The reactivity of CuX2 (X- = Cl-, Br-, MeCO-2) salts towards tris-pyrazolyl-borates of differing steric requirements. The single crystal X-ray structure of [CuCl(pzPhH)(HB{pzPh}3)] · CH2Cl2

Malcolm A. Halcrow; John E. Davies; Paul R. Raithby

doi:10.1016/S0277-5387(96)00434-2

The reactivity of CuX₂ (X^- = Cl^-, Br^-, MeCO^-₂) salts towards tris-pyrazolyl-borates of differing steric requirements. The single crystal X-ray structure of [CuCl(pz^PhH)(HB{pz^Ph}₃)] · CH₂Cl₂

Malcolm A. Halcrow, John E. Davies, Paul R. Raithby

University of Cambridge

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

31 Citations (SciVal)

Abstract

Treatment of CuX₂ (X^- = Cl^-, Br^-) with one molar equivalent of K[HB{pz^Ph}₃] (pz^PhH = 3-phenylpyrazole) in CH₂Cl₂: MeCN (4: 1) at room temperature afforded [CuX(pz^PhH)(HB{pz^Ph}₃)] (X = Cl , I; X^- = Br^-, II) in moderate to good yields. The crystal structure of the title compound shows a square-pyramidal copper(II) centre, with Cu - Cl = 2.2740(13) Å and Cu - N = 2.010(3), 2.031(3), 2.038(3), 2.241(3) Å. The complex exhibits an intramolecular N - H ⋯ Cl hydrogen bond, with N - H ⋯ Cl = 3.034(4) Å, N - H ⋯ Cl = 119.4°, and an intramolecular graphitic interaction between the pz^PhH pyrazole ring and a phenyl group from the tripodal ligand. Steric repulsions between this phenyl group and the bound Cl^- cause substantial distortions from an ideal square-pyramidal geometry. Reaction of K[HB{pz^Ph}₃] with Cu₂(O₂CMe)₄ · 2H₂O yields [Cu(O₂CMe)(HB{pz^Ph}₃)] (III). The EPR and UV-vis spectroscopic properties of I-III are consistent with a {d_x2-y2}¹ configuration at copper.

Original language	English
Pages (from-to)	1535-1541
Number of pages	7
Journal	Polyhedron
Volume	16
Issue number	9
DOIs	https://doi.org/10.1016/S0277-5387(96)00434-2
Publication status	Published - 31 Dec 1997

Bibliographical note

Funding Information:
for a University Research Fellowship to M.A.H., the E.P.S.R.C. for purchase of a diffractometer, the University of Cambridge and St Catharine's College for support. We also thank Dr G. Reid (University of Southampton) for the EPR spectrum of II.

Funding

for a University Research Fellowship to M.A.H., the E.P.S.R.C. for purchase of a diffractometer, the University of Cambridge and St Catharine's College for support. We also thank Dr G. Reid (University of Southampton) for the EPR spectrum of II.

Keywords

B - N cleavage
Copper
Crystal structure
Tris-pyrazolylborate

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

Access to Document

10.1016/S0277-5387(96)00434-2

Cite this

The reactivity of CuX₂ (X^- = Cl^-, Br^-, MeCO^-₂) salts towards tris-pyrazolyl-borates of differing steric requirements. The single crystal X-ray structure of [CuCl(pz^PhH)(HB{pz^Ph}₃)] · CH₂Cl₂. / Halcrow, Malcolm A.; Davies, John E.; Raithby, Paul R.
In: Polyhedron, Vol. 16, No. 9, 31.12.1997, p. 1535-1541.

