{1,3-Bis[(diphenyl­phosphanyl-κP)­oxy]propane}dicarbonyl­iron(0)

Abstract

The structure of the title compound, [Fe(C₂₇H₂₆O₂P₂)(CO)₂], exhibits a distorted tetra­hedral coordination [bond angle range = 96.31 (12)–119.37 (4)°], comprising two P-atom donors from the chelating 1,3-bis­[(diphenyl­phosphan­yl)­oxy]propane ligand [Fe—P = 2.1414 (10) and 2.1462 (10) Å] and two carbonyl ligands [Fe—C = 1.763 (4) and 1.765 (3) Å].

Related literature

For a related carbonyl­ation reaction, see: Klein et al. (2003 ▶). For general background to metal complexes with the 1,3-bis­[(diphenyl­phosphino)­oxy]propane ligand, see: Pandarus et al. (2008 ▶); Xu et al. (2009 ▶).

Experimental

Crystal data

• [Fe(C₂₇H₂₆O₂P₂)(CO)₂]

• M _r = 556.29

• Monoclinic,

• a = 12.589 (3) Å

• b = 15.191 (3) Å

• c = 14.384 (3) Å

• β = 106.14 (3)°

• V = 2642.4 (11) ų

• Z = 4

• Mo Kα radiation

• μ = 0.73 mm⁻¹

• T = 293 K

• 0.27 × 0.20 × 0.15 mm

Data collection

• Bruker SMART CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.828, T _max = 0.899

• 17176 measured reflections

• 5590 independent reflections

• 3864 reflections with I > 2σ(I)

• R _int = 0.080

Refinement

• R[F ² > 2σ(F ²)] = 0.049

• wR(F ²) = 0.094

• S = 0.99

• 5590 reflections

• 325 parameters

• H-atom parameters constrained

• Δρ_max = 0.55 e Å⁻³

• Δρ_min = −0.30 e Å⁻³

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); data reduction: SAINT; 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

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

supplementary crystallographic information

Comment

In recent years, the three-coordinated phosphine-based pincer (PCP) ligands with an aliphatic backbone have attracted much attention (Pandarus et al., 2008). Sometimes the ligand backbone has been found to be too flexibile to be metallated. We have reported that the central sp³ C—H bond of (Ph₂POCH₂)₂CH₂ could be activated by Fe(PMe₃)₄Me₂ to afford metallated PCP pincer compounds at room temperature (Xu et al., 2009). When a solution of (Ph₂POCH₂)₂CH₂ was mixed with Fe(PMe₃)₄, and then placed under an atmosphere of CO at 273 K, the title compound [1,3-bis((diphenylphosphino)oxy)propane]bis(carbonyl)iron(0) (I) was formed. In this, the PMe₃ ligands were replaced by CO. A similar carbonylation reaction was reported by Klein et al. (2003).

The molecular structure of the title compound is shown in Fig. 1. The Fe is coordinated by two phosphane P atoms from the chelating (Ph₂POCH₂)₂CH₂ ligand and two carbonyl C atoms, the complex exhibiting a distorted tetrahedral stereochemistry [Fe–P, 2.1414 (10), 2.1462 (10) Å; Fe–C, 1.763 (4), 1.765 (3) Å; bond angle range, 96.31 (12)–119.37 (4)°].

Experimental

Standard vacuum techniques were used in manipulations of volatile and air sensitive material. The title compound was synthesized by combining a solution of (Ph₂POCH₂)₂CH₂ (406 mg, 0.90 mmol) in 20 ml of diethylether with Fe(PMe₃)₄ (324 mg, 0.90 mmol) in 20 ml of diethylether at 273 K, at which time the color changed from yellow to red. After stirring for 12 h, the solution was placed under an atmosphere of CO at 273 K for a further 12 h, resulting in a color change back to yellow, after which the solution was concentrated and filtered. Yellow crystals (310 mg, 62% yield) were obtained by recrystallization from a diethylether solution maintained at 253 K.

Refinement

Hydrogen atoms were included in the refinement at calculated positions (C–H_aromatic = 0.93 Å; C–H_aliphatic = 0.97 Å) and treated as riding models, with Uiso(H) = 1.2 (1.5 for alkyl groups) times Ueq(C).

Figures

Fig. 1.

Atom numbering scheme for (I) with non-H atoms shown as 30% probability displacement ellipsoids.

