(+)-Chlorido[(1,2,3,4-η;κP 2′)-2′-diphenyl­phosphanyl-2-diphenyl­phosphoryl-1,1′-binaphth­yl]rhodium(I) methanol monosolvate

Antje Meissner; Carmen Selle; Hans-Joachim Drexler; Detlef Heller

doi:10.1107/S1600536812003418

. 2012 Feb 10;68(Pt 3):m259. doi: 10.1107/S1600536812003418

(+)-Chlorido[(1,2,3,4-η;κP ^2′)-2′-diphenylphosphanyl-2-diphenylphosphoryl-1,1′-binaphthyl]rhodium(I) methanol monosolvate

Antje Meissner ^a, Carmen Selle ^a, Hans-Joachim Drexler ^a,^*, Detlef Heller ^a

PMCID: PMC3297224 PMID: 22412414

Abstract

In the title complex, [RhCl(C₄₄H₃₂OP₂)]·CH₃OH, the Rh^I ion is coordinated by a naphthyl group of a partially oxidized 2,2′-bis(diphenylphosphanyl)-1,1′-binaphthyl (BINAP) ligand in a η⁴ mode, one P atom of the diphenylphosphanyl group and one Cl atom. The P=O group does not interact with the Rh^I ion but accepts an O—H⋯O hydrogen bond from the methanol solvent molecule.

Related literature

For general synthetic aspects of related compounds, see: Bunten et al. (2002 ▶). For related structures of rhodium complexes with BINAP and bisphosphine diolefin, see: Fischer et al. (2012 ▶); Preetz (2009 ▶); Preetz et al. (2010 ▶); Tani et al. (1985 ▶).

Experimental

Crystal data

[RhCl(C₄₄H₃₂OP₂)]·CH₄O
M _r = 809.04
Triclinic,
a = 9.2108 (18) Å
b = 9.7453 (19) Å
c = 11.354 (2) Å
α = 103.01 (3)°
β = 104.59 (3)°
γ = 105.09 (3)°
V = 905.0 (4) Å³
Z = 1
Mo Kα radiation
μ = 0.67 mm⁻¹
T = 200 K
0.20 × 0.15 × 0.15 mm

Data collection

Stoe IPDS-2 diffractometer
Absorption correction: numerical (X-SHAPE and X-RED; Stoe & Cie, 2002 ▶) T _min = 0.787, T _max = 0.953
10887 measured reflections
6247 independent reflections
5695 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.027
wR(F ²) = 0.043
S = 0.96
6247 reflections
462 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 0.64 e Å⁻³
Δρ_min = −0.34 e Å⁻³
Absolute structure: Flack (1983 ▶), 2858 Friedel pairs
Flack parameter: −0.012 (17)

Data collection: X-AREA (Stoe & Cie, 2002 ▶); cell refinement: X-AREA; data reduction: X-RED (Stoe & Cie, 2002 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812003418/hy2508sup1.cif

e-68-0m259-sup1.cif^{(34.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812003418/hy2508Isup2.hkl

e-68-0m259-Isup2.hkl^{(305.7KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O51—H51⋯O1ⁱ	0.82	1.95	2.755 (4)	169

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported by the Leibniz-Institut für Katalyse e.V. an der Universität Rostock.

supplementary crystallographic information

Comment

Ligand exchange between 1,5-cyclooctadiene (COD) and 2,2'-bis(diphenylphosphanyl)-1,1'-binaphthyl (BINAP, a chiral binaphthyl-based chelating diphosphine) in the complex [Rh(COD)(µ₂-Cl)]₂ has been investigated by Preetz (2009) and Bunten et al. (2002). When the reaction is carried out at room temperature, either in dichloromethane or toluene, the complex [Rh(BINAP)(µ₂-Cl)]₂ is formed in 99% yield. The title complex, [Rh(BINAP(O))Cl], containing monooxidized BINAP(O) was isolated from a solution of [Rh(BINAP)(µ₂-Cl)]₂ and methyl-(Z)-α-acetamidocinnamate (MAC) in MeOH, which contained obviously residual traces of oxygen. The molecular structure of [Rh(BINAP(O))Cl] is shown in Fig. 1.

In the title complex, the Rh^I atom is η⁴-coordinated to one of the binaphthyl moieties of the partially oxidized BINAP ligand but not to the O atom. Coordination to O atom is instead observed in the complex [Rh(BINAP(O))(CO)Cl] described by Bunten et al. (2002). This complex has a square-planar geometry with a CO ligand located trans to the O atom. The Rh—P distance of 2.1988 (10) Å in the title complex is by more than 0.1 Å shorter than that in the typical BINAP-rhodium complexes [2.304 (2)–2.335 (2) Å] (Preetz et al., 2010; Tani et al., 1985) and slightly shorter than in [Rh(BINAP(O))(CO)Cl] [2.242 (1) Å]. The Rh—C bond lengths, varying from 2.092 (3) to 2.497 (3) Å, are in the range of the known BINAP-rhodium complexes with benzene (2.226–2.241 Å) (Fischer et al., 2012). The Rh—Cl distance is 2.3222 (15) Å, comparable to that in [Rh(BINAP(O))(CO)Cl] [2.382 (1) Å] (Bunten et al., 2002). An O—H···O hydrogen bond between the methanol solvent molecule and the complex molecule is observed (Table 1).

Experimental

[Rh(COD)(µ₂-Cl)]₂ (0.03 g, 0.06 mmol) and BINAP (0.02 g, 0.03 mmol) were dissolved in tetrahydrofuran at room temperature under anaerobic conditions using standard schlenk-techniques. After stirring for 30 min, the solvent was removed under vacuum. The dark red colored residue was recystallized from CH₂Cl₂ to afford [Rh(BINAP)(µ₂-Cl)]₂.

[Rh(BINAP)(µ₂-Cl)]₂ (0.015 g, 0.01 mmol) and MAC (0.219 g, 1 mmol) were dissolved in 15 ml MeOH and stirred for 6 h under hydrogen. Crystals of the title compound were isolated after two days from the reaction solution, which contained residual traces of oxygen. ³¹P-NMR (300 MHz, THF-d₈): δ 55.3 p.p.m. (d, J_P—Rh = 198,3 Hz), δ 24.4 p.p.m.