Structure and Mechanism of Formation of a Novel π-Bonded Ketenimine Complex, Bis(tert-butyl isocyanide) (N-tert-butyldicyanoketenimine)nickel(0). Evidence for a Metal-Assisted Carbene Addition

D. J. Yarrow; James A. Ibers; Yoshitaka Tatsuno; Sei Otsuka

doi:10.1021/ja00807a015

Structure and Mechanism of Formation of a Novel π-Bonded Ketenimine Complex, Bis(tert-butyl isocyanide) (N-tert-butyldicyanoketenimine)nickel(0). Evidence for a Metal-Assisted Carbene Addition

D. J. Yarrow, James A. Ibers^*, Yoshitaka Tatsuno, Sei Otsuka

^*Corresponding author for this work

Chemistry

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Abstract

A single-crystal X-ray study was carried out on the product of the reaction between Ni(t-BuNC)₄ and diazodicyanomethane, N₂ C(CN)₂. The product is shown to be the ketenimine complex Ni(t-BuN═C═C(CN)₂)(t-BuNC)₂. Evidence is presented which shows that the reaction proceeds via an intermediate diazodicyanomethane complex, Ni(N₂ C(CN)₂)(t-BuNC)₃. The remarkably facile thermal decomposition of this complex is proposed to involve a metal-assisted carbene addition to a coordinated isocyanide. The ketenimine complex thus formed crystallizes in space group D_2h¹⁵-Pbca of the orthorhombic system, with eight molecules in a unit cell of dimensions a = 10.199 (3), b = 34.283 (9), and c = 12.662 (3) Å. The structure has been refined by least-squares techniques to a final R index of 4.1 % based on 1905 reflections above background. The coordination about the Ni atom is approximately trigonal, if the ketenimine is regarded as a monodentate ligand. The ketenimine is coordinated to the metal via the carbon-heteroatom unsaturation. The cumulene system N═C═C is severely distorted from linearity upon coordination, the bond angle around the central carbon atom being 144.2 (4)°. A comparison is made between the structural parameters of the coordinated ketenimine and those of uncomplexed ketenimines.

Original language	English (US)
Pages (from-to)	8590-8597
Number of pages	8
Journal	Journal of the American Chemical Society
Volume	95
Issue number	26
DOIs	https://doi.org/10.1021/ja00807a015
State	Published - Dec 1 1973

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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@article{31b1fe9db5a54a62865fed6c5e2b2d3a,

title = "Structure and Mechanism of Formation of a Novel π-Bonded Ketenimine Complex, Bis(tert-butyl isocyanide) (N-tert-butyldicyanoketenimine)nickel(0). Evidence for a Metal-Assisted Carbene Addition",

abstract = "A single-crystal X-ray study was carried out on the product of the reaction between Ni(t-BuNC)4 and diazodicyanomethane, N2 C(CN)2. The product is shown to be the ketenimine complex Ni(t-BuN═C═C(CN)2)(t-BuNC)2. Evidence is presented which shows that the reaction proceeds via an intermediate diazodicyanomethane complex, Ni(N2 C(CN)2)(t-BuNC)3. The remarkably facile thermal decomposition of this complex is proposed to involve a metal-assisted carbene addition to a coordinated isocyanide. The ketenimine complex thus formed crystallizes in space group D2h15-Pbca of the orthorhombic system, with eight molecules in a unit cell of dimensions a = 10.199 (3), b = 34.283 (9), and c = 12.662 (3) {\AA}. The structure has been refined by least-squares techniques to a final R index of 4.1 % based on 1905 reflections above background. The coordination about the Ni atom is approximately trigonal, if the ketenimine is regarded as a monodentate ligand. The ketenimine is coordinated to the metal via the carbon-heteroatom unsaturation. The cumulene system N═C═C is severely distorted from linearity upon coordination, the bond angle around the central carbon atom being 144.2 (4)°. A comparison is made between the structural parameters of the coordinated ketenimine and those of uncomplexed ketenimines.",

author = "Yarrow, {D. J.} and Ibers, {James A.} and Yoshitaka Tatsuno and Sei Otsuka",

year = "1973",

month = dec,

day = "1",

doi = "10.1021/ja00807a015",

language = "English (US)",

volume = "95",

pages = "8590--8597",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "26",

}

Structure and Mechanism of Formation of a Novel π-Bonded Ketenimine Complex, Bis(tert-butyl isocyanide) (N-tert-butyldicyanoketenimine)nickel(0). Evidence for a Metal-Assisted Carbene Addition. / Yarrow, D. J.; Ibers, James A.; Tatsuno, Yoshitaka et al.
In: Journal of the American Chemical Society, Vol. 95, No. 26, 01.12.1973, p. 8590-8597.

