DOI: 10.1002/anie.199007961. Synthesis and Structure of Novel Cu‐Clusters: [Cu30−xSe15(PiPr3)12] (x = 0,1) and [Cu36Se18(PtBu3)12]

Synthesis and Structure of Novel Cu‐Clusters: [Cu30−xSe15(PiPr3)12] (x = 0,1) and [Cu36Se18(PtBu3)12]

10.1002/anie.199007961

Crossref journal-article

Wiley

Angewandte Chemie International Edition in English (311)

Abstract

In contrast to the system phosphane/AgCl, the system phosphane/CuCl reacts with Se(SiMe3)2 below 20°C to give metal‐rich cluster complexes in yields of 60%. Above 100°C, binary copper selenides are formed. Compounds 1–3 were characterized by X‐ray structure analysis. They are the largest Cu cluster compounds so far known. The structures of 1 and 2 reveal a cluster framework whose polyhedral surfaces are covered with μ4‐Se, μ5‐Se, and μ6‐Se ligands. equation image

Bibliography

Fenske, D., Krautscheid, H., & Balter, S. (1990). Synthesis and Structure of Novel CuâClusters: [Cu30âxSe15(PiPr3)12] (x = 0,1) and [Cu36Se18(PtBu3)12]. Angewandte Chemie International Edition in English, 29(7), 796â799. Portico.

Authors 3

Dieter Fenske (first)
Harald Krautscheid (additional)
Silke Balter (additional)

References 42 Referenced 48

10.1002/ange.19881001006
10.1002/anie.198812771
10.1002/ange.19891011236
10.1002/anie.198916651
10.1002/ange.19891011026
10.1002/anie.198913921
10.1515/znb-1988-1001 / Z. Naturforsch by Maué P. G. (1988)
10.1515/znb-1989-0505 / Z. Naturforsch by Fenske D. (1989)
Procedures:1and2: 0.4 g (4 mmol) of CuCl was suspended in 50 mL of ether. On addition of 1.5 mL (8 mmol) cf PiPr3the CuCl dissolved. Upon subsequent treatment with 0.5 mL (2 mmol) of Se(SiMe3)2the solution turned dark brown and within2da mixture of1and2precipitated in the form of black crystals. These could be separated from each other by virtue of their different habits (yield 60%).3: A suspension of CuCl (0.4 g.4mmol) in THF (50 mL) was treated with 1 mL (4 mmol) of PtBu3. After addition of 0.5 mL (2 mmol) of Se(Si Me3)2at −30 °C the mixture was allowed to warm to room temperature over the course of several days. Brown crystals of3precipitated from the brown solution (yield 30%).
X‐ray structure analyses: Stoe Stadi IV MoKα empirical absorption correction; data collection and refinement: ω scan; Cu Se P anisotropic C isotropic.1(from diethyl ether): lattice constants (200 K):a= 1998.6(8) b= 1898.2(7) c= 2367.7(10) pm α = 89.80(3) β = 93.86(4) γ = 92.05(4)° V= 8956 x 106pm3; space group P1 Z= 2 μ(MoKα) = 64.9 cm−1. Profile analysis 2θmax= 45° 25 400 reflections 10 895 withI> 2σ(I) 854 parameters R1= 0.12;R2= 0.10. The poorRvalue arises as the result of a disorder of theiPr groups.2(from diethyl ether): lattice constants (190 K):a= 2396.6(13) b= 2624.9(12) c= 2831.4(12) β = 91.80(4) V= 17804 x 106pm3. Space groupP21/c Z= 4 μ(MoKα= 65.2cm−1). Profile analysis 2θmax= 45° 23 251 reflections 11 875 withI> 2σ(I) 937 parameters R1= 0.081 R2= 0.073.3(from THF):3crystallizes with six molecules THF/formula unit. Lattice constants (200 K):a= 2117.4(12) b= 3593.2(13) c= 3059.2(6) pm β = 89.22(2)° V= 23 273 x 106pm3. Space groupC2/c Z= 4 (MoKα) = 59.7 cm−1. Profile analysis 2θmax= 48° 19243 reflections 11 430 withI> 2σ(I) 631 parameters R1= 0.063 R2= 0.060. Further details of the crystal structure investigations are available on request from the Fachinformationszentrum Karlsruhe Gesellschaft für wissenschaftlich‐technische Information mbH Eggenstein‐Leopoldshafen2(FRG) on quoting the depository number CSD‐54560 the names of the authors and the journal citation.
10.1002/ange.19860980106
10.1002/anie.198600561
10.1515/znb-1987-0701 / Z. Naturforsch. by Fenske D. (1987)
10.1139/v76-122
{'key': 'e_1_2_1_6_2', 'first-page': '50', 'volume': '43', 'author': 'Müller A.', 'year': '1989', 'journal-title': 'Chimia'} / Chimia by Müller A. (1989)
10.1016/S0277-5387(00)81131-6
The refinement of the structure of2yielded a residual electron density of 6–8 electrons in the cluster center. We cannot as yet make any statements about the nature of the atom that has been encapsulated.
10.1002/ange.19850970523
10.1002/anie.198504091
{'key': 'e_1_2_1_8_4', 'first-page': '1156', 'volume': '1983', 'author': 'Gambarotta S.', 'journal-title': 'J. Chem. Soc. Chem. Commun.'} / J. Chem. Soc. Chem. Commun. by Gambarotta S.
{'key': 'e_1_2_1_8_5', 'first-page': '475', 'volume': '1973', 'author': 'Jarvis J. A. J.', 'journal-title': 'J. Chem. Soc. Chem. Commun.'} / J. Chem. Soc. Chem. Commun. by Jarvis J. A. J.
10.1002/ange.19840960516
10.1002/anie.198403781
{'key': 'e_1_2_1_8_8', 'first-page': '314', 'volume': '1984', 'author': 'Henkel G.', 'journal-title': 'J. Chem. Soc. Chem. Commun.'} / J. Chem. Soc. Chem. Commun. by Henkel G.
10.1002/ange.19840960412
10.1002/anie.198403111
{'key': 'e_1_2_1_8_11', 'first-page': 'L41', 'volume': '1976', 'author': 'Dance I. G.', 'journal-title': 'Inorg. Chim. Acta'} / Inorg. Chim. Acta by Dance I. G.
10.1021/ic50212a030
{'key': 'e_1_2_1_8_13', 'first-page': '1031', 'volume': '1988', 'author': 'Block E.', 'journal-title': 'J. Chem. Soc. Chem. Commun.'} / J. Chem. Soc. Chem. Commun. by Block E.
10.1021/ja00229a021
10.1016/S0022-328X(00)95088-5
10.1021/ic50186a032
C.Kölmel R.Ahlrichs J. Phys. Chem. in press;
10.1021/ic00285a022
10.1002/ange.19870990927
10.1002/anie.198708971
10.1002/ange.19850970824
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{'key': 'e_1_2_1_10_6', 'first-page': '218', 'volume': '1987', 'author': 'Mednikov E. G.', 'journal-title': 'J. Chem. Soc. Chem. Commun.'} / J. Chem. Soc. Chem. Commun. by Mednikov E. G.
10.1002/cber.19811141116
10.1021/ja00198a072
10.1021/ja00208a023

