Synthesis and Catalytic Properties of Novel Ruthenacarboranes Based on nido-[5-Me-7,8-C2B9H10]2− and nido-[5,6-Me2-7,8-C2B9H9]2− Dicarbollide Ligands
Abstract
:1. Introduction
2. Results
2.1. Synthesis of B-Methylated nido-Carboranes
2.2. Synthesis of closo-Ruthenaboranes
2.3. X-ray Diffraction Study of the Complexes
2.4. Electrochemical Studies
2.5. Catalytic Activity in Radical Polymerization
3. Experimental Part
3.1. Materials and Methods
3.2. Preparation of Carborane Ligands
3.3. Synthesis of Ruthenacarboranes
3.4. X-ray Diffraction Study
3.5. Polymerization Procedure
Supplementary Materials
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Parameter | Compound | ||||
---|---|---|---|---|---|
5 [21] | 3 [20] | 4(A) | 7 | 9(A) | |
Bond lengths, Ǻ | |||||
Ru-P(1) | 2.3670(5) | 2.3701(6) | 2.3620(8) | 2.3688(8) | 2.3509(9) |
Ru-P(2) | 2.3305(5) | 2.3382(6) | 2.3429(9) | 2.2954(8) | 2.2703(9) |
Ru-H | 1.51(3) | 1.53(3) | 1.50(4) | ||
Ru-Cl | 2.4463(5) | 2.4384(5) | 2.4278(8) | 2.3740(8) | 2.3864(8) |
Ru-C(1) | 2.258(3) | 2.220(2) | 2.281(3) | 2.240(3) | 2.202(3) |
Ru-C(2) | 2.229(2) | 2.198(2) | 2.229(3) | 2.256(3) | 2.246(3) |
Ru-B(4) | 2.315(2) | 2.296(2) | 2.322(3) | 2.251(3) | 2.249(4) |
Ru-B(7) | 2.230(2) | 2.265(2) | 2.224(4) | 2.232(3) | 2.225(4) |
Ru-B(8) | 2.282(2) | 2.298(2) | 2.266(4) | 2.291(3) | 2.260(4) |
C(1)-C(2) | 1.624(3) | 1.624(3) | 1.624(3) | 1,601(4) | 1,617(5) |
B(9)-B(12) | 1.789(4) | 1.798(4) | 1.814(6) | 1.800(5) | 1.818(8) |
B(8)-B(12) | 1.805(3) | 1.812(4) | 1.818(5) | 1.825(5) | 1.825(7) |
B(8)-B(9) | 1.804(4) | 1.810(3) | 1.816(6) | 1.836(5) | 1.833(7) |
B(10)-B(12) | 1.782(4) | 1.791(3) | 1.798(6) | 1.776(5) | 1.801(9) |
B(10)-B(9) | 1.776(3) | 1.783(4) | 1.796(5) | 1.776(5) | 1.783(8) |
B(8)-C(38) | 1.587(4) | 1.595(5) | |||
B(4)-C(32) | 1.586(5) | ||||
Valence angles, deg. | |||||
Cl-Ru-H | 136(1) | 136.40(1) | 138.5(14) | ||
P-Ru-P | 102.51(2) | 102.28(2) | 102.14(3) | 90.11(3) | 91.08(3) |
P(1)-Ru-Cl | 80.48(2) | 80.48(2) | 80.36(3) | 90.24(3) | 90.04(3) |
P(2)-Ru-Cl | 83.12(2) | 83.16(2) | 82.84(3) | 95.68(3) | 89.02(3) |
Transition | Compound | |||||||||
---|---|---|---|---|---|---|---|---|---|---|
3 | 4 | 10 [13] | 6 | 7 | 12 [13] | 11 [13] | 8 | 9 | ||
M−/M | Epa, mV | - | - | −316 | −383 | −417 | −425 | −358 | −419 | −454 |
Epc, mV | - | - | −393 | −463 | −487 | −496 | −428 | −510 | −540 | |
E1/2, mV | - | - | −354 | −423 | −452 | −461 | −393 | −464 | −497 | |
M/M+ | Epa, mV | 1010 | 960 | 683 | 600 | 576 | 554 | 627 | 601 | 571 |
Epc, mV | - | - | - | - | - | - | 551 | 509 | 488 | |
E1/2, mV | - | - | - | - | - | - | 589 | 554 | 530 |
