DOI: 10.1002/anie.201605061. Dispersion‐Force‐Assisted Disproportionation: A Stable Two‐Coordinate Copper(II) Complex

Dispersion‐Force‐Assisted Disproportionation: A Stable Two‐Coordinate Copper(II) Complex

10.1002/anie.201605061

Crossref journal-article

Wiley

Angewandte Chemie International Edition (311)

Abstract

AbstractThe synthesis of the first linear coordinated CuII complex Cu{N(SiMe3)Dipp}2 (1 Dipp=C6H5‐2,6Pri2) and its CuI counterpart [Cu{N(SiMe3)Dipp}2]− (2) is described. The formation of 1 proceeds through a dispersion force‐driven disproportionation, and is the reaction product of a CuI halide and LiN(SiMe3)Dipp in a non‐donor solvent. The synthesis of 2 is accomplished by preventing the disproportionation into 1 by using the complexing agent 15‐crown‐5. EPR spectroscopy of 1 provides the first detailed study of a two‐coordinate transition‐metal complex indicating strong covalency in the Cu−N bonds.

Bibliography

Wagner, C. L., Tao, L., Thompson, E. J., Stich, T. A., Guo, J., Fettinger, J. C., Berben, L. A., Britt, R. D., Nagase, S., & Power, P. P. (2016). DispersionâForceâAssisted Disproportionation: A Stable TwoâCoordinate Copper(II) Complex. Angewandte Chemie International Edition, 55(35), 10444â10447. Portico.

Authors 10

Clifton L. Wagner (first)
Lizhi Tao (additional)
Emily J. Thompson (additional)
Troy A. Stich (additional)
Jingdong Guo (additional)
James C. Fettinger (additional)
Louise A. Berben (additional)
R. David Britt (additional)
Shigeru Nagase (additional)
Philip P. Power (additional)

References 66 Referenced 43

10.1039/C2SC20801F
10.1126/science.1092641
10.1002/anie.201005055
10.1002/ange.201005055
10.1021/ic200788f
10.1039/c2cc32974c
10.1021/ic402105m
10.1021/ic501925e
10.1021/cr2004647
10.1021/om401107f
10.1002/chem.201503980
10.1039/c39850001380
10.1039/c39850001807
10.1002/1521-3749(200104)627:4<715::AID-ZAAC715>3.0.CO;2-0
10.1016/S0020-1693(02)01309-9
10.1021/ja00258a069
10.1002/9780470740385
10.1021/ja403244w
10.1016/j.ccr.2010.02.003
10.1039/C5CS00513B
10.1039/b810941a
10.1021/ja042958q
10.1039/C0DT01247E
10.1002/anie.199503251
10.1002/ange.19951070330
10.1021/om00007a029
10.1039/9781847559616-00056
10.1021/ja991533e
10.1021/cr400327t
10.1002/anie.201003676
10.1002/ange.201003676
10.1021/ic501534f
10.1016/S0022-2836(02)00885-9
10.1021/ja300654t
10.1021/ic403108z
10.1038/nchem.1004
10.1002/anie.201103615
10.1002/ange.201103615
10.1021/ic300824u
10.1002/anie.201503476
10.1002/ange.201503476
10.1039/C5SC02707A
10.1016/j.jorganchem.2004.06.010
The neutral [Cu{N(SiMe3)Dipp]ncould then disproportionate to yield Cu{N(SiMe3)Dipp}2and Cu metal. However [Cu{N(SiMe3)Dipp}]3(unpublished work) displays no evidence of conversion to Cu{N(SiMe3)Dipp}2up to its decomposition temperature of 132–135 °C.
10.1021/ic971341p
10.1039/C4CC00912F
CCDC 1480973 (1) and 1480974 (2) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge fromThe Cambridge Crystallographic Data Centre.
10.1021/ic0203668
10.1021/ja408151h
10.1002/(SICI)1521-3749(200003)626:3<747::AID-ZAAC747>3.0.CO;2-L
10.1039/dt9960002601
10.1021/ja403802a
10.1021/ja063322x
10.1021/acscatal.5b01354
10.1080/02603598408080072
10.1021/ja809834k
10.1016/0022-2364(78)90284-6
10.1021/ic026099n
10.1021/ja00762a056