Dates

Type	When
Created	21 years, 7 months ago (Dec. 30, 2003, 7:07 p.m.)
Deposited	1 year, 10 months ago (Oct. 22, 2023, 2:55 p.m.)
Indexed	1 year, 6 months ago (Feb. 11, 2024, 2:19 a.m.)
Issued	35 years, 1 month ago (July 1, 1990)
Published	35 years, 1 month ago (July 1, 1990)
Published Online	21 years, 8 months ago (Dec. 22, 2003)
Published Print	35 years, 1 month ago (July 1, 1990)

Funders 0

None

BibTeX

@article{Fenske_1990, title={Synthesis and Structure of Novel Cu‐Clusters: [Cu30−xSe15(PiPr3)12] (x = 0,1) and [Cu36Se18(PtBu3)12]}, volume={29}, ISSN={0570-0833}, url={http://dx.doi.org/10.1002/anie.199007961}, DOI={10.1002/anie.199007961}, number={7}, journal={Angewandte Chemie International Edition in English}, publisher={Wiley}, author={Fenske, Dieter and Krautscheid, Harald and Balter, Silke}, year={1990}, month=jul, pages={796–799} }

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  "abstract": "<jats:p><jats:bold>In contrast to the system phosphane/AgCl</jats:bold>, the system phosphane/CuCl reacts with Se(SiMe<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub> below 20\u00b0C to give metal\u2010rich cluster complexes in yields of 60%. Above 100\u00b0C, binary copper selenides are formed. Compounds <jats:bold>1</jats:bold>\u2013<jats:bold>3</jats:bold> were characterized by X\u2010ray structure analysis. They are the largest Cu cluster compounds so far known. The structures of <jats:bold>1</jats:bold> and <jats:bold>2</jats:bold> reveal a cluster framework whose polyhedral surfaces are covered with \u03bc<jats:sub>4</jats:sub>\u2010Se, \u03bc<jats:sub>5</jats:sub>\u2010Se, and \u03bc<jats:sub>6</jats:sub>\u2010Se ligands.<jats:disp-formula>\n<jats:graphic xmlns:xlink=\"http://www.w3.org/1999/xlink\" position=\"anchor\" xlink:href=\"urn:x-wiley:05700833:media:ANIE199007961:nueqn001\"><jats:alt-text>equation image</jats:alt-text></jats:graphic>\n</jats:disp-formula></jats:p>",
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