Complex | Conversion | Mn × 10−3 | Mw/Mn |
---|---|---|---|
6 | 66 | 28.6 | 1.38 |
7 | 56 | 21.2 | 1.38 |
8 | 62 | 30.7 | 1.47 |
9 | 94 | 39.2 | 1.34 |
Identification Code | 4 | 7 | 9 |
---|---|---|---|
CCDC No | 2117788 | 2117789 | 2117790 |
Empirical formula | C32H44B9ClP2Ru | C32H41B9ClP2Ru | C32H39B9ClP2Ru CH2Cl2 |
Molecular weight | 724.42 | 721.40 | 804.31 |
Crystal size (mm) | 0.16 × 0.10 × 0.06 | 0.22 × 0.16 × 0.02 | 0.16 × 0.12 × 0.04 |
Temperature (K) | 150(2) | 100(2) | 100(2) |
Crystal system | monoclinic | monoclinic | monoclinic |
Space group | P21/c | P21/c | P21/n |
a (Å) | 16.8803(10) | 13.9369(18) | 11.0895(3) |
b (Å) | 20.5774(12) | 12.4716(16) | 18.9868(5) |
c (Å) | 20.9312(12) | 20.085(3) | 34.9643(10) |
β (deg) | 106.242(2) | 93.786(4) | 90.0597(10) |
V (Å3) | 6980.3(7) | 3483.5(8) | 7361.9(3) |
Z | 8 | 4 | 8 |
Dcalcd (g.cm–3) | 1.379 | 1.376 | 1.451 |
linear absorption μ (cm–1) | 6.41 | 6.42 | 7.56 |
Tmin/Tmax | 0.904/0.963 | 0.913/0.987 | 0.898/0.970 |
2θmax (deg) | 56 | 60 | 56 |
Reflections collected | 90,541 | 70,986 | 70,362 |
Independent reflections (Rint) | 16,854 (0.0878) | 10,170 (0.0659) | 17,778 (0.0618) |
Observed reflections (I > 2σ(I)) | 11,813 | 8543 | 13,228 |
Number of parameters | 900 | 440 | 938 |
R1 (on F for I > 2σ(I)) a | 0.0419 | 0.0570 | 0.0474 |
wR2 (on F2 for all data) b | 0.0918 | 0.0985 | 0.1088 |
GOOF | 1.024 | 1.177 | 1.029 |
Largest diff. peak/hole (e Å−3) | 0.506/−0.710 | 1.257/−1.175 | 1.163/−1.081 |
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Grishin, I.D.; Zimina, A.M.; Anufriev, S.A.; Knyazeva, N.A.; Piskunov, A.V.; Dolgushin, F.M.; Sivaev, I.B. Synthesis and Catalytic Properties of Novel Ruthenacarboranes Based on nido-[5-Me-7,8-C2B9H10]2− and nido-[5,6-Me2-7,8-C2B9H9]2− Dicarbollide Ligands. Catalysts 2021, 11, 1409. https://0-doi-org.brum.beds.ac.uk/10.3390/catal11111409
Grishin ID, Zimina AM, Anufriev SA, Knyazeva NA, Piskunov AV, Dolgushin FM, Sivaev IB. Synthesis and Catalytic Properties of Novel Ruthenacarboranes Based on nido-[5-Me-7,8-C2B9H10]2− and nido-[5,6-Me2-7,8-C2B9H9]2− Dicarbollide Ligands. Catalysts. 2021; 11(11):1409. https://0-doi-org.brum.beds.ac.uk/10.3390/catal11111409
Chicago/Turabian StyleGrishin, Ivan D., Anastasiya M. Zimina, Sergey A. Anufriev, Nadezhda A. Knyazeva, Alexander V. Piskunov, Fedor M. Dolgushin, and Igor B. Sivaev. 2021. "Synthesis and Catalytic Properties of Novel Ruthenacarboranes Based on nido-[5-Me-7,8-C2B9H10]2− and nido-[5,6-Me2-7,8-C2B9H9]2− Dicarbollide Ligands" Catalysts 11, no. 11: 1409. https://0-doi-org.brum.beds.ac.uk/10.3390/catal11111409