Dates

Type	When
Created	9 years, 1 month ago (July 15, 2016, 6:40 a.m.)
Deposited	1 year, 11 months ago (Sept. 9, 2023, 10:52 p.m.)
Indexed	2 weeks, 3 days ago (Aug. 7, 2025, 5:13 p.m.)
Issued	9 years, 1 month ago (July 15, 2016)
Published	9 years, 1 month ago (July 15, 2016)
Published Online	9 years, 1 month ago (July 15, 2016)
Published Print	9 years ago (Aug. 22, 2016)

Funders 1

National Science Foundation 10.13039/100000001
Region: Americas
gov (National government)
Labels4
1. U.S. National Science Foundation
2. NSF
3. US NSF
4. USA NSF
Awards4
1. CHE-1213699
2. CHE-1565501
3. 1531193
4. CHE-1263760

BibTeX

@article{Wagner_2016, title={Dispersion‐Force‐Assisted Disproportionation: A Stable Two‐Coordinate Copper(II) Complex}, volume={55}, ISSN={1521-3773}, url={http://dx.doi.org/10.1002/anie.201605061}, DOI={10.1002/anie.201605061}, number={35}, journal={Angewandte Chemie International Edition}, publisher={Wiley}, author={Wagner, Clifton L. and Tao, Lizhi and Thompson, Emily J. and Stich, Troy A. and Guo, Jingdong and Fettinger, James C. and Berben, Louise A. and Britt, R. David and Nagase, Shigeru and Power, Philip P.}, year={2016}, month=jul, pages={10444–10447} }