Crystal data

[Fe(C27H26O2P2)(CO)2]	F(000) = 1152
Mr = 556.29	Dx = 1.398 Mg m−3
Monoclinic, P21/n	Melting point: 385 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 12.589 (3) Å	Cell parameters from 17176 reflections
b = 15.191 (3) Å	θ = 1.9–26.8°
c = 14.384 (3) Å	µ = 0.73 mm−1
β = 106.14 (3)°	T = 293 K
V = 2642.4 (11) Å3	Block, yellow
Z = 4	0.27 × 0.20 × 0.15 mm

Data collection

Bruker SMART CCD area-detector diffractometer	5590 independent reflections
Radiation source: fine-focus sealed tube	3864 reflections with I > 2σ(I)
graphite	Rint = 0.080
φ and ω scans	θmax = 26.8°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→14
Tmin = 0.828, Tmax = 0.899	k = −19→15
17176 measured reflections	l = −18→18

Refinement

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.094	H-atom parameters constrained
S = 0.99	w = 1/[σ2(Fo2) + (0.035P)2] where P = (Fo2 + 2Fc2)/3
5590 reflections	(Δ/σ)max = 0.001
325 parameters	Δρmax = 0.55 e Å−3
0 restraints	Δρmin = −0.30 e Å−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Fe1	0.86496 (4)	0.14441 (3)	0.60132 (3)	0.01955 (11)
P1	0.80915 (7)	0.11051 (5)	0.72478 (5)	0.02269 (17)
P2	0.94395 (6)	0.26876 (5)	0.59809 (5)	0.02229 (17)
C1	0.6609 (3)	0.1013 (2)	0.7101 (2)	0.0233 (6)
C2	0.5887 (3)	0.0808 (2)	0.6205 (2)	0.0310 (7)
H2	0.6157	0.0750	0.5669	0.037*
C3	0.4769 (3)	0.0689 (3)	0.6105 (2)	0.0363 (8)
H3	0.4296	0.0545	0.5503	0.044*
C4	0.4353 (3)	0.0783 (2)	0.6893 (2)	0.0337 (8)
H4	0.3603	0.0702	0.6825	0.040*
C5	0.5061 (3)	0.0997 (2)	0.7781 (2)	0.0314 (7)
H5	0.4782	0.1069	0.8311	0.038*
C6	0.6177 (3)	0.1107 (2)	0.7895 (2)	0.0281 (7)
H6	0.6645	0.1245	0.8501	0.034*
C7	0.8558 (3)	0.0063 (2)	0.7873 (2)	0.0262 (7)
C8	0.8773 (3)	−0.0665 (2)	0.7358 (2)	0.0310 (7)
H8	0.8735	−0.0605	0.6706	0.037*
C9	0.9041 (3)	−0.1472 (2)	0.7806 (2)	0.0361 (8)
H9	0.9192	−0.1949	0.7458	0.043*
C10	0.9086 (3)	−0.1566 (2)	0.8773 (2)	0.0356 (8)
H10	0.9250	−0.2112	0.9071	0.043*
C11	0.8887 (3)	−0.0852 (2)	0.9300 (2)	0.0342 (8)
H11	0.8927	−0.0916	0.9952	0.041*
C12	0.8629 (3)	−0.0040 (2)	0.8852 (2)	0.0290 (7)
H12	0.8502	0.0440	0.9208	0.035*
C14	0.9435 (3)	0.2174 (2)	0.8523 (2)	0.0280 (7)
