Chloridotris[tris­(4-fluoro­phen­yl)phosphine]rhodium(I) methanol solvate

Fabio Lorenzini; Brian O Patrick; Brian R James

doi:10.1107/S1600536808005485

. 2008 Mar 5;64(Pt 4):m512–m513. doi: 10.1107/S1600536808005485

Chloridotris[tris(4-fluorophenyl)phosphine]rhodium(I) methanol solvate

Fabio Lorenzini ^a, Brian O Patrick ^a, Brian R James ^a,^*

PMCID: PMC2960913 PMID: 21201983

Abstract

In the title compound, [RhCl{P(p-FC₆H₄)₃}₃]·CH₃OH, the Rh atom adopts a distorted square-planar geometry. Rh, Cl and one P atom lie on a mirror plane, as does the solvent molecule. There are two intermolecular hydrogen bonds, one between the methanol O atom and an aryl H atom (2.51 Å), and one between the Cl atom and the hydroxy H atom of methanol [2.34 (3) Å]. The complex precipitates in trace amounts from a reaction between RhCl(cod)(thp) [cod is 1,5-cyclooctadiene and thp is tris(hydroxymethyl)phosphine] and P(p-FC₆H₄)₃ under argon in CD₃OD. Two C₆H₄-F units are disordered over two positions; for one the site occupancy factors are ca. 0.53 and 0.47, for the other the values are ca. 0.64 and 0.36. The methyl H atoms of the solvent molecule are disordered across the mirror plane.

Related literature

For related literature, see: Beck et al. (1999 ▶) and references therein; Bennett & Donaldson (1977 ▶); Bennett et al. (1971 ▶); Evans et al. (1999 ▶); Higham et al. (2004 ▶); Hoye et al. (1993 ▶); Jones et al. (1980 ▶); Lorenzini et al. (2007a ▶,b ▶,c ▶, 2008a ▶,b ▶); Montelatici et al. (1968 ▶); Young et al. (1965 ▶).

Experimental

Crystal data

[RhCl(C₁₈H₁₂F₃P)₃]·CH₄O
M _r = 1119.14
Monoclinic,
a = 10.831 (3) Å
b = 23.724 (7) Å
c = 9.845 (3) Å
β = 108.213 (8)°
V = 2403.0 (12) Å³
Z = 2
Mo Kα radiation
μ = 0.59 mm⁻¹
T = 173.0 (1) K
0.30 × 0.15 × 0.03 mm

Data collection

Bruker X8 APEXII diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ▶) T _min = 0.544, T _max = 0.983
10921 measured reflections
3312 independent reflections
3094 reflections with I > 2σ(I)
R _int = 0.048

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.075
S = 1.03
3312 reflections
372 parameters
15 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.67 e Å⁻³
Δρ_min = −0.47 e Å⁻³
Absolute structure: Flack (1983 ▶), 812 Friedel pairs
Flack parameter: −0.03 (3)

Data collection: SAINT (Bruker, 2003 ▶); cell refinement: SAINT; data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808005485/rk2075sup1.cif

e-64-0m512-sup1.cif^{(31.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808005485/rk2075Isup2.hkl

e-64-0m512-Isup2.hkl^{(159.2KB, 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
C3—H3⋯O1ⁱ	0.95	2.51	3.458 (9)	172
O1—H1O⋯Cl1ⁱⁱ	1.03 (5)	2.34 (5)	3.369 (9)	174 (11)

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

The authors thank the Natural Sciences and Engineering Research Council of Canada for financial support via a Discovery Grant.

supplementary crystallographic information

Comment

We have reported recently on the syntheses of water-soluble Rh^I–thp complexes such as RhCl(cod)(thp), where thp = tris(hydroxymethyl)phosphine, P(CH₂OH)₃, and cod = 1,5-cyclooctadiene (Lorenzini et al., 2007a). This complex reacts with PRR'₂ phosphines (R = or ≠ R') in solution under Ar to generate, concomitantly with R'H, the phosphine-phosphinite derivatives RhCl(PRR'₂)[P,P-R'(R)POCH₂P(CH₂OH)₂] in two isomeric cis- and trans-forms, where cis and trans refer to the disposition of the P atoms with the R and R' substituents. In some of these systems, trace amounts of the trans-RhCl(CO)(PRR'₂)₂ complexes are formed (Lorenzini et al., 2007b), and these have been characterized by X-ray crystallography, for example, for the PEtPh₂ and P(p-tolyl)₃ systems (Lorenzini et al., 2008b; Lorenzini et al., submitted). The CO ligand almost certainly derives from the formaldehyde (Beck et al., 1999), which can be readily formed from transition metal–thp species (Higham et al., 2004; Hoye et al., 1993). The RhCl(cod)(thp)/phosphine reactions, when carried out under H₂, give high yield formation of the dihydrido complexes cis,mer-Rh(H)₂Cl(PRR'₂)₃ (where R' = Ph, and R = Me or Cy), although in some systems (e.g. with PMePh₂) partial loss of H₂ occurs and the RhCl(PRR'₂)₃ species has been detected in solution (Lorenzini et al., 2007c). Now, during a reaction of the Rh precursor with P(p-FC₆H₄)₃ in MeOH under Ar, we have found that a few crystals of RhCl[P(p-FC₆H₄)₃]₃.CH₃OH in low overall yield are precipitated.

The so-called "Wilkinson" hydrogenation catalyst, RhCl(PPh₃)₃, was first reported in 1965 (Young et al., 1965), and since then 22 Rh(I) complexes of general formula RhCl(PRR'₂)₃ have been structurally characterized; the first such complex was RhCl(PF₂NEt₂)₂(PPh₃) (Bennett et al., 1971), while there are just 3 of the type RhCl(PR₃)₃ where R = Ph (Bennett & Donaldson, 1977), Me (Jones et al., 1980) and OPh (Evans et al., 1999). The title P(p-FC₆H₄)₃ complex was first isolated in 1968 (Montelatici et al., 1968), but an X-ray structure has not been reported.

Experimental

General. The RhCl(1,5-cod)(thp) complex was synthesized by our recently reported method (Lorenzini et al., 2007a); P(p-FC₆H₄)₃ was used as received from Strem Chemicals, CD₃OD (Cambridge Isotope Laboratory) was used as received. The Rh-phosphine reaction was carried out under Ar using standard Schlenk techniques.

RhCl[P(p-FC₆H₄)₃]₃.CH₃OH. Addition of P(p-FC₆H₄)₃ (10 mg, 0.031 mmol) in CD₃OD (0.5 ml) to a yellow CD₃OD solution (0.5 ml) of RhCl(1,5-cod)(thp) (5.6 mg, 0.015 mmol) at room temperature under Ar results in the immediate formation of a brown solution. Over 12 h, a few X-ray quality, yellow plate crystals of the solvated complex deposit from the solution.