Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680301081X/na6236sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680301081X/na6236Isup2.hkl |
CCDC reference: 214794
The title compound was obtained using standard Schlenk methods under an atmosphere of carefully purified nitrogen: 4.1 ml of 0.18 M solution of Na/naphthalide was added dropwise to a solution of 0.144 g (0.439 mmol) (Et3P)2PdCl2 and 0.059 g (0.174 mmol) tBu2P—P=PtBu2(Me) in 6 ml tetrahydrofuran. This solution turned slowly dark while it was stirred for 2 d at room temperature. The reaction mixture was evaporated to dryness in vacuum and naphthalene was sublimed from the residue. The residue was dissolved in Et2O, filtered and recrystallized three times at 229 K from Et2O, yielding a small amount of [{Pd(µ-PtBu2)(PEt3)}2](Pd—Pd). 1H NMR(C6D6): δ 1.86 [PCH2, d of quartets, 2J(H,H) = 5 Hz, 2J(P,H) = 3 Hz], δ 1.52 (tBu2P, pseudo-t, J = 5.7 and 6.1 Hz), δ 1.12 [CH3, d of t, 2J(H,H) = 5 Hz, 3J(P,H) = 7.6 Hz]; 31P {1H} NMR (C6D6): δ 284.9 [PEt3, t, 2J(P,P) = 38.1 Hz], δ 14.6 (tBu2P, t) 13C {1H} (C6D6): δ 34.2 (PtBu2, CH3, t, J = 6.1 Hz), δ 30.9 [tBu2P, C, s), δ 23.5 (PCH2, d of t), δ 10.2 (CH3, s).
Data collection: CAD-4 Operations Manual (Enraf-Nonius, 1977); cell refinement: CAD-4 Operations Manual; data reduction: PROCESS MolEN (Fair, 1990); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1990).
Fig. 1. The structure of (I) (Johnson, 1976), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 25% probability level and all H atoms have been omitted. |
[Pd2(C8H18P)2(C6H15P)2] | Z = 1.0 |
Mr = 739.53 | F(000) = 386.00 |
Triclinic, P1 | Dx = 1.327 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.9820 (9) Å | Cell parameters from 24 reflections |
b = 10.935 (2) Å | θ = 11–14° |
c = 11.296 (2) Å | µ = 1.16 mm−1 |
α = 114.15 (1)° | T = 233 K |
β = 103.67 (1)° | Cut fragment, red |
γ = 101.72 (1)° | 0.40 × 0.25 × 0.25 mm |
V = 925.8 (3) Å3 |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.019 |
θ/2θ scans | θmax = 26.0°, θmin = 3.3° |
Absorption correction: empirical (using intensity measurements) (North et al., 1968) | h = −11→11 |
Tmin = 0.695, Tmax = 0.749 | k = −13→13 |
4955 measured reflections | l = −13→4 |
3623 independent reflections | 3 standard reflections every 120 min |
3266 reflections with I > 2σ(I) | intensity decay: 0.5% |
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)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.134 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.04P)2 + 8P] where P = (Fo2 + 2Fc2)/3 |
3617 reflections | (Δ/σ)max = 0.003 |
163 parameters | Δρmax = 1.30 e Å−3 |
0 restraints | Δρmin = −0.55 e Å−3 |
[Pd2(C8H18P)2(C6H15P)2] | γ = 101.72 (1)° |
