Full Papers
doi.org/10.1002/cctc.202100622
ChemCatChem
121.9 (CAr), 121.0 (CAr), 118.4 (CAr), 116.8 (CAr), 92.1 (C5(CH3)5), 45.8 (X
of ABX, N-CH2-P), 45.1 (X of ABX, N-CH2-P), 39.4 (X of ABX, Cy), 27.6
(Cy), 27.3 (X of ABX, Cy), 27.0 (X of ABX, Cy), 26.9 (X of ABX, Cy), 26.1
(Cy), 10.2 (C5(CH3)5), 4.2 (NC-CH3). 31P{1H} NMR (243 MHz, CD2Cl2): δ
General Procedure for [Ru(Cp/Cp*)(PCy2NPh2)]PF6 Complex Syn-
thesis. TlPF6 was used in this procedure. Thallium is extremely
TOXIC and due care is needed.[27] Solid waste and solution waste
contaminated with thallium were placed in a separate containers
marked for thallium waste. Glassware contaminated with thallium
were heated in water to dissolve residual thallium salts. A 4 mL vial
was charged with [RuCl(Cp)(PCy2NPh2)] (0.010–0.011 mmol, 1 eq) in
DCM (3 mL) or [RuCl(Cp*)(PCy2NPh2)] (0.010–0.011 mmol, 1 eq) in
C6H5F (3 mL) and TlPF6 (0.011 mmol, 1.1 eq). The reaction was
stirred for 2 h during which precipitation of a white solid, TlCl, and
a distinct colour change from light yellow to red was observed. The
suspension was filtered through a microfibre pipette filter to
remove the precipitate followed by solvent removal under reduced
pressure. Both complexes were isolated as red powders and stored
under inert atmosphere.
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36.0 (s, Ru-P), À 143.9 (sept, JP-F =711.2 Hz). IR (neat) ν(cm–1) 2919
(m), 2849 (m), 1655 (m), 1595 (s), 1492 (s), 1192 (s), 840 (s), 739 (m).
MALDI MS (pyrene matrix): Calc. m/z=703.3 [Ru(Cp*)(P2CyN2Ph)]+,
Obs. m/z=703.2.
[Ru(Cp*)(PPh2NPh2)(MeCN)][PF6] (2c). Yield=82%. 1H NMR (600 MHz,
CD2Cl2): δ 7.71-7.58 (m, Ph-H, 11H), 7.45-7.38 (t, Ph-H, 1H), 7.29-7.20
(m, Ph-H, 4H), 7.09-7.04 (t, Ph-H, 1H), 6.90-6.83 (m, Ph-H, 3H), 4.12–
4.02 (m, PCH2N, 4H), 3.98-3.91 (m, PCH2N, 2H), 3.88-3.81 (m, PCH2N,
2H), 2.22 (s, CH3CN, 3H), 1.36 (s, C5(CH3)5, 15H). 13C{1H} NMR
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(151 MHz, CD2Cl2): δ 153.7 (t, 3JC-P =6.9 Hz, CAr), 151.8 (t, JC-P
=
6.0 Hz, CAr), 132.2 (X of ABX, CAr), 131.6 (CAr), 130.9 (X of ABX, CAr),
130.2 (CAr), 130.2 (CAr), 130.1 (X of ABX, CAr), 127.7 (NCCH3), 122.8
(CAr), 121.1 (CAr), 119.0 (CAr), 117.4 (s, CAr), 93.9 (C5(CH3)5), 53.3 (X of
[Ru(Cp)(k2-PCy2NPh2)(N2)][PF6] (5b-N2) and [Ru(Cp)(k3-PCy2NPh2)][PF6]
(k3-(P,P,Ar)-5b). Yield=82%. IR (neat) ν(cmÀ 1) 2925 (w), 2851 (w),
1594 (w), 1492 (w), 1194 (w), 833 (s), 743 (m), 853 (m). MALDI MS
(pyrene matrix): Calc. m/z=633.21 [Ru(Cp*)(P2CyN2Ph)]+, Obs. m/z=
633.2.