H14A	0.9913	0.1969	0.8143	0.034*
H14B	0.9749	0.1985	0.9188	0.034*
C15	0.9355 (3)	0.3167 (2)	0.8480 (2)	0.0276 (7)
H15A	0.8859	0.3362	0.8847	0.033*
H15B	1.0079	0.3416	0.8779	0.033*
C16	0.8941 (3)	0.3508 (2)	0.7457 (2)	0.0267 (6)
H16A	0.8238	0.3236	0.7135	0.032*
H16B	0.8834	0.4140	0.7464	0.032*
C18	0.8717 (2)	0.3468 (2)	0.5048 (2)	0.0246 (6)
C19	0.8872 (3)	0.4367 (2)	0.5213 (2)	0.0295 (7)
H19	0.9362	0.4564	0.5785	0.035*
C20	0.8308 (3)	0.4973 (2)	0.4537 (2)	0.0347 (8)
H20	0.8409	0.5572	0.4662	0.042*
C21	0.7590 (3)	0.4685 (2)	0.3673 (2)	0.0350 (8)
H21	0.7213	0.5090	0.3215	0.042*
C22	0.7440 (3)	0.3796 (3)	0.3498 (2)	0.0352 (8)
H22	0.6965	0.3602	0.2918	0.042*
C23	0.7994 (3)	0.3186 (2)	0.4183 (2)	0.0294 (7)
H23	0.7881	0.2587	0.4062	0.035*
C24	1.0822 (3)	0.2664 (2)	0.5825 (2)	0.0241 (6)
C25	1.1746 (3)	0.2932 (2)	0.6554 (2)	0.0309 (7)
H25	1.1658	0.3147	0.7134	0.037*
C26	1.2795 (3)	0.2883 (3)	0.6426 (3)	0.0376 (8)
H26	1.3408	0.3058	0.6920	0.045*
C27	1.2931 (3)	0.2572 (3)	0.5554 (3)	0.0401 (9)
H27	1.3632	0.2545	0.5460	0.048*
C28	1.2025 (3)	0.2307 (3)	0.4837 (2)	0.0412 (9)
H28	1.2115	0.2097	0.4256	0.049*
C29	1.0982 (3)	0.2345 (3)	0.4964 (2)	0.0365 (8)
H29	1.0377	0.2156	0.4471	0.044*
C30	0.7896 (3)	0.1023 (2)	0.4877 (2)	0.0328 (8)
C31	0.9862 (3)	0.0802 (2)	0.6249 (2)	0.0351 (8)
O1	0.7392 (2)	0.0776 (2)	0.41268 (18)	0.0520 (7)
O2	1.0661 (2)	0.0395 (2)	0.6391 (2)	0.0513 (7)
O3	0.83459 (18)	0.18051 (15)	0.81476 (13)	0.0262 (5)
O4	0.97462 (18)	0.33011 (14)	0.69448 (14)	0.0261 (5)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Fe1	0.0221 (2)	0.0190 (2)	0.02022 (18)	−0.0018 (2)	0.01025 (15)	−0.00077 (17)
P1	0.0277 (4)	0.0196 (4)	0.0234 (3)	0.0002 (3)	0.0115 (3)	0.0013 (3)
P2	0.0239 (4)	0.0228 (4)	0.0225 (3)	−0.0020 (3)	0.0104 (3)	−0.0002 (3)
C1	0.0275 (17)	0.0175 (15)	0.0284 (14)	0.0019 (13)	0.0136 (12)	0.0040 (12)
C2	0.0341 (19)	0.0316 (18)	0.0306 (15)	−0.0026 (15)	0.0145 (13)	−0.0005 (13)
C3	0.033 (2)	0.039 (2)	0.0369 (17)	−0.0055 (16)	0.0100 (14)	−0.0038 (15)
C4	0.0288 (19)	0.0318 (19)	0.0442 (18)	−0.0003 (15)	0.0163 (14)	0.0019 (15)
C5	0.0348 (19)	0.0283 (18)	0.0369 (16)	0.0054 (15)	0.0198 (14)	0.0042 (14)
