBr2(CNXyl)2, are presented. Additionally, crystals grown from a cold diethyl ether solution of zero-valent Fe(CNXyl)5 produced a structure containing a cocrystallization of mononuclear Fe(CNXyl)5 and the previously unknown dinuclear [Fe(CNXyl)3]2(-2-CNXyl)3, namely pentakis(2,6-dimethylphenyl isocyanide)iron(0) tris(-2-2,6-dimethylphenyl isocyanide)bis[tris(2,6-dimethylphenyl isocyanide)iron(0)], [Fe(C9H9N)5][Fe2(C9H9N)9]. The (M)C- N-C(Xyl) angles of the isocyanide ligand are nearly linear for the metals in the +2 oxidation state, for which the ligands function essentially as pure donors. The -CN stretching frequencies for these divalent metal isocyanides are at or above that of the free ligand. Relative to FeII, in the structure containing iron in the formally zero-valent oxidation state, the Fe-C bond lengths have shortened, the C N bond lengths have elongated, the (M)C-N-C(Xyl) angles of the terminal CNXyl ligands are more bent, and the -CN stretching frequencies have shifted to lower energies, all indicative of substantial M(d-)!- backbonding.

AB - Structures and spectroscopic characterization of the divalent complexes cisdibromidotetrakis( 2,6-dimethylphenyl isocyanide)iron(II) dichloromethane 0.771-solvate, [FeBr2(C9H9N)4]-0.771CH2Cl2 or cis-FeBr2(CNXyl)4-0.771CH2Cl2 (Xyl = 2,6-dimethylphenyl), trans-dibromidotetrakis(2,6-dimethylphenyl isocyanide)-iron(II), [FeBr2(C9H9N)4] or trans-FeBr2(CNXyl)4, trans-dibromidotetrakis(2,6-dimethylphenyl isocyanide)cobalt(II), [CoBr2(C9H9N)4] or trans-CoBr2(CNXyl)4, and trans-dibromidobis(2,6-dimethylphenyl isocyanide)nickel(II), [NiBr2(C9H9N)2] or trans-NiBr2(CNXyl)2, are presented. Additionally, crystals grown from a cold diethyl ether solution of zero-valent Fe(CNXyl)5 produced a structure containing a cocrystallization of mononuclear Fe(CNXyl)5 and the previously unknown dinuclear [Fe(CNXyl)3]2(-2-CNXyl)3, namely pentakis(2,6-dimethylphenyl isocyanide)iron(0) tris(-2-2,6-dimethylphenyl isocyanide)bis[tris(2,6-dimethylphenyl isocyanide)iron(0)], [Fe(C9H9N)5][Fe2(C9H9N)9]. The (M)C- N-C(Xyl) angles of the isocyanide ligand are nearly linear for the metals in the +2 oxidation state, for which the ligands function essentially as pure donors. The -CN stretching frequencies for these divalent metal isocyanides are at or above that of the free ligand. Relative to FeII, in the structure containing iron in the formally zero-valent oxidation state, the Fe-C bond lengths have shortened, the C N bond lengths have elongated, the (M)C-N-C(Xyl) angles of the terminal CNXyl ligands are more bent, and the -CN stretching frequencies have shifted to lower energies, all indicative of substantial M(d-)!- backbonding.

KW - 2 6-dimethylphenyl isocyanide

KW - IR spectroscopy

KW - NMR.

KW - cobalt

KW - crystal structure

KW - iron

KW - nickel

KW - xylyl isocyanide

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U2 - 10.1107/S205322961900963X

DO - 10.1107/S205322961900963X

M3 - Article

C2 - 31380794

AN - SCOPUS:85069458697

SN - 2053-2296

VL - 75

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JO - Acta Crystallographica Section C: Structural Chemistry

JF - Acta Crystallographica Section C: Structural Chemistry

ER -

Crystal structures and spectroscopic characterization of MBr2(CNXyl)n (M = Fe and Co, n = 4; M = Ni, n = 2; Xyl = 2,6-dimethylphenyl), and of formally zero-valent iron as a cocrystal of Fe(CNXyl)5 and Fe2(CNXyl)9

Abstract

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