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Copper(I) complexes with a Cu4S6- and CuS4-type core obtained from the reaction of copper(0) with HN(SPPh2)(2)•I-2

Copper(I) complexes with a Cu4S6- and CuS4-type core obtained from the reaction of copper(0) with HN(SPPh2)(2)•I-2
Copper(I) complexes with a Cu4S6- and CuS4-type core obtained from the reaction of copper(0) with HN(SPPh2)(2)•I-2
The copper(I) compounds [CU4I(L)(3)]I-3 (1) and [Cu-I(HL)(2)]-I-3•CH3CN (2) [HL = HN(SPPh2)(2)] have been obtained from the reaction of the adduct (HLI2)-I-. with copper(O) powder in diethyl ether solution. Compound I contains a tetrahedron of Cu atoms with three anionic L ligands coordinated to the coppers through the sulfur atoms to build a CU4S6 core. The mean Cu-Cu and Cu-S bond lengths related to the CU4S6 core in copper-loaded transcription factors CuAce1 and CuMac1, and in the model compound [Cu-4(SPh)(6)](2-), have been compared with those of the [Cu-4(L)(3)](+) cation, and the geometric volumes of the Cu-4 cores have been evaluated. The results suggest that the cation [Cu-4(L)31' is a possible structural model compound for the metal site in Ace1 and Mac1 transcription factors. In compound 2, two neutral HL ligands bind a Cu-I ion in an S,S'-isobidentate chelating fashion to form a slightly distorted tetrahedral CuS4 core. The P-31 NMR spectroscopic data of compound 1 are consistent with the maintenance of its structure in solution. Moreover, phosphorus variable-temperature measurements indicate a change from a two-spin coupled AB system at 0 degrees C to an A(2) spin system at 40 degrees C. The reaction of [Cu-4(L)(3)](+) with HI, monitored by P-31 NMR spectroscopy, leads to the protonation of the complexed ligands at the CU4 core and formation of the cation [Cu-4(HL)(3)](4+). The protonation reaction is reversible: increasing the amount of organic base 1,8-bis(dimethylamino)naphthalene (DMAN) regenerates the starting cation [CU4(L)(3)](+). (c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006).
cluster compounds, copper, coordination chemistry, phosphanes, s ligands cuprous-thiolate clusters, crystal-structure, tetraphenyldithioimidodiphosphinic acid, derivatives, adduct, model
1434-1948
200-206
Aragoni, M. Carla
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Arca, Massimiliano
f90b59f6-4dfb-471d-912e-3515e6507165
Carrea, M. Bonaria
a2ef07e8-0043-49e2-81e9-b41b9c6ada78
Demartin, Francesco
f2d77165-ac45-445d-a3bb-126098718b79
Devillanova, Francesco A.
a1015716-6d8a-4517-aac8-593b78e91561
Garau, Alessandra
0dbe375e-901e-4003-9700-45926d87a771
Hursthouse, Michael B.
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Huth, Susanne L.
b1cb7019-3459-4842-9d38-6db10f67384d
Isaia, Francesco
11f997fe-81a3-4298-bbdc-15e5f2bf18cc
Lippolis, Vito
d9833a14-4aab-4827-a2ba-be818871dcf5
Ogilvie, Helen R.
667a68cc-7f86-47e6-a7fb-e9d3b7fdd488
Verani, Gaetano
2b49b8a9-fe0a-47aa-b29b-4978e07d5aa9
Aragoni, M. Carla
3e73ed7a-2cf7-4f5e-9359-61d6e34a6cd5
Arca, Massimiliano
f90b59f6-4dfb-471d-912e-3515e6507165
Carrea, M. Bonaria
a2ef07e8-0043-49e2-81e9-b41b9c6ada78
Demartin, Francesco
f2d77165-ac45-445d-a3bb-126098718b79
Devillanova, Francesco A.
a1015716-6d8a-4517-aac8-593b78e91561
Garau, Alessandra
0dbe375e-901e-4003-9700-45926d87a771
Hursthouse, Michael B.
57a2ddf9-b1b3-4f38-bfe9-ef2f526388da
Huth, Susanne L.
b1cb7019-3459-4842-9d38-6db10f67384d
Isaia, Francesco
11f997fe-81a3-4298-bbdc-15e5f2bf18cc
Lippolis, Vito
d9833a14-4aab-4827-a2ba-be818871dcf5
Ogilvie, Helen R.
667a68cc-7f86-47e6-a7fb-e9d3b7fdd488
Verani, Gaetano
2b49b8a9-fe0a-47aa-b29b-4978e07d5aa9