JSON

{
  "indexed": {
    "date-parts": [
      [
        2025,
        8,
        7
      ]
    ],
    "date-time": "2025-08-07T21:13:40Z",
    "timestamp": 1754601220958
  },
  "reference-count": 66,
  "publisher": "Wiley",
  "issue": "35",
  "license": [
    {
      "start": {
        "date-parts": [
          [
            2017,
            7,
            15
          ]
        ],
        "date-time": "2017-07-15T00:00:00Z",
        "timestamp": 1500076800000
      },
      "content-version": "am",
      "delay-in-days": 365,
      "URL": "http://onlinelibrary.wiley.com/termsAndConditions#am"
    },
    {
      "start": {
        "date-parts": [
          [
            2016,
            7,
            15
          ]
        ],
        "date-time": "2016-07-15T00:00:00Z",
        "timestamp": 1468540800000
      },
      "content-version": "vor",
      "delay-in-days": 0,
      "URL": "http://onlinelibrary.wiley.com/termsAndConditions#vor"
    }
  ],
  "funder": [
    {
      "DOI": "10.13039/100000001",
      "name": "National Science Foundation",
      "doi-asserted-by": "publisher",
      "award": [
        "CHE-1263760",
        "CHE-1565501",
        "CHE-1213699",
        "1531193"
      ],
      "id": [
        {
          "id": "10.13039/100000001",
          "id-type": "DOI",
          "asserted-by": "publisher"
        }
      ]
    }
  ],
  "content-domain": {
    "domain": [],
    "crossmark-restriction": false
  },
  "published-print": {
    "date-parts": [
      [
        2016,
        8,
        22
      ]
    ]
  },
  "abstract": "<jats:title>Abstract</jats:title><jats:p>The synthesis of the first linear coordinated Cu<jats:sup>II</jats:sup> complex Cu{N(SiMe<jats:sub>3</jats:sub>)Dipp}<jats:sub>2</jats:sub> (<jats:bold>1</jats:bold> Dipp=C<jats:sub>6</jats:sub>H<jats:sub>5</jats:sub>\u20102,6Pr<jats:sup><jats:italic>i</jats:italic></jats:sup><jats:sub>2</jats:sub>) and its Cu<jats:sup>I</jats:sup> counterpart [Cu{N(SiMe<jats:sub>3</jats:sub>)Dipp}<jats:sub>2</jats:sub>]<jats:sup>\u2212</jats:sup> (<jats:bold>2</jats:bold>) is described. The formation of <jats:bold>1</jats:bold> proceeds through a dispersion force\u2010driven disproportionation, and is the reaction product of a Cu<jats:sup>I</jats:sup> halide and LiN(SiMe<jats:sub>3</jats:sub>)Dipp in a non\u2010donor solvent. The synthesis of <jats:bold>2</jats:bold> is accomplished by preventing the disproportionation into <jats:bold>1</jats:bold> by using the complexing agent 15\u2010crown\u20105. EPR spectroscopy of <jats:bold>1</jats:bold> provides the first detailed study of a two\u2010coordinate transition\u2010metal complex indicating strong covalency in the Cu\u2212N bonds.</jats:p>",
  "DOI": "10.1002/anie.201605061",
  "type": "journal-article",
  "created": {
    "date-parts": [
      [
        2016,
        7,
        15
      ]
    ],
    "date-time": "2016-07-15T10:40:34Z",
    "timestamp": 1468579234000
  },
  "page": "10444-10447",
  "source": "Crossref",
  "is-referenced-by-count": 43,
  "title": "Dispersion\u2010Force\u2010Assisted Disproportionation: A Stable Two\u2010Coordinate Copper(II) Complex",
  "prefix": "10.1002",
  "volume": "55",
  "author": [
    {
      "given": "Clifton L.",
      "family": "Wagner",
      "sequence": "first",
      "affiliation": [
        {
          "name": "Department of Chemistry University of California, Davis  One Shield Avenue Davis CA 95616 USA"
        }
      ]
    },
    {
      "given": "Lizhi",
      "family": "Tao",
      "sequence": "additional",
      "affiliation": [
        {
          "name": "Department of Chemistry University of California, Davis  One Shield Avenue Davis CA 95616 USA"
        }
      ]
    },
    {
      "given": "Emily J.",
      "family": "Thompson",
      "sequence": "additional",
      "affiliation": [
        {
          "name": "Department of Chemistry University of California, Davis  One Shield Avenue Davis CA 95616 USA"
        }
      ]
    },
    {
      "given": "Troy A.",
      "family": "Stich",
      "sequence": "additional",
      "affiliation": [
        {
          "name": "Department of Chemistry University of California, Davis  One Shield Avenue Davis CA 95616 USA"
        }
      ]
    },
    {
      "given": "Jingdong",
      "family": "Guo",
      "sequence": "additional",
      "affiliation": [
        {
          "name": "Fukui Institute for Fundamental Chemistry Kyoto University  Takano Nishi-Hiraki-cho 34-4, Sakyo-ku Kyoto, 606\u20138103 Japan"
        }
      ]
    },
    {
      "given": "James C.",
      "family": "Fettinger",
      "sequence": "additional",
      "affiliation": [
        {
          "name": "Department of Chemistry University of California, Davis  One Shield Avenue Davis CA 95616 USA"
        }
      ]
    },
    {
      "given": "Louise A.",
      "family": "Berben",
      "sequence": "additional",
      "affiliation": [
        {
          "name": "Department of Chemistry University of California, Davis  One Shield Avenue Davis CA 95616 USA"
        }
      ]
    },
    {
      "given": "R. David",
      "family": "Britt",
      "sequence": "additional",
      "affiliation": [
        {
          "name": "Department of Chemistry University of California, Davis  One Shield Avenue Davis CA 95616 USA"