C6	0.0331 (18)	0.0277 (17)	0.0263 (14)	0.0038 (15)	0.0130 (13)	0.0050 (12)
C7	0.0248 (17)	0.0256 (17)	0.0292 (15)	−0.0013 (14)	0.0094 (12)	0.0011 (12)
C8	0.0336 (19)	0.0287 (19)	0.0332 (16)	−0.0018 (15)	0.0132 (14)	0.0005 (13)
C9	0.0334 (19)	0.0242 (17)	0.0494 (18)	0.0038 (16)	0.0095 (15)	−0.0026 (16)
C10	0.0270 (18)	0.030 (2)	0.0446 (18)	0.0009 (15)	0.0011 (14)	0.0128 (15)
C11	0.0318 (19)	0.035 (2)	0.0344 (16)	0.0019 (16)	0.0061 (14)	0.0073 (14)
C12	0.0289 (18)	0.0275 (18)	0.0310 (15)	0.0014 (14)	0.0090 (13)	0.0025 (13)
C14	0.0313 (17)	0.0315 (18)	0.0215 (13)	0.0009 (15)	0.0079 (12)	0.0011 (12)
C15	0.0315 (18)	0.0294 (17)	0.0242 (14)	−0.0069 (14)	0.0113 (12)	−0.0064 (12)
C16	0.0303 (17)	0.0236 (16)	0.0300 (14)	0.0009 (15)	0.0144 (12)	−0.0033 (13)
C18	0.0249 (16)	0.0243 (16)	0.0281 (14)	0.0008 (14)	0.0131 (12)	0.0022 (12)
C19	0.0320 (19)	0.0294 (18)	0.0294 (15)	−0.0067 (14)	0.0121 (13)	−0.0010 (13)
C20	0.045 (2)	0.0235 (17)	0.0374 (17)	−0.0017 (16)	0.0145 (15)	0.0024 (14)
C21	0.038 (2)	0.032 (2)	0.0370 (17)	0.0044 (16)	0.0142 (15)	0.0112 (15)
C22	0.0351 (19)	0.041 (2)	0.0287 (15)	−0.0011 (16)	0.0078 (13)	0.0003 (13)
C23	0.0353 (19)	0.0239 (16)	0.0292 (15)	−0.0013 (14)	0.0094 (13)	−0.0004 (12)
C24	0.0267 (16)	0.0215 (15)	0.0277 (14)	0.0013 (13)	0.0137 (12)	0.0072 (12)
C25	0.0308 (18)	0.0331 (19)	0.0283 (15)	0.0019 (15)	0.0075 (13)	0.0037 (13)
C26	0.0234 (17)	0.040 (2)	0.0465 (19)	0.0029 (16)	0.0047 (14)	0.0070 (16)
C27	0.0310 (19)	0.045 (2)	0.051 (2)	0.0065 (17)	0.0230 (16)	0.0102 (17)
C28	0.036 (2)	0.056 (3)	0.0379 (18)	0.0045 (19)	0.0204 (15)	0.0033 (16)
C29	0.0315 (19)	0.048 (2)	0.0340 (16)	0.0007 (17)	0.0149 (14)	−0.0026 (15)
C30	0.0326 (19)	0.0322 (19)	0.0375 (17)	−0.0062 (16)	0.0164 (14)	−0.0004 (14)
C31	0.035 (2)	0.0329 (19)	0.0398 (17)	−0.0043 (17)	0.0143 (15)	−0.0019 (14)
O1	0.0560 (18)	0.0581 (19)	0.0394 (14)	−0.0176 (15)	0.0092 (12)	−0.0174 (13)
O2	0.0384 (16)	0.0501 (18)	0.0686 (18)	0.0134 (14)	0.0201 (13)	0.0018 (14)
O3	0.0305 (12)	0.0251 (11)	0.0260 (10)	−0.0031 (10)	0.0126 (9)	−0.0013 (8)
O4	0.0270 (11)	0.0290 (13)	0.0264 (10)	−0.0060 (9)	0.0141 (8)	−0.0047 (8)

