(1-Ferrocenyl-4,4,4-trifluoro­butane-1,3-dionato-κ2 O,O)bis­(triphenyl­phosphane)copper(I)

Tobias Rüffer; Chris C Joubert; Blenerhassit E Buitendach; Jannie C Swarts; Alexander Jakob; Heinrich Lang

doi:10.1107/S1600536811001796

. 2011 Jan 22;67(Pt 2):m231–m232. doi: 10.1107/S1600536811001796

(1-Ferrocenyl-4,4,4-trifluorobutane-1,3-dionato-κ² O,O)bis(triphenylphosphane)copper(I)

Tobias Rüffer ^a, Chris C Joubert ^b, Blenerhassit E Buitendach ^b, Jannie C Swarts ^b, Alexander Jakob ^a, Heinrich Lang ^a,^*

PMCID: PMC3051674 PMID: 21522889

Abstract

In the title mononuclear coordination complex, [CuFe(C₅H₅)(C₉H₅F₃O₂)(C₁₈H₁₅P)₂], the Cu^I ion is coordinated by the chelating β-diketonate 1-ferrocenyl-4,4,4-trifluorobutane-1,3-dione ligand through two O atoms and the two datively bonded triphenylphosphane ligands resulting in a distorted tetrahedral coordination sphere. The Cu^I ion, together with its chelating butane-1,3-dione group, is mutually coplanar [greatest displacement of an atom from this plane = 0.037 (1) Å], and the Cu^I ion lies slightly above [0.013 (1) Å] the plane. The overall geometry, including the bond distances and angles within the complex, corresponds to those of other reported copper(I) β-diketonates featuring organic groups at the β-diketonate ligand.

Related literature

For β-diketone chelates in lanthanide coordination chemistry, see: Tsukube et al. (2002 ▶); Kaizaki (2006 ▶). For the chemistry of platina-β-diketones, see: Steinborn (2005 ▶). For the structure of Cu(II)-β-diketones, see: Gromilov & Baidina (2004 ▶). For the preparation of volatile Cu(I)-β-diketones and their chemistry, see: Shin et al. (1991 ▶); Chi et al. (1992 ▶) and for the application of volatile Cu(I)-β-diketones in CVD processes (CVD = chemical vapour deposition), see: Fahlman (2006 ▶); Tiitta & Niinistou (1997 ▶); Chen et al. (2001 ▶); Doppelt (1997 ▶). For photoelectron spectroscopy and electronic structure studies of metal-β-diketones, see: Vovna et al. (1998 ▶). For the application of Cu(I)-β-diketones in ALD processes (ALD = atomic layer deposition), see: Waechtler et al. (2009 ▶). For applications of Cu(I)-hexafluoroacetonates, see: Pampaloni et al. (2005 ▶); Doyle et al. (1985 ▶). For other copper(I) β-diketonate derivatives, see: Yang et al. (2001 ▶); Marchetti et al. (2000 ▶); Croxtall et al. (2003 ▶); Herberhold et al. (2004 ▶). For a related ferrocenyl derivative of the title compound, see: du Plessis et al. (1999 ▶).

Experimental

Crystal data

[CuFe(C₅H₅)(C₉H₅F₃O₂)(C₁₈H₁₅P)₂]
M _r = 911.15
Monoclinic,
a = 11.02755 (13) Å
b = 16.8178 (2) Å
c = 12.50787 (14) Å
β = 115.2456 (14)°
V = 2098.15 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.98 mm⁻¹
T = 120 K
0.56 × 0.48 × 0.18 mm

Data collection

Oxford Diffraction Gemini S diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006 ▶) T _min = 0.943, T _max = 1.000
21096 measured reflections
8248 independent reflections
7761 reflections with I > 2σ(I)
R _int = 0.015

Refinement

R[F ² > 2σ(F ²)] = 0.020
wR(F ²) = 0.052
S = 1.03
8248 reflections
532 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.25 e Å⁻³
Absolute structure: Flack (1983 ▶), 3945 Friedel pairs
Flack parameter: −0.010 (6)

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811001796/si2308sup1.cif

e-67-0m231-sup1.cif^{(44.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811001796/si2308Isup2.hkl

e-67-0m231-Isup2.hkl^{(395.3KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Enhanced figure: interactive version of Fig. 2

Table 1. Selected bond lengths (Å).