ABX, N-CH2-P), 48.4 (X of ABX, N-CH2-P), 10.1 (C5(CH3)3), 4.6 (NC-CH3).
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31P{1H} NMR (162 MHz, CD2Cl2): δ 31.0 (s, Ru-P), –144.2 (sept, JP-F
=
710.0 Hz). IR (neat) ν(cm–1) 3058 (vs), 2896 (w), 2847 (w), 1659 (m),
1594 (m), 1189 (m), 832 (s), 691 (m), 556 (m). MALDI MS (pyrene
matrix): Calc. m/z=691.2 [Ru(Cp*)(P2CyN2Ph)]+, Obs. m/z=691.1.
(5b-N2). Mixture of 5b-N2 and k3-(P,P,Ar)-5b, signals identified via
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elimination of known k3-(P,P,Ar)-5b signals. Integration of H NMR
General Procedure for [RuCl(Cp/Cp*)(PCy2NPh2)] Complex Synthe-
sis. A 100 mL Schlenk flask was charge with a stir bar, [RuCl
(Cp)(PPh3)2] (0.12 mmol, 1 equiv) or [RuCl(Cp*)(PPh3)2] (0.12 mmol,
inaccurate due to mixture of signal overlap. 1H NMR (400 MHz,
CD3NO2): δ 7.17-7.07 (m, Ph-H, XH), 6.97-6.90 (m, Ph-H, XH), 6.86-
6.81 (m, Ph-H, XH), 6.67-6.61 (m, Ph-H, XH), 4.62 (C5H5, XH), 3.77-3.70
(m, PCH2N, XH), 3.64-3.60 (m, PCH2N, XH), 3.34-3.28 (m, PCH2N, XH),
2.41-2.20 (m, Cy-H, XH), 1.96-1.80 (m, Cy-H, XH), 1.72-1.66 (m, Cy-H,
XH), 1.44-1.25 (m, Cy-H, XH). 13C{1H} NMR (151 MHz, CD2Cl2): δ 155.4
(t, 3JC-P =7.1 Hz, CAr), 152.7 (t, 3JC-P =5.9 Hz, CAr), 134.5 (CAr), 130.8
(CAr), 130.7 (t, 3JC-P =3.1 Hz, CAr), 120.2 (CAr), 119.3 (CAr), 119.0 (m, CAr)
116.7 (CAr), 115.6 (s, CAr), 81.4 (C5H5), 48.6 (X of ABX, N-CH2-P), 45.5 (X
of ABX, N-CH2-P), 43.1 (X of ABX, Cy–C), 41.9 (X of ABX, Cy–C), 30.3
(Cy–C), 29.3 (Cy–C), 28.4 (X of ABX, Cy–C), 28.1 (X of ABX, Cy–C),
27.8 (X of ABX, Cy–C), 27.6 (Cy–C), 27.2 (Cy–C), 26.7 (Cy–C), 9.2
(C5CH3)5. 31P{1H} NMR (162 MHz, CD2Cl2): δ 43.9 (Ru-P, k2-P,P), À 144.7
(sept, 1JP-F =708.0 Hz, PF6).
1 equiv), PCy2NPh ligand (0.12 mmol, 1 equiv), and toluene (20 mL).
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The flask was refluxed under a flow of argon for 72 h and a colour
change from orange to yellow was observed. The solvent was
cooled to room temperature and then removed in vacuo resulting
in a yellow oil. The oil was triturated with hexanes to give a yellow
powder which was subsequently washed with hexanes (3×5 mL)
and dried under reduced pressure.