Mr = 739.53 | V = 925.8 (3) Å3 |
Triclinic, P1 | Z = 1.0 |
a = 8.9820 (9) Å | Mo Kα radiation |
b = 10.935 (2) Å | µ = 1.16 mm−1 |
c = 11.296 (2) Å | T = 233 K |
α = 114.15 (1)° | 0.40 × 0.25 × 0.25 mm |
β = 103.67 (1)° |
Enraf-Nonius CAD-4 diffractometer | 3266 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) (North et al., 1968) | Rint = 0.019 |
Tmin = 0.695, Tmax = 0.749 | 3 standard reflections every 120 min |
4955 measured reflections | intensity decay: 0.5% |
3623 independent reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.134 | H-atom parameters constrained |
S = 1.03 | Δρmax = 1.30 e Å−3 |
3617 reflections | Δρmin = −0.55 e Å−3 |
163 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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. |
x | y | z | Uiso*/Ueq | ||
Pd | 0.53266 (5) | 0.93446 (5) | 0.56989 (4) | 0.02742 (15) | |
P1 | 0.35742 (18) | 0.82055 (16) | 0.33932 (15) | 0.0300 (3) | |
P2 | 0.5901 (2) | 0.81973 (17) | 0.69239 (17) | 0.0347 (4) | |
C1 | 0.4247 (8) | 0.7051 (7) | 0.2006 (6) | 0.0382 (14) | |
C2 | 0.3496 (12) | 0.6947 (12) | 0.0612 (8) | 0.072 (3) | |
H2A | 0.3647 | 0.7906 | 0.0722 | 0.094* | |
H2B | 0.2330 | 0.6401 | 0.0225 | 0.094* | |
H2C | 0.4024 | 0.6468 | −0.0018 | 0.094* | |
C3 | 0.3926 (17) | 0.5565 (10) | 0.1821 (11) | 0.092 (4) | |
H3A | 0.4215 | 0.4991 | 0.1040 | 0.119* | |
H3B | 0.2770 | 0.5133 | 0.1632 | 0.119* | |
H3C | 0.4586 | 0.5605 | 0.2670 | 0.119* | |
C4 | 0.6061 (11) | 0.7793 (12) | 0.2528 (11) | 0.085 (3) | |
H4A | 0.6567 | 0.7871 | 0.3438 | 0.111* | |
H4B | 0.6278 | 0.8747 | 0.2616 | 0.111* | |
H4C | 0.6518 | 0.7241 | 0.1871 | 0.111* | |
C5 | 0.1329 (8) | 0.7433 (7) | 0.2995 (6) | 0.0398 (14) | |
C6 | 0.0284 (9) | 0.7211 (11) | 0.1605 (9) | 0.068 (2) | |
H6A | −0.0865 | 0.6939 | 0.1509 | 0.089* | |
H6B | 0.0446 | 0.6454 | 0.0853 | 0.089* | |
H6C | 0.0595 | 0.8097 | 0.1556 | 0.089* | |
C7 | 0.0965 (10) | 0.8548 (10) | 0.4130 (9) | 0.070 (3) | |
H7A | 0.1354 | 0.9472 | 0.4166 | 0.091* | |
H7B | 0.1520 | 0.8623 | 0.5028 | 0.091* | |
H7C | −0.0212 | 0.8268 | 0.3928 | 0.091* | |
C8 | 0.0852 (12) | 0.6046 (10) | 0.3040 (13) | 0.084 (3) | |
H8A | −0.0311 | 0.5738 | 0.2891 | 0.109* | |
H8B | 0.1485 | 0.6187 | 0.3949 | 0.109* | |
H8C | 0.1074 | 0.5316 | 0.2311 | 0.109* | |
C9 | 0.4145 (9) | 0.7102 (9) | 0.7022 (9) | 0.0521 (18) | |
H9A | 0.3440 | 0.6349 | 0.6082 | 0.068* | |
H9B | 0.4527 | 0.6644 | 0.7561 | 0.068* | |
C10 | 0.3165 (12) | 0.7967 (13) | 0.7688 (11) | 0.078 (3) | |
H10A | 0.3856 | 0.8701 | 0.8639 | 0.102* | |
H10B | 0.2235 | 0.7337 | 0.7709 | 0.102* | |
H10C | 0.2771 | 0.8420 | 0.7147 | 0.102* | |
C11 | 0.6868 (10) | 0.6887 (8) | 0.6243 (8) | 0.0520 (18) | |
