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Catalytic hydrogenation using abnormal N-heterocyclic carbene palladium complexes: catalytic scope and mechanistic insights

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Catalytic Hydrogenation Using Abnormal N-Heterocyclic Carbene Palladium Complexes: Catalytic Scope and

Mechanistic Insights

Marion Heckenroth,

[a]

Vsevolod Khlebnikov,

[b]

Antonia Neels,

[c]

Peter Schurtenberger,

[d]

and

Martin Albrecht*

[a, b]

(2)

S-1

Figure S1. Time-conversion profile for the 4b-catalyzed cyclooctene hydrogenation at different temperatures.

(3)

S-2

Table S1. Temperature dependence of the equilibrium constant K.

N N N

N

Pd MeOH

MeOH (BF4)2

4b'

N N N

N

Pd

(BF4)2

5 cod

MeOH

T molar fraction 5 molar fraction 4b’ K

213 0.760 0.240 13.219

233 0.753 0.247 12.388

253 0.699 0.301 7.702

273 0.720 0.280 9.175

298 0.605 0.395 3.879

312 0.542 0.458 2.589

333 0.450 0.550 1.484

Under the applied conditions (MeOH as solvent), K results from equation 1:

K = [5] [4b’]

–1

[cod]

–1

(1)

where [cod] represents the concentration of unbound cyclooctadiene, and [cod] = [4b’].

A plot of ln(K) vs 1/T is linear within the –60 to 0 °C temperature range (Figure S2) and provides the standard enthalpy and standard entropy for this equilibrium (equation 2):

ln(K) = – Δ H° R

–1

T

–1

+ Δ S° R

–1

(2)

Figure S2. Plot of ln(K) vs 1/T.

(4)

S-3

Table S2. Crystallographic data for complexes 2, 4a, 4b, 4c, 5.

2 4a 4b 4c 5

color, shape colourless block colourless plate colourless rod orange block colourless rod crystal size/mm 0.40 × 0.40 × 0.30 0.45 × 0.45 × 0.05 0.45 × 0.30 × 0.20 0.40 × 0.35 × 0.10 0.45 × 0.35 × 0.30 empirical formula C13H20B2F8N4Pd

× 2 CH3CN

C15H22B2F8N6Pd C19H30B2F8N6Pd

C31H38B2F8N6Pd × CH3CN

C23H36B2 F8N8Pd

Fw 594.46 566.41 622.51 811.72 648.58

T/K 173(2) 173(2) 173(2) 173(2) 173(2)

cryst syst monoclinic monoclinic monoclinic monoclinic monoclinic space group P21/n (no. 14) P21/c (no. 14) P21/c (no. 14) P21/c (no. 14) P21/n (no. 14)

unit cell

a/Å 11.4368(11) 12.1881(11) 11.4832(7) 10.6896(5) 11.9038(10) b/Å 11.4788(10) 12.5443(8) 12.0296(5) 11.2230(6) 21.5551(13) c/Å 19.375(2) 14.9813(14) 19.3860(12) 31.5382(14) 22.0173(14) β/deg 103.495(11) 106.608(7) 98.470(5) 94.861(4) 90 V/Å3 2473.3(4) 2195.0(3) 2648.7(3) 3770.0(3) 5649.4

Z 4 4 4 4 8

Dcalc/g cm-3 1.596 1.714 1.561 1.430 1.525

µ/mm-1(Mo Kα) 0.827 0.927 0.776 0.565 0.729

no. of total, unique reflns 17458, 4358 41500, 5954 50369, 7185 39767, 6717 42818, 5546

Rint 0.1778 0.0658 0.0406 0.0394 0.0970

transmn range 0.174–0.646 0.537–0.947 0.738–0.867 0.782–0.905 0.789–0.816 no. paras, restr. 307, 1 296, 0 314, 16 435, 0 313, 0

R,aRw,b 0.0984, 0.2445 0.0624, 0.1616 0.0583, 0.1601 0.0501, 0.1424 0.0692, 0.1751

GOF 1.048 1.038 1.038 1.051 0.899

min, max resid density/e Å-3 –1.446, 1.393 –0.831, 0.0996 –1.628, 1.246 –0.864, 0.977 -1.717, 1.664

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