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

TY - JOUR

T1 - Structure and Mechanism of Formation of a Novel π-Bonded Ketenimine Complex, Bis(tert-butyl isocyanide) (N-tert-butyldicyanoketenimine)nickel(0). Evidence for a Metal-Assisted Carbene Addition

AU - Yarrow, D. J.

AU - Ibers, James A.

AU - Tatsuno, Yoshitaka

AU - Otsuka, Sei

PY - 1973/12/1

Y1 - 1973/12/1

N2 - A single-crystal X-ray study was carried out on the product of the reaction between Ni(t-BuNC)4 and diazodicyanomethane, N2 C(CN)2. The product is shown to be the ketenimine complex Ni(t-BuN═C═C(CN)2)(t-BuNC)2. Evidence is presented which shows that the reaction proceeds via an intermediate diazodicyanomethane complex, Ni(N2 C(CN)2)(t-BuNC)3. The remarkably facile thermal decomposition of this complex is proposed to involve a metal-assisted carbene addition to a coordinated isocyanide. The ketenimine complex thus formed crystallizes in space group D2h15-Pbca of the orthorhombic system, with eight molecules in a unit cell of dimensions a = 10.199 (3), b = 34.283 (9), and c = 12.662 (3) Å. The structure has been refined by least-squares techniques to a final R index of 4.1 % based on 1905 reflections above background. The coordination about the Ni atom is approximately trigonal, if the ketenimine is regarded as a monodentate ligand. The ketenimine is coordinated to the metal via the carbon-heteroatom unsaturation. The cumulene system N═C═C is severely distorted from linearity upon coordination, the bond angle around the central carbon atom being 144.2 (4)°. A comparison is made between the structural parameters of the coordinated ketenimine and those of uncomplexed ketenimines.

AB - A single-crystal X-ray study was carried out on the product of the reaction between Ni(t-BuNC)4 and diazodicyanomethane, N2 C(CN)2. The product is shown to be the ketenimine complex Ni(t-BuN═C═C(CN)2)(t-BuNC)2. Evidence is presented which shows that the reaction proceeds via an intermediate diazodicyanomethane complex, Ni(N2 C(CN)2)(t-BuNC)3. The remarkably facile thermal decomposition of this complex is proposed to involve a metal-assisted carbene addition to a coordinated isocyanide. The ketenimine complex thus formed crystallizes in space group D2h15-Pbca of the orthorhombic system, with eight molecules in a unit cell of dimensions a = 10.199 (3), b = 34.283 (9), and c = 12.662 (3) Å. The structure has been refined by least-squares techniques to a final R index of 4.1 % based on 1905 reflections above background. The coordination about the Ni atom is approximately trigonal, if the ketenimine is regarded as a monodentate ligand. The ketenimine is coordinated to the metal via the carbon-heteroatom unsaturation. The cumulene system N═C═C is severely distorted from linearity upon coordination, the bond angle around the central carbon atom being 144.2 (4)°. A comparison is made between the structural parameters of the coordinated ketenimine and those of uncomplexed ketenimines.

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U2 - 10.1021/ja00807a015

DO - 10.1021/ja00807a015

M3 - Article

AN - SCOPUS:0342606106

SN - 0002-7863

VL - 95

SP - 8590

EP - 8597

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 26

ER -

Structure and Mechanism of Formation of a Novel π-Bonded Ketenimine Complex, Bis(tert-butyl isocyanide) (N-tert-butyldicyanoketenimine)nickel(0). Evidence for a Metal-Assisted Carbene Addition

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