H11A | 0.7003 | 0.6421 | 0.6821 | 0.068* | |
H11B | 0.6139 | 0.6155 | 0.5303 | 0.068* | |
C12 | 0.8496 (13) | 0.7484 (13) | 0.6190 (13) | 0.086 (3) | |
H12A | 0.8398 | 0.8029 | 0.5687 | 0.111* | |
H12B | 0.8870 | 0.6702 | 0.5710 | 0.111* | |
H12C | 0.9282 | 0.8110 | 0.7137 | 0.111* | |
C13 | 0.7248 (10) | 0.9301 (8) | 0.8759 (7) | 0.0543 (19) | |
H13A | 0.8268 | 0.9866 | 0.8788 | 0.071* | |
H13B | 0.6739 | 0.9972 | 0.9226 | 0.071* | |
C14 | 0.7681 (12) | 0.8562 (10) | 0.9613 (9) | 0.074 (3) | |
H14A | 0.6680 | 0.7963 | 0.9577 | 0.097* | |
H14B | 0.8333 | 0.9280 | 1.0579 | 0.097* | |
H14C | 0.8310 | 0.7969 | 0.9232 | 0.097* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd | 0.0306 (2) | 0.0268 (2) | 0.0249 (2) | 0.01086 (17) | 0.00725 (17) | 0.01340 (18) |
P1 | 0.0310 (8) | 0.0274 (7) | 0.0271 (7) | 0.0087 (6) | 0.0064 (6) | 0.0118 (6) |
P2 | 0.0392 (9) | 0.0369 (8) | 0.0362 (8) | 0.0167 (7) | 0.0126 (7) | 0.0236 (7) |
C1 | 0.050 (4) | 0.031 (3) | 0.031 (3) | 0.018 (3) | 0.015 (3) | 0.010 (3) |
C2 | 0.090 (7) | 0.104 (7) | 0.041 (4) | 0.056 (6) | 0.033 (4) | 0.036 (5) |
C3 | 0.174 (12) | 0.050 (5) | 0.089 (7) | 0.064 (7) | 0.086 (8) | 0.034 (5) |
C4 | 0.045 (5) | 0.110 (8) | 0.076 (6) | 0.028 (5) | 0.029 (5) | 0.017 (6) |
C5 | 0.032 (3) | 0.043 (4) | 0.033 (3) | 0.005 (3) | 0.007 (3) | 0.015 (3) |
C6 | 0.034 (4) | 0.104 (7) | 0.058 (5) | 0.014 (4) | 0.002 (3) | 0.043 (5) |
C7 | 0.046 (5) | 0.079 (6) | 0.063 (5) | 0.013 (4) | 0.031 (4) | 0.012 (5) |
C8 | 0.056 (5) | 0.063 (6) | 0.127 (9) | 0.002 (4) | 0.019 (6) | 0.056 (6) |
C9 | 0.049 (4) | 0.059 (5) | 0.065 (5) | 0.021 (4) | 0.023 (4) | 0.042 (4) |
C10 | 0.071 (6) | 0.125 (9) | 0.084 (7) | 0.050 (6) | 0.045 (5) | 0.074 (7) |
C11 | 0.068 (5) | 0.053 (4) | 0.060 (5) | 0.038 (4) | 0.031 (4) | 0.037 (4) |
C12 | 0.078 (7) | 0.115 (9) | 0.113 (9) | 0.063 (7) | 0.062 (7) | 0.070 (8) |
C13 | 0.068 (5) | 0.050 (4) | 0.033 (4) | 0.014 (4) | 0.002 (3) | 0.021 (3) |
C14 | 0.085 (7) | 0.077 (6) | 0.047 (5) | 0.017 (5) | −0.004 (4) | 0.038 (5) |
Pd—P2 | 2.2584 (15) | C6—H6C | 0.9801 |
Pd—P1i | 2.3240 (17) | C7—H7A | 0.9801 |
Pd—P1 | 2.3293 (16) | C7—H7B | 0.9801 |
Pd—Pdi | 2.5782 (9) | C7—H7C | 0.9801 |
P1—C5 | 1.884 (7) | C8—H8A | 0.9801 |
P1—C1 | 1.884 (6) | C8—H8B | 0.9801 |
P2—C11 | 1.822 (7) | C8—H8C | 0.9801 |
P2—C9 | 1.832 (7) | C9—C10 | 1.519 (12) |
P2—C13 | 1.842 (7) | C9—H9A | 0.9800 |
C1—C2 | 1.506 (10) | C9—H9B | 0.9800 |
C1—C3 | 1.507 (10) | C10—H10A | 0.9801 |
C1—C4 | 1.509 (11) | C10—H10B | 0.9801 |
C2—H2A | 0.9801 | C10—H10C | 0.9801 |
C2—H2B | 0.9801 | C11—C12 | 1.500 (12) |
C2—H2C | 0.9801 | C11—H11A | 0.9800 |
C3—H3A | 0.9801 | C11—H11B | 0.9800 |
C3—H3B | 0.9801 | C12—H12A | 0.9801 |