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[RuCl(Cp)(PCy2NPh2)] (3b). Yield=86%. H NMR (600 MHz, CD2Cl2): δ
7.28-7.24 (m, Ph-H, 2H), 7.22-7.17 (m, Ph-H, 2H), 7.03-6.99 (m, Ph-H,
2H), 6.90-6.86 (m, Ph-H, 1H), 6.78-6.74 (m, Ph-H, 2H), 6.71-6.67 (m,
Ph-H, 1H), 4.53 (s, Cp-H, 5H), 4.23-4.16 (m, PCH2N, 2H), 3.74-3.69 (m,
PCH2N, 2H), 3.52-3.44 (m, PCH2N, 2H), 3.39-3.33 (m, PCH2N, 2H),
2.44-2.39 (m, Cy-H, 2H), 2.12-2.05 (m, Cy-H, 2H), 2.00-1.88 (m, Cy-H,
6H), 1.83-1.77 (m, Cy-H, 2H), 1.72-1.63 (m, Cy-H, 2H), 1.46-1.29 (m,
(k3-(P,P,Ar)-5b). 1H NMR (400 MHz, CD2Cl2): δ 7.41-7.27 (m, Ph-H,
2H), 7.25-7.12 (m, Ph-H, 2H), 7.09-6.87 (m, Ph-H, 5H), 6.46-6.36 (m,
Ph-H, 1H), 4.52 (C5H5, 5H), 4.17-4.06 (m, PCH2N, 2H), 3.67-3.58 (m,
PCH2N, 2H), 3.47-3.35 (m, PCH2N, 2H), 3.31-3.20 (m, PCH2N, 2H),
2.27-2.15 (m, CyÀ H, 4H), 2.06-1.93 (m, CyÀ H, 8H), 1.90-1.78 (m,
CyÀ H, 4H), 1.52-1.43 (m, CyÀ H, 8H), 1.38-1.33 (m, CyÀ H, 2H). 13C{1H}
NMR (101 MHz, CD2Cl2): δ 152.0 (CAr), 151.3 (CAr), 133.1 (CAr), 129.9
(CAr), 122.4 (CAr), 120.9 (CAr), 118.4 (CAr), 95.8 (CAr), 79.9 (C5H5), 55.6 (P-
CH2-N), 49.3 (P-CH2-N), 40.7 (X of ABX, Cy), 29.1 (X of ABX, Cy), 27.0
(Cy), 25.9 (Cy), 18.8 (Cy). 31P{1H} NMR (162 MHz, CD2Cl2): δ 73.6 (s,
Ru-P, k3-P,P,Ar), –144.2 (sept, 1JP-F =708.0 Hz, PF6).
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Cy-H, 8H). 13C{1H} NMR (151 MHz, CD2Cl2): δ 154.2 (t, JC-P =7.0 Hz,
CAr), 150.9 (t, 3JC-P =4.1 Hz, CAr), 129.3 (CAr), 129.2 (CAr), 120.4 (CAr),
117.9 (CAr), 117.8 (CAr), 114.4 (CAr), 77.6 (C5H5), 46.7 (X of ABX, N-CH2-
P), 43.6 (X of ABX, N-CH2-P), 42.6 (X of ABX, Cy), 28.6 (Cy), 27.9 (Cy),
27.2 (X of ABX, Cy), 26.8 (X of ABX, Cy), 26.4 (Cy). 31P{1H} NMR
(212 MHz, CD2Cl2): δ 46.6 (s, Ru-P). IR (neat) ν(cm–1) 2923 (m), 2846
(m), 1596 (m), 1499 (m), 1204 (m), 913 (m), 729 (s), 691 (s). MALDI
MS (pyrene matrix): Calc. m/z=668.2 [RuCl(Cp)(P2CyNPh 2)]+, Obs. m/
z=668.1.
