A singlet biradicaloid zinc compound and its nonradical counterpart

Amit Pratap Singh; Prinson P. Samuel; Herbert W. Roesky; Martin C. Schwarzer; Gernot Frenking; Navdeep S. Sidhu; Birger Dittrich

doi:10.1021/ja402351x

A singlet biradicaloid zinc compound and its nonradical counterpart

Amit Pratap Singh, Prinson P. Samuel, Herbert W. Roesky, Martin C. Schwarzer, Gernot Frenking, Navdeep S. Sidhu, Birger Dittrich

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

89 Scopus citations

Abstract

Metal ions with radical centers in their coordination sphere are key participants in biological and catalytic processes. In the present study, we describe the synthesis of the cAAC:ZnCl₂ adduct (1) using a cyclic alkylaminocarbene (cAAC) as donor ligand. Compound 1 was treated with 2 equiv of KC₈ and LiB(sec-Bu)₃H to yield a deep blue-colored dicarbene zinc compound (cAAC)₂Zn (2) and the colorless hydrogenated zinc compound (cAACH)₂Zn (3), respectively. Compounds 2 and 3 were well characterized by spectroscopic methods and single-crystal X-ray structural analysis. Density functional theory calculations were performed for 2 which indicate that this molecule possesses a singlet biradicaloid character. Moreover, we show the application of 2 in CO₂ activation, which yields a zwitterionic cAAC·CO₂ adduct.

Original language	English
Pages (from-to)	7324-7329
Number of pages	6
Journal	Journal of the American Chemical Society
Volume	135
Issue number	19
DOIs	https://doi.org/10.1021/ja402351x
State	Published - 15 May 2013
Externally published	Yes

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abstract = "Metal ions with radical centers in their coordination sphere are key participants in biological and catalytic processes. In the present study, we describe the synthesis of the cAAC:ZnCl2 adduct (1) using a cyclic alkylaminocarbene (cAAC) as donor ligand. Compound 1 was treated with 2 equiv of KC8 and LiB(sec-Bu)3H to yield a deep blue-colored dicarbene zinc compound (cAAC)2Zn (2) and the colorless hydrogenated zinc compound (cAACH)2Zn (3), respectively. Compounds 2 and 3 were well characterized by spectroscopic methods and single-crystal X-ray structural analysis. Density functional theory calculations were performed for 2 which indicate that this molecule possesses a singlet biradicaloid character. Moreover, we show the application of 2 in CO2 activation, which yields a zwitterionic cAAC·CO2 adduct.",

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T1 - A singlet biradicaloid zinc compound and its nonradical counterpart

AU - Singh, Amit Pratap

AU - Samuel, Prinson P.

AU - Roesky, Herbert W.

AU - Schwarzer, Martin C.

AU - Frenking, Gernot

AU - Sidhu, Navdeep S.

AU - Dittrich, Birger

PY - 2013/5/15

Y1 - 2013/5/15

N2 - Metal ions with radical centers in their coordination sphere are key participants in biological and catalytic processes. In the present study, we describe the synthesis of the cAAC:ZnCl2 adduct (1) using a cyclic alkylaminocarbene (cAAC) as donor ligand. Compound 1 was treated with 2 equiv of KC8 and LiB(sec-Bu)3H to yield a deep blue-colored dicarbene zinc compound (cAAC)2Zn (2) and the colorless hydrogenated zinc compound (cAACH)2Zn (3), respectively. Compounds 2 and 3 were well characterized by spectroscopic methods and single-crystal X-ray structural analysis. Density functional theory calculations were performed for 2 which indicate that this molecule possesses a singlet biradicaloid character. Moreover, we show the application of 2 in CO2 activation, which yields a zwitterionic cAAC·CO2 adduct.

AB - Metal ions with radical centers in their coordination sphere are key participants in biological and catalytic processes. In the present study, we describe the synthesis of the cAAC:ZnCl2 adduct (1) using a cyclic alkylaminocarbene (cAAC) as donor ligand. Compound 1 was treated with 2 equiv of KC8 and LiB(sec-Bu)3H to yield a deep blue-colored dicarbene zinc compound (cAAC)2Zn (2) and the colorless hydrogenated zinc compound (cAACH)2Zn (3), respectively. Compounds 2 and 3 were well characterized by spectroscopic methods and single-crystal X-ray structural analysis. Density functional theory calculations were performed for 2 which indicate that this molecule possesses a singlet biradicaloid character. Moreover, we show the application of 2 in CO2 activation, which yields a zwitterionic cAAC·CO2 adduct.

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A singlet biradicaloid zinc compound and its nonradical counterpart

Abstract

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