C3—H3C | 0.9801 | C12—H12B | 0.9801 |
C4—H4A | 0.9801 | C12—H12C | 0.9801 |
C4—H4B | 0.9801 | C13—C14 | 1.524 (10) |
C4—H4C | 0.9801 | C13—H13A | 0.9800 |
C5—C8 | 1.515 (11) | C13—H13B | 0.9800 |
C5—C6 | 1.518 (9) | C14—H14A | 0.9801 |
C5—C7 | 1.523 (10) | C14—H14B | 0.9801 |
C6—H6A | 0.9801 | C14—H14C | 0.9801 |
C6—H6B | 0.9801 | ||
P2—Pd—P1i | 123.52 (6) | C5—C6—H6C | 109.5 |
P2—Pd—P1 | 123.77 (6) | H6A—C6—H6C | 109.5 |
P1i—Pd—P1 | 112.71 (5) | H6B—C6—H6C | 109.5 |
P2—Pd—Pdi | 179.95 (6) | C5—C7—H7A | 109.5 |
P1i—Pd—Pdi | 56.45 (4) | C5—C7—H7B | 109.5 |
P1—Pd—Pdi | 56.26 (4) | H7A—C7—H7B | 109.5 |
C5—P1—C1 | 111.7 (3) | C5—C7—H7C | 109.5 |
C5—P1—Pdi | 117.3 (2) | H7A—C7—H7C | 109.5 |
C1—P1—Pdi | 117.2 (2) | H7B—C7—H7C | 109.5 |
C5—P1—Pd | 118.3 (2) | C5—C8—H8A | 109.5 |
C1—P1—Pd | 118.5 (2) | C5—C8—H8B | 109.5 |
Pdi—P1—Pd | 67.29 (5) | H8A—C8—H8B | 109.5 |
C11—P2—C9 | 100.5 (4) | C5—C8—H8C | 109.5 |
C11—P2—C13 | 102.8 (4) | H8A—C8—H8C | 109.5 |
C9—P2—C13 | 102.7 (4) | H8B—C8—H8C | 109.5 |
C11—P2—Pd | 115.6 (2) | C10—C9—P2 | 112.3 (6) |
C9—P2—Pd | 115.8 (2) | C10—C9—H9A | 109.1 |
C13—P2—Pd | 117.1 (2) | P2—C9—H9A | 109.1 |
C2—C1—C3 | 108.4 (7) | C10—C9—H9B | 109.1 |
C2—C1—C4 | 108.5 (7) | P2—C9—H9B | 109.1 |
C3—C1—C4 | 109.0 (8) | H9A—C9—H9B | 107.9 |
C2—C1—P1 | 113.5 (5) | C9—C10—H10A | 109.5 |
C3—C1—P1 | 112.9 (5) | C9—C10—H10B | 109.5 |
C4—C1—P1 | 104.2 (5) | H10A—C10—H10B | 109.5 |
C1—C2—H2A | 109.5 | C9—C10—H10C | 109.5 |
C1—C2—H2B | 109.5 | H10A—C10—H10C | 109.5 |
H2A—C2—H2B | 109.5 | H10B—C10—H10C | 109.5 |
C1—C2—H2C | 109.5 | C12—C11—P2 | 114.6 (6) |
H2A—C2—H2C | 109.5 | C12—C11—H11A | 108.6 |
H2B—C2—H2C | 109.5 | P2—C11—H11A | 108.6 |
C1—C3—H3A | 109.5 | C12—C11—H11B | 108.6 |
C1—C3—H3B | 109.5 | P2—C11—H11B | 108.6 |
H3A—C3—H3B | 109.5 | H11A—C11—H11B | 107.6 |
C1—C3—H3C | 109.5 | C11—C12—H12A | 109.5 |
H3A—C3—H3C | 109.5 | C11—C12—H12B | 109.5 |
H3B—C3—H3C | 109.5 | H12A—C12—H12B | 109.5 |
C1—C4—H4A | 109.5 | C11—C12—H12C | 109.5 |
C1—C4—H4B | 109.5 | H12A—C12—H12C | 109.5 |
H4A—C4—H4B | 109.5 | H12B—C12—H12C | 109.5 |
C1—C4—H4C | 109.5 | C14—C13—P2 | 118.5 (6) |
H4A—C4—H4C | 109.5 | C14—C13—H13A | 107.7 |
H4B—C4—H4C | 109.5 | P2—C13—H13A | 107.7 |
C8—C5—C6 | 108.7 (7) | C14—C13—H13B | 107.7 |
C8—C5—C7 | 108.6 (7) | P2—C13—H13B | 107.7 |
C6—C5—C7 | 107.9 (7) | H13A—C13—H13B | 107.1 |
C8—C5—P1 | 113.6 (5) | C13—C14—H14A | 109.5 |
C6—C5—P1 | 112.8 (5) | C13—C14—H14B | 109.5 |
C7—C5—P1 | 104.9 (5) | H14A—C14—H14B | 109.5 |
C5—C6—H6A | 109.5 | C13—C14—H14C | 109.5 |
C5—C6—H6B | 109.5 | H14A—C14—H14C | 109.5 |
H6A—C6—H6B | 109.5 | H14B—C14—H14C | 109.5 |
Symmetry code: (i) −x+1, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Pd2(C8H18P)2(C6H15P)2] |