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

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title = "The reactivity of CuX2 (X- = Cl-, Br-, MeCO-2) salts towards tris-pyrazolyl-borates of differing steric requirements. The single crystal X-ray structure of [CuCl(pzPhH)(HB{pzPh}3)] · CH2Cl2",

abstract = "Treatment of CuX2 (X- = Cl-, Br-) with one molar equivalent of K[HB{pzPh}3] (pzPhH = 3-phenylpyrazole) in CH2Cl2: MeCN (4: 1) at room temperature afforded [CuX(pzPhH)(HB{pzPh}3)] (X = Cl , I; X- = Br-, II) in moderate to good yields. The crystal structure of the title compound shows a square-pyramidal copper(II) centre, with Cu - Cl = 2.2740(13) {\AA} and Cu - N = 2.010(3), 2.031(3), 2.038(3), 2.241(3) {\AA}. The complex exhibits an intramolecular N - H ⋯ Cl hydrogen bond, with N - H ⋯ Cl = 3.034(4) {\AA}, N - H ⋯ Cl = 119.4°, and an intramolecular graphitic interaction between the pzPhH pyrazole ring and a phenyl group from the tripodal ligand. Steric repulsions between this phenyl group and the bound Cl- cause substantial distortions from an ideal square-pyramidal geometry. Reaction of K[HB{pzPh}3] with Cu2(O2CMe)4 · 2H2O yields [Cu(O2CMe)(HB{pzPh}3)] (III). The EPR and UV-vis spectroscopic properties of I-III are consistent with a {dx2-y2}1 configuration at copper.",

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AU - Halcrow, Malcolm A.

AU - Davies, John E.

AU - Raithby, Paul R.

N1 - Funding Information: for a University Research Fellowship to M.A.H., the E.P.S.R.C. for purchase of a diffractometer, the University of Cambridge and St Catharine's College for support. We also thank Dr G. Reid (University of Southampton) for the EPR spectrum of II.

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N2 - Treatment of CuX2 (X- = Cl-, Br-) with one molar equivalent of K[HB{pzPh}3] (pzPhH = 3-phenylpyrazole) in CH2Cl2: MeCN (4: 1) at room temperature afforded [CuX(pzPhH)(HB{pzPh}3)] (X = Cl , I; X- = Br-, II) in moderate to good yields. The crystal structure of the title compound shows a square-pyramidal copper(II) centre, with Cu - Cl = 2.2740(13) Å and Cu - N = 2.010(3), 2.031(3), 2.038(3), 2.241(3) Å. The complex exhibits an intramolecular N - H ⋯ Cl hydrogen bond, with N - H ⋯ Cl = 3.034(4) Å, N - H ⋯ Cl = 119.4°, and an intramolecular graphitic interaction between the pzPhH pyrazole ring and a phenyl group from the tripodal ligand. Steric repulsions between this phenyl group and the bound Cl- cause substantial distortions from an ideal square-pyramidal geometry. Reaction of K[HB{pzPh}3] with Cu2(O2CMe)4 · 2H2O yields [Cu(O2CMe)(HB{pzPh}3)] (III). The EPR and UV-vis spectroscopic properties of I-III are consistent with a {dx2-y2}1 configuration at copper.

AB - Treatment of CuX2 (X- = Cl-, Br-) with one molar equivalent of K[HB{pzPh}3] (pzPhH = 3-phenylpyrazole) in CH2Cl2: MeCN (4: 1) at room temperature afforded [CuX(pzPhH)(HB{pzPh}3)] (X = Cl , I; X- = Br-, II) in moderate to good yields. The crystal structure of the title compound shows a square-pyramidal copper(II) centre, with Cu - Cl = 2.2740(13) Å and Cu - N = 2.010(3), 2.031(3), 2.038(3), 2.241(3) Å. The complex exhibits an intramolecular N - H ⋯ Cl hydrogen bond, with N - H ⋯ Cl = 3.034(4) Å, N - H ⋯ Cl = 119.4°, and an intramolecular graphitic interaction between the pzPhH pyrazole ring and a phenyl group from the tripodal ligand. Steric repulsions between this phenyl group and the bound Cl- cause substantial distortions from an ideal square-pyramidal geometry. Reaction of K[HB{pzPh}3] with Cu2(O2CMe)4 · 2H2O yields [Cu(O2CMe)(HB{pzPh}3)] (III). The EPR and UV-vis spectroscopic properties of I-III are consistent with a {dx2-y2}1 configuration at copper.

KW - B - N cleavage

KW - Copper

KW - Crystal structure

KW - Tris-pyrazolylborate

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