Aragoni, M. Carla, Arca, Massimiliano, Carrea, M. Bonaria, Demartin, Francesco, Devillanova, Francesco A., Garau, Alessandra, Hursthouse, Michael B., Huth, Susanne L., Isaia, Francesco, Lippolis, Vito, Ogilvie, Helen R. and Verani, Gaetano (2006) Copper(I) complexes with a Cu4S6- and CuS4-type core obtained from the reaction of copper(0) with HN(SPPh2)(2)•I-2. European Journal of Inorganic Chemistry, (1), 200-206. (doi:10.1002/ejic.200500639).

Record type: Article

Abstract

The copper(I) compounds [CU4I(L)(3)]I-3 (1) and [Cu-I(HL)(2)]-I-3•CH3CN (2) [HL = HN(SPPh2)(2)] have been obtained from the reaction of the adduct (HLI2)-I-. with copper(O) powder in diethyl ether solution. Compound I contains a tetrahedron of Cu atoms with three anionic L ligands coordinated to the coppers through the sulfur atoms to build a CU4S6 core. The mean Cu-Cu and Cu-S bond lengths related to the CU4S6 core in copper-loaded transcription factors CuAce1 and CuMac1, and in the model compound [Cu-4(SPh)(6)](2-), have been compared with those of the [Cu-4(L)(3)](+) cation, and the geometric volumes of the Cu-4 cores have been evaluated. The results suggest that the cation [Cu-4(L)31' is a possible structural model compound for the metal site in Ace1 and Mac1 transcription factors. In compound 2, two neutral HL ligands bind a Cu-I ion in an S,S'-isobidentate chelating fashion to form a slightly distorted tetrahedral CuS4 core. The P-31 NMR spectroscopic data of compound 1 are consistent with the maintenance of its structure in solution. Moreover, phosphorus variable-temperature measurements indicate a change from a two-spin coupled AB system at 0 degrees C to an A(2) spin system at 40 degrees C. The reaction of [Cu-4(L)(3)](+) with HI, monitored by P-31 NMR spectroscopy, leads to the protonation of the complexed ligands at the CU4 core and formation of the cation [Cu-4(HL)(3)](4+). The protonation reaction is reversible: increasing the amount of organic base 1,8-bis(dimethylamino)naphthalene (DMAN) regenerates the starting cation [CU4(L)(3)](+). (c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006).

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Published date: 2006
Keywords: cluster compounds, copper, coordination chemistry, phosphanes, s ligands cuprous-thiolate clusters, crystal-structure, tetraphenyldithioimidodiphosphinic acid, derivatives, adduct, model

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Local EPrints ID: 44359
URI: http://eprints.soton.ac.uk/id/eprint/44359
ISSN: 1434-1948
PURE UUID: f35b6d6d-8610-4179-a7ac-d59c66ec6c80

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Date deposited: 28 Feb 2007
Last modified: 13 Mar 2019 21:07

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Contributors

Author: M. Carla Aragoni
Author: Massimiliano Arca
Author: M. Bonaria Carrea
Author: Francesco Demartin
Author: Francesco A. Devillanova
Author: Alessandra Garau
Author: Susanne L. Huth
Author: Francesco Isaia
Author: Vito Lippolis
Author: Helen R. Ogilvie
Author: Gaetano Verani

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