O1—Cu1	2.0821 (12)
O2—Cu1	2.0783 (11)
Cu1—P2	2.2405 (5)
Cu1—P1	2.2529 (5)

Open in a new tab

Acknowledgments

Financial assistance from the Deutsche Forschungsgemeinschaft, the Fonds der Chemischen Industrie, the South African NRF and the University of the Free State is gratefully acknowledged.

supplementary crystallographic information

Comment

Well known coordination compounds in transition metal chemistry are metal β-diketonates and Lewis-base metal β-diketonates, see: Gromilov & Baidina (2004); Steinborn (2005); Tsukube et al. (2002); Kaizaki (2006); Vovna et al. (1998). A multitude of diverse derivatives have been prepared to date using different synthesis methodologies with copper(I) β-diketonates and Lewis-base copper(I) β-diketonates being one family of compounds. These molecules are, for example, very well suited as volatile CVD (= Chemical Vapor Deposition), see: (Fahlman (2006); Tiitta & Niinistou, (1997); Chen et al. (2001); Doppelt (1997), and ALD (= Atomic Layer Deposition), see: Waechtler et al. (2009) precursors in the deposition of highly pure and thin copper layers on different substrates, i. e. TiN-coated silicon oxide substrate materials.

The title coordination compound is a derivative of the family of transition metal β-diketonates in which the copper(I) center possesses a pseudo-tetrahedral environment set-up by the chelate-bonded organometallic 1-ferrocenyl-4,4,4-trifluorobutane-1,3-dione (see: du Plessis et al. (1999)) unit and the two datively-bonded triphenylphosphino ligands. The coordination geometry around copper(I) is best described as a distorted tetrahedron that resembles other complexes including (hfac)Cu(1,5-COD), see: Pampaloni et al. (2005); Doyle et al. (1985), or (Me₃P)₂Cu(acac), see: Shin et al. (1991); Chi et al. (1992). The bond distances Cu–P, Cu–O, Fe–D1 (1.6401 (9) Å) and Fe–D2 (1.6466 (9) Å) (D1 = centroid of C1 - C5; D2 = centroid of C6 - C10) as well as the bond angles P2–Cu1–P1, P2–Cu1–O1, P2–Cu1–O2, P1–Cu1–O1, P1–Cu1–O2, O2–Cu1–O1 are similar to those ones found for other copper(I) β-diketonate derivatives, see, for example: Yang et al. (2001); Marchetti et al. (2000); Croxtall et al. (2003); Herberhold et al. (2004). The atoms Cu1, O1, O2, and C11 - C13 are, as expected, in plane bound (r. m. s. d. of a calculated mean plane = 0.024 Å).

Experimental

The title complex was synthesized by the consecutive reaction of 100 mg (0.31 mmol) of 1-ferrocenyl-4,4,4-trifluorobutane-1,3-dione (see: du Plessis et al. (1999)) with 40 mg (0.36 mmol) of potassium t-butanolate (diethyl ether, 298 K, 4 h) followed by addition of 180 mg (0.29 mmol) of [(Ph₃P)₂CuCl] (diethyl ether, 298 K, 12 h). After filtration of the reaction mixture through a pad of Celite and removal of all volatile materials in oil-pump vacuum gave the title complex as an orange solid in a yield of 120 mg (0.13 mmol, 45%) based on [(Ph₃P)₂CuCl]). This complex is stable in air and light over a period of days. It nicely dissolves in common organic solvents.