[Ru(Cp*)(PCy2NPh2)]PF6 (6b). Yield=88%. 1H NMR (400 MHz,
CD3NO2): δ 7.36-7.26 (m, Ph-H, 4H), 7.25-7.19 (m, Ph-H, 2H), 7.18-
7.12 (m, Ph-H, 2H), 7.03-6.92 (m, Ph-H, 2H), 4.13-4.04 (m, PCH2N, 2H),
3.96-3.88 (m, PCH2N, 2H), 3.88-3.81 (m, PCH2N, 2H), 3.53-3.41 (m,
PCH2N, 4H), 2.45-2.32 (m, Cy-H, 2H), 2.29-2.07 (m, Cy-H, 4H), 2.04-
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[RuCl(Cp*)(PCy2NPh2)] (4b) Yield=86%. H NMR (600 MHz, CD2Cl2): δ
7.27-7.16 (m, Ph-H, 4H), 7.03-6.97 (m, Ph-H, 2H), 6.96-6.91 (m, Ph-H,
2H), 6.83-6.77 (m, Ph-H, 2H), 4.08-4.00 (m, PCH2N, 2H), 3.69-3.57 (m,
PCH2N, 4H), 3.10-3.03 (m, PCH2N, 2H), 2.45-2.37 (m, Cy-H, 2H), 2.26-
2.17 (m, Cy-H, 2H), 2.07-2.00 (m, Cy-H, 2H), 1.95-1.88 (m, Cy-H, 4H),
1.81-1.74 (m, Cy-H, 2H), 1.67 (s, C5(CH3)5, 15H), 1.62-1.21 (m, Cy-H,
8H), 1.12-0.98 (m, Cy-H, 2H). 13C{1H} NMR (101 MHz, CD2Cl2): δ 154.9
(t, 3JC-P =6.5 Hz, CAr), 153.7 (t, 3JC-P =8.5 Hz, CAr), 129.7 (CAr), 120.5
(CAr), 119.8 (CAr), 118.0 (CAr), 116.2 (CAr), 89.7 (C5(CH3)5), 46.0 (X of
ABX, N-CH2-P), 42.8 (X of ABX, N-CH2-P), 41.4 (X of ABX, Cy), 28.6
(Cy), 27.9 (Cy), 27.2 (X of ABX, Cy), 28.4 (Cy), 28.1 (X of ABX, Cy), 27.9
4 (X of ABX, Cy), δ 27.1 (Cy). 31P{1H} NMR (162 MHz, CD2Cl2): δ 34.4
(Ru-P). IR (neat) ν(cm–1) 2914 (m), 2848 (m), 1590 (m), 1501 (s), 1212
(m), 738 (s), 685 (s). MALDI MS (pyrene matrix): Calc. m/z=738.3
[RuCl(Cp*)(P2CyN2Ph)]+, Obs. m/z=738.2.
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1.90 (m, Cy-H, 2H), 1.91 (t, JH-P =1.56, C5(CH3)5, 15H), 1.85-1.76 (m,
Cy-H, 4H), 1.59-1.45 (m, Cy-H, 4H), 1.44-1.20 (m, Cy-H, 6H). 13C{1H}
3
3
NMR (101 MHz, CD NO2): ): δ 153.2 (t, JC-P =7.9 Hz, C ), 152.4 (t, J
P =9.9 Hz, CAr), 1293.4 (CAr), 129.3 (CAr), 122.2 (CAr), 12A1r.3 (CAr), 119.C0-
(CAr), 117.4 (CAr), 95.8 (C5(CH3)5), 45.8 (X of ABX, N-CH2-P), 45.5 (X of
ABX, N-CH2-P), 38.2 (X of ABX, Cy), 27.4 (Cy), 26.7 (X of ABX, Cy),
25.7 (X of ABX, Cy), 9.2 (C5CH3)5. 31P{1H} NMR (162 MHz, CD3NO2): δ
1
33.5 (s, Ru-P), À 144.2 (sept, JP-F =706.2 Hz). IR (neat) ν(cmÀ 1) 2921
(w), 2580 (w), 1595 (m), 1492 (m), 1192 (m), 834 (vs), 752 (m), 595
(m). MALDI MS (pyrene matrix): Calc. m/z=703.29 [Ru-
(Cp*)(P2CyN2Ph)]+, Obs. m/z=703.3.
ChemCatChem 2021, 13, 1–13
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