Mr | 739.53 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 233 |
a, b, c (Å) | 8.9820 (9), 10.935 (2), 11.296 (2) |
α, β, γ (°) | 114.15 (1), 103.67 (1), 101.72 (1) |
V (Å3) | 925.8 (3) |
Z | 1.0 |
Radiation type | Mo Kα |
µ (mm−1) | 1.16 |
Crystal size (mm) | 0.40 × 0.25 × 0.25 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | Empirical (using intensity measurements) (North et al., 1968) |
Tmin, Tmax | 0.695, 0.749 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4955, 3623, 3266 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.134, 1.03 |
No. of reflections | 3617 |
No. of parameters | 163 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.30, −0.55 |
Computer programs: CAD-4 Operations Manual (Enraf-Nonius, 1977), CAD-4 Operations Manual, PROCESS MolEN (Fair, 1990), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 1990).
Pd—P2 | 2.2584 (15) | Pd—P1 | 2.3293 (16) |
Pd—P1i | 2.3240 (17) | Pd—Pdi | 2.5782 (9) |
P2—Pd—P1i | 123.52 (6) | P1i—Pd—Pdi | 56.45 (4) |
P2—Pd—P1 | 123.77 (6) | P1—Pd—Pdi | 56.26 (4) |
P1i—Pd—P1 | 112.71 (5) | Pdi—P1—Pd | 67.29 (5) |
P2—Pd—Pdi | 179.95 (6) |
Symmetry code: (i) −x+1, −y+2, −z+1. |
Di-tert-butylphosphine–phosphanylidene–σ4-di-tert- butyl(methyl)phosphorane, tBu2P—P═PtBu2(Me) is a convenient source for the di-tert-butylphosphine-phosphanylidene ligand tBu2P—P (Fritz & Scheer, 2000; Olkowska-Oetzel & Pikies, 2003). Up to now only the Pt0 d10 ML2 metal centre was found to be capable to stabilize this ligand (Krautscheid et al., 1997). Despite of many quite similar properties, the Pt0 d10 ML2 centre does not stabilize this species. In the reaction of tBu2P—P=PtBu2(Me) and (Et3P)2PdCl2 with Na/naphthalide, instead of the expected product (Et3P)2Pd(η2-tBu2P—P), crystalline [{Pd(µ-PtBu2)(PEt3)}2](Pd—Pd), (I), was isolated among other products which could not be fully characterized. The molecular structure of (I) is shown in Fig. 1. To the best of our knowledge, only three similar examples are known, viz. [{Pd(µ-PtBu2)(PMe3)}2](Pd—Pd) (Arif et al., 1987), [{Pd(µ-PtBu2)(PtBu2H)}2](Pd—Pd) (Leoni et al., 1992) and [{Pd(µ-PcHex2)(PcHex2OPh)}2](Pd—Pd) (Sommovigo et al., 1994). The Pd—Pd distance of 2.5782 (9) Å in (I) is slightly longer than in [{Pd(µ-PtBu2)(PMe3)}2](Pd—Pd) (2.571 Å). The P2—Pd—Pd angle of 179.95 (6)° in (I) is similar to the Me3P—Pd—Pd angle in [{Pd(µ-PtBu2)(PMe3)}2](Pd—Pd) (178.4°). For related complexes with bulky phosphine ligands, an essential deviation of the R3P—Pd—Pd—PR3 moiety from linearity was observed. For [{Pd(µ-PtBu2)(PtBu2H)}2](Pd—Pd) the tBu2(H)P—Pd—Pd angle is 173.2° and for [{Pd(µ-PcHex2)(PcHex2OPh)}2](Pd—Pd) the corresponding P—Pd—Pd angle is 170.5°.