        }
      ]
    },
    {
      "given": "Shigeru",
      "family": "Nagase",
      "sequence": "additional",
      "affiliation": [
        {
          "name": "Fukui Institute for Fundamental Chemistry Kyoto University  Takano Nishi-Hiraki-cho 34-4, Sakyo-ku Kyoto, 606\u20138103 Japan"
        }
      ]
    },
    {
      "given": "Philip P.",
      "family": "Power",
      "sequence": "additional",
      "affiliation": [
        {
          "name": "Department of Chemistry University of California, Davis  One Shield Avenue Davis CA 95616 USA"
        }
      ]
    }
  ],
  "member": "311",
  "published-online": {
    "date-parts": [
      [
        2016,
        7,
        15
      ]
    ]
  },
  "reference": [
    {
      "key": "e_1_2_2_1_1",
      "unstructured": "\u00a0"
    },
    {
      "key": "e_1_2_2_2_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1039/C2SC20801F"
    },
    {
      "key": "e_1_2_2_3_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1126/science.1092641"
    },
    {
      "key": "e_1_2_2_4_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/anie.201005055"
    },
    {
      "key": "e_1_2_2_4_3",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/ange.201005055"
    },
    {
      "key": "e_1_2_2_5_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ic200788f"
    },
    {
      "key": "e_1_2_2_6_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1039/c2cc32974c"
    },
    {
      "key": "e_1_2_2_7_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ic402105m"
    },
    {
      "key": "e_1_2_2_8_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ic501925e"
    },
    {
      "key": "e_1_2_2_9_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/cr2004647"
    },
    {
      "key": "e_1_2_2_10_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/om401107f"
    },
    {
      "key": "e_1_2_2_11_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/chem.201503980"
    },
    {
      "key": "e_1_2_2_12_1",
      "doi-asserted-by": "publisher",
      "DOI": "10.1039/c39850001380"
    },
    {
      "key": "e_1_2_2_13_1",
      "doi-asserted-by": "publisher",
      "DOI": "10.1039/c39850001807"
    },
    {
      "key": "e_1_2_2_14_1",
      "unstructured": "\u00a0"
    },
    {
      "key": "e_1_2_2_15_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/1521-3749(200104)627:4<715::AID-ZAAC715>3.0.CO;2-0"
    },
    {
      "key": "e_1_2_2_16_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1016/S0020-1693(02)01309-9"
    },
    {
      "key": "e_1_2_2_17_1",
      "unstructured": "\u00a0"
    },
    {
      "key": "e_1_2_2_18_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ja00258a069"
    },
    {
      "key": "e_1_2_2_19_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/9780470740385"
    },
    {
      "key": "e_1_2_2_20_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ja403244w"
    },
    {
      "key": "e_1_2_2_21_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1016/j.ccr.2010.02.003"
    },
    {
      "key": "e_1_2_2_22_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1039/C5CS00513B"
    },
    {
      "key": "e_1_2_2_23_1",
      "doi-asserted-by": "publisher",
      "DOI": "10.1039/b810941a"
    },
    {
      "key": "e_1_2_2_24_1",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ja042958q"
    },
    {
      "key": "e_1_2_2_25_1",
      "unstructured": "\u00a0"
    },
    {
      "key": "e_1_2_2_26_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1039/C0DT01247E"
    },
    {
      "key": "e_1_2_2_27_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/anie.199503251"
    },
    {
      "key": "e_1_2_2_27_3",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/ange.19951070330"
    },
    {
      "key": "e_1_2_2_28_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/om00007a029"
    },
    {
      "key": "e_1_2_2_29_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1039/9781847559616-00056"
    },
    {
      "key": "e_1_2_2_30_1",
      "unstructured": "\u00a0"
    },
    {
      "key": "e_1_2_2_31_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ja991533e"
    },
    {
      "key": "e_1_2_2_32_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/cr400327t"
    },
    {
      "key": "e_1_2_2_33_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/anie.201003676"
    },
    {
      "key": "e_1_2_2_33_3",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/ange.201003676"
    },
    {
      "key": "e_1_2_2_34_1",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ic501534f"
    },
    {
      "key": "e_1_2_2_35_1",
      "doi-asserted-by": "publisher",
      "DOI": "10.1016/S0022-2836(02)00885-9"
    },
    {
      "key": "e_1_2_2_36_1",
      "unstructured": "\u00a0"
    },
    {
      "key": "e_1_2_2_37_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ja300654t"
    },
    {
      "key": "e_1_2_2_38_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ic403108z"
    },
    {
      "key": "e_1_2_2_39_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1038/nchem.1004"
    },
    {
      "key": "e_1_2_2_40_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/anie.201103615"
