"NON CLASSICAL BONDING IN THE NEUTRAL COMPLEX {[(C6H5)2(C6H3Me2)]P}2RuCl2"
Walter Baratta 1, Eberhardt Herdtweck 2
1 Dipartimento
di Scienze e Tecnologie Chimiche, Universita di Udine,Via Cotonificio108, I-33100 Udine, Italy; Email: inorg@dstc.uniud.it
2 Anorganisch-chemisches
Institut, Technische Universität München, Lichtenbergstrasse 4,
D-85747 Garching, Germany; Email:
drhemail@zaphod.anorg.chemie.tu-muenchen.de
Keywords: Ruthenium
complex, non classical bonding, catalysis
Figure 1
Compounds of the general formula (PR3)2X2Ru=R' (X = Cl, Br, I; PR3 = PPh3, PiPr3, PCy3, PiPr2Ph; etc) are well defined olefine metathesis catalysts, including acylic olefin metathesis, ring-opening metathesis polymerization (ROMP), alkyne polymerization, carbonyl olefination, acylic diene metathesis polymerization (ADMET), and ring-closing metathesis (RCM). Stability toward air, moisture, and acids make this class of compounds attractive for industrial applications.
The present investigation was undertaken to enlarge the capabilities of the Ru-compounds. Up to now, catalysis with small and functionalized olefines ends in low yields. [1,2 ]
The title compound (1) is the first neutral transition metal complex with two nonclassical (agostic) bonded methyl groups. [3]
1 crystalizes with 1 mol
toluene: C40H38Cl2P2Ru.C7H8; Mr
= 844.80, triclinic, P1_, a = 1060.63(7), b =
1279.63(10), c = 1498.12(10) pm, a =
90.202(8)°, b = 89.943(8)°, g =
96.509(9)°, V = 2020.2(2) ·106 pm3 ; Z = 2; rcalcd = 1.389 gcm-3, F000 = 872, m = 6.3 cm-1. 33597 data were collected at 193 K, 8706
unique data (Rint = 0.0211), R1 = 0.0235 and wR2
= 0.0569. All hydrogen atoms were located in the difference
Fourier map.
Table 1 - Bond
Distances (pm) and Angles (°)
| Ru | - Cl(1) | 239.94(4) | Cl(1) | - Ru | - Cl(2) | 168.00(2) | |
| Ru | - Cl(2) | 239.76(4) | Cl(1) | - Ru | - P(1) | 94.69(2) | |
| Ru | - P(1) | 225.82(4) | Cl(1) | - Ru | - P(2) | 92.93(2) | |
| Ru | - P(2) | 225.25(3) | Cl(1) | - Ru | - C(10) | 84.09(4) | |
| Ru | ... C(10) | 265.34(16) | Cl(1) | - Ru | - C(40) | 89.17(4) | |
| Ru | ... C(40) | 264.86(16) | Cl(2) | - Ru | - P(1) | 92.42(2) | |
| P(1) | - C(11) | 184.74(14) | Cl(2) | - Ru | - P(2) | 95.05(2) | |
| P(1) | - C(21) | 183.16(12) | Cl(2) | - Ru | - C(10) | 87.94(4) | |
| P(1) | - C(31) | 183.83(14) | Cl(2) | - Ru | - C(40) | 83.75(4) | |
| P(2) | - C(41) | 185.28(13) | P(1) | - Ru | - P(2) | 101.91(1) | |
| P(2) | - C(51) | 183.68(13) | P(1) | - Ru | - C(10) | 78.17(4) | |
| P(2) | - C(61) | 182.79(14) | P(1) | - Ru | - C(40) | 176.14(4) | |
| P(2) | - Ru | - C(10) | 177.01(4) | ||||
| C(10) | -C(12) | 150.2(2) | P(2) | - Ru | - C(40) | 77.94(4) | |
| C(40) | -C(46) | 150.0(2) | C(10) | - Ru | - C(40) | 102.18(5) |