Tricarbonylbis­(triphenyl­phosphane-κP)iridium(I) hexa­fluoridophosphate methanol monosolvate

Ilana Engelbrecht; Hendrik G Visser; Andreas Roodt

doi:10.1107/S1600536812035593

. 2012 Aug 23;68(Pt 9):m1187–m1188. doi: 10.1107/S1600536812035593

Tricarbonylbis(triphenylphosphane-κP)iridium(I) hexafluoridophosphate methanol monosolvate

Ilana Engelbrecht ^a,^*, Hendrik G Visser ^a, Andreas Roodt ^a

PMCID: PMC3435607 PMID: 22969480

Abstract

In the title compound, [Ir(C₁₈H₁₅P)₂(CO)₃]PF₆·CH₃OH, the Ir^I atom is coordinated by two triphenylphosphine ligands in axial sites and three carbonyl ligands in the equatorial plane of a fairly regular trigonal bipyramid: the equatorial C—Ir—C angles range from 115.45 (9) to 126.42 (10)°. The small deviations from the ideal tetrahedral geometry around the P atoms are illustrated by C—P—C angles ranging from 104.08 (9) to 106.46 (9)°. In the crystal, the molecules are linked by weak C—H⋯F, C—H⋯O and C—H⋯π interactions.

Related literature

For related complexes, see: Randall et al. (1991 ▶, 1994 ▶); Raper & McDonald (1973 ▶). For other P-donor ligands, see: Purcell et al. (1995 ▶); Otto & Roodt (2001 ▶); Otto et al. (2005 ▶); Muller et al. (2008 ▶). For their use in catalytic olefin transformation reactions, see: Haumann et al. (2004 ▶); Crous et al. (2005 ▶); Booyens et al. (2007 ▶); Ferreira et al. (2007 ▶).

Experimental

Crystal data

[Ir(C₁₈H₁₅P)₂(CO)₃]PF₆·CH₄O
M _r = 977.80
Monoclinic,
a = 16.487 (5) Å
b = 13.571 (4) Å
c = 20.903 (5) Å
β = 125.297 (5)°
V = 3817 (2) Å³
Z = 4
Mo Kα radiation
μ = 3.69 mm⁻¹
T = 100 K
0.18 × 0.14 × 0.06 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.556, T _max = 0.809
68611 measured reflections
9501 independent reflections
8699 reflections with I > 2σ(I)
R _int = 0.037

Refinement

R[F ² > 2σ(F ²)] = 0.019
wR(F ²) = 0.044
S = 1.03
9501 reflections
489 parameters
H-atom parameters constrained
Δρ_max = 1.01 e Å⁻³
Δρ_min = −0.75 e Å⁻³

Data collection: APEX2 (Bruker, 2011 ▶); cell refinement: SAINT-Plus (Bruker, 2008 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812035593/hb6932sup1.cif

e-68-m1187-sup1.cif^{(43.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812035593/hb6932Isup2.hkl

e-68-m1187-Isup2.hkl^{(455.3KB, hkl)}

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

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

Cg1, Cg2 and Cg3 are the centroids of the C11–C16, C21–C26 and C41–C46 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C15—H15⋯F3ⁱ	0.95	2.39	3.281 (3)	157
C16—H16⋯F6ⁱ	0.95	2.53	3.319 (3)	141
C42—H42⋯F6ⁱ	0.95	2.38	3.138 (3)	136
C43—H43⋯F2ⁱ	0.95	2.49	3.386 (3)	158
C45—H45⋯O01ⁱⁱ	0.95	2.50	3.281 (3)	139
C64—H64⋯F4ⁱⁱⁱ	0.95	2.47	3.200 (3)	133
O01—H01⋯F3ⁱ	0.84	2.27	3.059 (3)	157
C53—H53⋯Cg1^iv	0.95	2.68	3.523 (2)	148
C35—H35⋯Cg3^iv	0.95	2.91	3.587 (2)	129
C13—H13⋯Cg2^v	0.95	2.97	3.744 (2)	140

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) .

Acknowledgments

Financial assistance from the Department of Science and Technology (DST) of South Africa, the South African National Research Foundation (SA-NRF/THRIP), the DST–NRF centre of excellence (c*change), the University of the Free State and INKABA yeAfrica funding projects are gratefully acknowledged.

supplementary crystallographic information

Comment

P donor ligands (Muller et al., 2008; Purcell et al., 1995; Otto et al., 2005; Otto & Roodt, 2001) form part of ongoing research in different catalytic olefin transformation reactions such as hydroformylation (Haumann et al., 2004; Crous et al., 2005), metathesis (Booyens et al., 2007) and methoxycarbonylation (Ferreira et al., 2007). As part of our studies in this area, we now describe the structure of the title compound: all bond distances and angles fall within the range for similar complexes (Randall et al. 1991, 1994; Raper & McDonald, 1973).

The main fragment of the crystal structure of the title compound, [Ir(CO)₃(PPh₃)₂](PF₆).MeOH, was originally reported by Randall et al., 1991, in the trigonal form, crystallizing in the space group R3 with hydrogen sulfate as counter ion. In this case, the Ir(I) complex (Figure 1) crystallizes with one hexafluoridophosphate anion and a methanol solvent molecule in the P2₁/c spacegroup. The trigonal bipyramidal complex consists of three carbonyl groups in the equatorial plane and two triphenylphosphine ligands in the axial plane.

Similar Ir—P distances (2.3620 (8) and 2.3599 (8) Å) and P1—Ir—P2 angle of 177.047 (18) ° make the phosphine ligands equally trans. Ir—C3 distance of 1.947 (2) Å is slightly longer than for Ir—C1 and Ir—C2 distances, both equal to 1.938 (2) Å. Ir—C—O angles are close to linear (175.6 (2) - 178.8 (2) °) and C—O distances range from 1.107 (3) - 1.135 (3) Å, with C3—O3 distance the shortest. Angles between the equatorial ligands show some distortion with C2—Ir1—C3 = 115.45 (9) ° and C1—Ir1—C3 = 118.13 (9) ° compared to C2—Ir1—C1 = 126.42 (10) °. C—P—C angles range from 104.07 (9) - 106.46 (9) ° illustrating the distorted tetrahedral geometry around the P atoms.

In the crystal, weak C—H···F, C—H···O and C—H···π, interactions link the molecules into a supra-molecular network (Table 1).

Experimental

CO was bubbled through a solution of [Ir(COD)(PPh₃)₂]PF₆ (cod = 1,5-cyclooctadiene) (50.0 mg, 0.0515 mmol) in benzene while the mixture was vigorously stirred under gentle reflux. Rapid displacement of COD occurs after which all solvents were evaporated. The product was filtered after the addition of methanol and diethyl ether. Slow evaporation of methanol solution gave yellow blocks. (Yield: 40.1 mg, 82%)