Geometric parameters (Å, °)

Fe1—C31	1.763 (4)	C14—C15	1.513 (5)
Fe1—C30	1.765 (3)	C14—H14A	0.9700
Fe1—P2	2.1414 (10)	C14—H14B	0.9700
Fe1—P1	2.1462 (10)	C15—C16	1.509 (4)
P1—O3	1.636 (2)	C15—H15A	0.9700
P1—C1	1.824 (3)	C15—H15B	0.9700
P1—C7	1.834 (3)	C16—O4	1.443 (4)
P2—O4	1.625 (2)	C16—H16A	0.9700
P2—C24	1.816 (3)	C16—H16B	0.9700
P2—C18	1.832 (3)	C18—C23	1.389 (4)
C1—C2	1.390 (4)	C18—C19	1.390 (5)
C1—C6	1.402 (4)	C19—C20	1.382 (5)
C2—C3	1.387 (5)	C19—H19	0.9300
C2—H2	0.9300	C20—C21	1.389 (5)
C3—C4	1.382 (5)	C20—H20	0.9300
C3—H3	0.9300	C21—C22	1.377 (5)
C4—C5	1.378 (5)	C21—H21	0.9300
C4—H4	0.9300	C22—C23	1.391 (5)
C5—C6	1.378 (5)	C22—H22	0.9300
C5—H5	0.9300	C23—H23	0.9300
C6—H6	0.9300	C24—C25	1.394 (4)
C7—C12	1.395 (4)	C24—C29	1.395 (4)
C7—C8	1.399 (5)	C25—C26	1.386 (5)
C8—C9	1.382 (5)	C25—H25	0.9300
C8—H8	0.9300	C26—C27	1.395 (5)
C9—C10	1.385 (5)	C26—H26	0.9300
C9—H9	0.9300	C27—C28	1.369 (5)
C10—C11	1.385 (5)	C27—H27	0.9300
C10—H10	0.9300	C28—C29	1.377 (5)
C11—C12	1.387 (5)	C28—H28	0.9300
C11—H11	0.9300	C29—H29	0.9300
C12—H12	0.9300	C30—O1	1.152 (4)
C14—O3	1.440 (4)	C31—O2	1.150 (4)
C31—Fe1—C30	101.01 (16)	C15—C14—H14A	109.9
C31—Fe1—P2	96.31 (12)	O3—C14—H14B	109.9
C30—Fe1—P2	115.62 (12)	C15—C14—H14B	109.9
C31—Fe1—P1	99.98 (12)	H14A—C14—H14B	108.3
C30—Fe1—P1	117.64 (11)	C16—C15—C14	112.6 (2)
P2—Fe1—P1	119.37 (4)	C16—C15—H15A	109.1
O3—P1—C1	96.34 (13)	C14—C15—H15A	109.1
O3—P1—C7	101.98 (13)	C16—C15—H15B	109.1
C1—P1—C7	99.68 (14)	C14—C15—H15B	109.1
O3—P1—Fe1	117.47 (9)	H15A—C15—H15B	107.8
C1—P1—Fe1	118.84 (10)	O4—C16—C15	108.8 (2)
C7—P1—Fe1	118.60 (11)	O4—C16—H16A	109.9
O4—P2—C24	96.22 (13)	C15—C16—H16A	109.9
O4—P2—C18	101.85 (13)	O4—C16—H16B	109.9
C24—P2—C18	102.69 (14)	C15—C16—H16B	109.9
O4—P2—Fe1	119.27 (9)	H16A—C16—H16B	108.3
C24—P2—Fe1	116.88 (11)	C23—C18—C19	118.8 (3)
C18—P2—Fe1	116.62 (11)	C23—C18—P2	121.6 (3)
C2—C1—C6	118.4 (3)	C19—C18—P2	119.6 (2)
C2—C1—P1	120.6 (2)	C20—C19—C18	120.9 (3)
C6—C1—P1	120.9 (2)	C20—C19—H19	119.6
C3—C2—C1	120.6 (3)	C18—C19—H19	119.6
C3—C2—H2	119.7	C19—C20—C21	119.9 (3)
C1—C2—H2	119.7	C19—C20—H20	120.0
C4—C3—C2	120.4 (3)	C21—C20—H20	120.0
C4—C3—H3	119.8	C22—C21—C20	119.6 (3)
C2—C3—H3	119.8	C22—C21—H21	120.2
C5—C4—C3	119.3 (3)	C20—C21—H21	120.2
C5—C4—H4	120.4	C21—C22—C23	120.5 (3)
C3—C4—H4	120.4	C21—C22—H22	119.7
C6—C5—C4	121.0 (3)	C23—C22—H22	119.7
C6—C5—H5	119.5	C18—C23—C22	120.2 (3)
C4—C5—H5	119.5	C18—C23—H23	119.9
C5—C6—C1	120.3 (3)	C22—C23—H23	119.9
C5—C6—H6	119.9	C25—C24—C29	118.3 (3)
C1—C6—H6	119.9	C25—C24—P2	122.0 (2)
C12—C7—C8	118.5 (3)	C29—C24—P2	119.8 (2)
C12—C7—P1	120.9 (3)	C26—C25—C24	120.7 (3)
C8—C7—P1	120.4 (2)	C26—C25—H25	119.6
C9—C8—C7	120.9 (3)	C24—C25—H25	119.6
C9—C8—H8	119.6	C25—C26—C27	119.9 (3)
C7—C8—H8	119.6	C25—C26—H26	120.1
C8—C9—C10	119.8 (3)	C27—C26—H26	120.1
C8—C9—H9	120.1	C28—C27—C26	119.5 (3)
C10—C9—H9	120.1	C28—C27—H27	120.3
C9—C10—C11	120.3 (3)	C26—C27—H27	120.3
C9—C10—H10	119.8	C27—C28—C29	120.9 (3)
C11—C10—H10	119.8	C27—C28—H28	119.5
C10—C11—C12	119.8 (3)	C29—C28—H28	119.5
C10—C11—H11	120.1	C28—C29—C24	120.7 (3)
C12—C11—H11	120.1	C28—C29—H29	119.6
C11—C12—C7	120.6 (3)	C24—C29—H29	119.6
C11—C12—H12	119.7	O1—C30—Fe1	177.8 (3)
C7—C12—H12	119.7	O2—C31—Fe1	178.6 (3)
O3—C14—C15	109.1 (3)	C14—O3—P1	120.4 (2)
O3—C14—H14A	109.9	C16—O4—P2	121.75 (19)