    },
    {
      "key": "e_1_2_2_40_3",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/ange.201103615"
    },
    {
      "key": "e_1_2_2_41_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ic300824u"
    },
    {
      "key": "e_1_2_2_42_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/anie.201503476"
    },
    {
      "key": "e_1_2_2_42_3",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/ange.201503476"
    },
    {
      "key": "e_1_2_2_43_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1039/C5SC02707A"
    },
    {
      "key": "e_1_2_2_44_1",
      "doi-asserted-by": "publisher",
      "DOI": "10.1016/j.jorganchem.2004.06.010"
    },
    {
      "key": "e_1_2_2_45_1",
      "unstructured": "The neutral [Cu{N(SiMe3)Dipp]ncould then disproportionate to yield Cu{N(SiMe3)Dipp}2and Cu metal. However [Cu{N(SiMe3)Dipp}]3(unpublished work) displays no evidence of conversion to Cu{N(SiMe3)Dipp}2up to its decomposition temperature of 132\u2013135\u2009\u00b0C."
    },
    {
      "key": "e_1_2_2_46_1",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ic971341p"
    },
    {
      "key": "e_1_2_2_47_1",
      "doi-asserted-by": "publisher",
      "DOI": "10.1039/C4CC00912F"
    },
    {
      "key": "e_1_2_2_48_1",
      "unstructured": "CCDC\u20051480973 (1) and 1480974 (2) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge fromThe Cambridge Crystallographic Data Centre."
    },
    {
      "key": "e_1_2_2_49_1",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ic0203668"
    },
    {
      "key": "e_1_2_2_50_1",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ja408151h"
    },
    {
      "key": "e_1_2_2_51_1",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/(SICI)1521-3749(200003)626:3<747::AID-ZAAC747>3.0.CO;2-L"
    },
    {
      "key": "e_1_2_2_52_1",
      "doi-asserted-by": "publisher",
      "DOI": "10.1039/dt9960002601"
    },
    {
      "key": "e_1_2_2_53_1",
      "unstructured": "\u00a0"
    },
    {
      "key": "e_1_2_2_54_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ja403802a"
    },
    {
      "key": "e_1_2_2_55_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ja063322x"
    },
    {
      "key": "e_1_2_2_56_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/acscatal.5b01354"
    },
    {
      "key": "e_1_2_2_57_1",
      "doi-asserted-by": "publisher",
      "DOI": "10.1080/02603598408080072"
    },
    {
      "key": "e_1_2_2_58_1",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ja809834k"
    },
    {
      "key": "e_1_2_2_59_1",
      "doi-asserted-by": "publisher",
      "DOI": "10.1016/0022-2364(78)90284-6"
    },
    {
      "key": "e_1_2_2_60_1",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ic026099n"
    },
    {
      "key": "e_1_2_2_61_1",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ja00762a056"
    }
  ],
  "container-title": "Angewandte Chemie International Edition",
  "original-title": [],
  "language": "en",
  "link": [
    {
      "URL": "https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fanie.201605061",
      "content-type": "application/pdf",
      "content-version": "vor",
      "intended-application": "text-mining"
    },
    {
      "URL": "https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fanie.201605061",
      "content-type": "unspecified",
      "content-version": "vor",
      "intended-application": "text-mining"
    },
    {
      "URL": "https://onlinelibrary.wiley.com/doi/pdf/10.1002/anie.201605061",
      "content-type": "application/pdf",
      "content-version": "vor",
      "intended-application": "text-mining"
    },
    {
      "URL": "https://onlinelibrary.wiley.com/doi/full-xml/10.1002/anie.201605061",
      "content-type": "application/xml",
      "content-version": "vor",
      "intended-application": "text-mining"
    },
    {
      "URL": "https://onlinelibrary.wiley.com/doi/am-pdf/10.1002/anie.201605061",
      "content-type": "application/pdf",
      "content-version": "am",
      "intended-application": "syndication"
    },
    {
      "URL": "https://onlinelibrary.wiley.com/doi/pdf/10.1002/anie.201605061",
      "content-type": "unspecified",
      "content-version": "vor",
      "intended-application": "similarity-checking"
    }
  ],
  "deposited": {
    "date-parts": [
      [
        2023,
        9,
        10
      ]
    ],
    "date-time": "2023-09-10T02:52:43Z",
    "timestamp": 1694314363000
  },
  "score": 1,
  "resource": {
    "primary": {
      "URL": "https://onlinelibrary.wiley.com/doi/10.1002/anie.201605061"
    }
  },
  "subtitle": [],
  "short-title": [],
  "issued": {
    "date-parts": [
      [
        2016,
        7,
        15
      ]
    ]
  },
  "references-count": 66,
  "journal-issue": {
    "issue": "35",
    "published-print": {
      "date-parts": [
        [
          2016,
          8,
          22
        ]
      ]
    }
  },
  "alternative-id": [
    "10.1002/anie.201605061"
  ],
  "URL": "http://dx.doi.org/10.1002/anie.201605061",
  "relation": {},
  "ISSN": [
    "1433-7851",
    "1521-3773"
  ],
  "subject": [],
  "container-title-short": "Angew Chem Int Ed",
  "published": {
    "date-parts": [
      [
        2016,
        7,
        15
      ]
    ]
  }
}