trans-Carbonyl­chloridobis(tri-p-tolyl­phosphine)rhodium(I) acetone solvate

Fabio Lorenzini; Brian O Patrick; Brian R James

doi:10.1107/S1600536808003528

. 2008 Feb 8;64(Pt 3):m464–m465. doi: 10.1107/S1600536808003528

trans-Carbonylchloridobis(tri-p-tolylphosphine)rhodium(I) acetone solvate

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

PMCID: PMC2960764 PMID: 21201856

Abstract

The title compound, [RhCl(C₂₁H₂₁P)₂(CO)]·C₃H₆O, was precipitated in trace yield from a reaction of RhCl(cod)(THP) with P(p-tol)₃ in a 1:1 acetone-d ₆/CD₃OD solution under a hydrogen atmosphere [p-tol = p-tolyl, THP = tris(hydroxymethyl)phosphine, P(CH₂OH)₃, and cod = 1,5-cyclooctadiene]. The complex displays a square-planar geometry around the Rh^I atom. The complex molecules and the acetone molecules are linked into a chain along the a axis by intermolecular C—H⋯Cl and C—H⋯O hydrogen bonds.

Related literature

For related literature, see: Beck et al. (1999 ▶, and references therein); Evans et al. (1990 ▶); Higham et al. (2004 ▶); Hoye et al. (1993 ▶); Lorenzini et al. (2007a ▶,b ▶, 2008a ▶,b ▶); Vallarino (1957 ▶).

Experimental

Crystal data

[RhCl(C₂₁H₂₁P)₂(CO)]·C₃H₆O
M _r = 833.14
Triclinic,
a = 10.784 (2) Å
b = 12.859 (3) Å
c = 17.086 (3) Å
α = 70.852 (7)°
β = 84.790 (7)°
γ = 71.012 (6)°
V = 2116.2 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.58 mm⁻¹
T = 173 (2) K
0.25 × 0.10 × 0.07 mm

Data collection

Bruker X8 APEXII diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ▶) T _min = 0.683, T _max = 0.960
31662 measured reflections
9909 independent reflections
6378 reflections with I > 2σ(I)
R _int = 0.063

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.115
S = 1.00
9909 reflections
477 parameters
H-atom parameters constrained
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.44 e Å⁻³

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); 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/S1600536808003528/ci2547sup1.cif

e-64-0m464-sup1.cif^{(31.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808003528/ci2547Isup2.hkl

e-64-0m464-Isup2.hkl^{(474.8KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

C43—Rh1	1.812 (4)
P1—Rh1	2.3449 (9)
P2—Rh1	2.3283 (9)
Cl1—Rh1	2.3822 (9)

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C43—Rh1—P2	91.43 (10)
C43—Rh1—P1	90.55 (10)
P2—Rh1—P1	177.46 (3)
C43—Rh1—Cl1	178.12 (10)
P2—Rh1—Cl1	86.69 (3)
P1—Rh1—Cl1	91.33 (3)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10⋯O2ⁱ	0.95	2.38	3.302 (8)	163
C46—H46A⋯Cl1	0.98	2.81	3.773 (7)	168

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Symmetry code: (i) Inline graphic .

Acknowledgments

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

supplementary crystallographic information

Comment

We have very recently reported the structure of trans-RhCl(CO)(PEtPh₂)₂, crystals of which precipitated serendipitously in trace yield from a reaction between PEtPh₂ and RhCl(cod)(THP), where cod = 1,5-cyclooctadiene and THP = tris(hydroxymethyl)phosphine, P(CH₂OH)₃, in an acetone/MeOH solvent mixture under a hydrogen atmosphere (Lorenzini et al., 2008b). Such reaction conditions with a phosphine of general formula PRR'₂ (R = or ≠ R') lead to formation of the dihydrido complexes cis,mer-Rh(H)₂Cl(PRR'₂)₃ (when R' = Ph, and R = Me or Cy) (Lorenzini et al., 2008a) or, if the reaction is carried out under Ar, the phosphine–phosphinite derivatives RhCl(PRR'₂)[P,P-R'(R)POCH₂P(CH₂OH)₂] and trace amounts of the trans-RhCl(CO)(PRR'₂)₂ species (Lorenzini et al., 2007b). The THP plays a critical role in formation of the dihydrides and the carbonyl complexes (Lorenzini et al., 2008a); the CO ligand is thought to result from decarbonylation of formaldehyde (Beck et al., 1999), which can be readily formed from transition metal–THP species (Higham et al., 2004; Hoye et al., 1993). A corresponding reaction between the p-tolyl phosphine P(p-tol)₃ and RhCl(cod)(THP) has now similarly led to formation of trace amounts of trans-RhCl(CO)[P(p-tol)₃]₂ that was identified by an X-ray structure as an acetone solvated species. The complex has been synthesized previously in high yield from RhCl₃.3H₂O (Evans et al., 1990), while the method first reported 50 years ago used [RhCl(CO)₂]₂ as the precursor (Vallarino, 1957). Our structure is a further example of the 125 or so of the type with a trans-RhCl(CO) moiety associated with two trans phosphorus donor atoms (Cambridge Crystallography Data Base).

Experimental

General. The RhCl(cod)(THP) precursor complex was synthesized by our reported method (Lorenzini et al., 2007a); P(p-tol)₃ (a Strem Chemicals product), and the deuterated solvents (Cambridge Isotope Laboratory) were used as received. The reaction between these reagents was performed under Ar or H₂ using standard Schlenk techniques. ³¹P{¹H}-NMR spectra were measured in acetone-d₆/CD₃OD at room temperature (~300 K) on a Bruker AV400 spectrometer, relative to external 85% aq H₃PO₄.

trans-RhCl(CO)[P(p-tol)₃]₂.(CH₃)₂CO. P(p-tol)₃ (18.3 µl, 0.059 mmol) in acetone-d₆ (0.3 ml) was added to a yellow CD₃OD solution (0.3 ml) of RhCl(cod)(THP) (10.2 mg, 0.028 mmol) at room temperature under Ar to give rapid formation of a brown solution. Replacement of the Ar by H₂ and subsequent shaking of the vessel resulted in a yellow solution. Over 12 h, a minute quantity of X-ray quality, yellow prism crystals of trans-RhCl(CO)[P(p-tol)₃]₂.(CH₃)₂CO deposited from the solution; the ³¹P{¹H} spectrum of the solution revealed a complex mixture of species.