Inorganic Chemistry
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OCH3); p-MeOC6H4SH, δ 5.75 (AA′XX′, 4H, m-H), 3.84 (AA′XX′,
4H, o-H), 3.02 (s, 6H, OCH3), −2.45 (s, 2H, SH). As above, the porp
m-H signals are not seen.
MeC6H4SH, δ 5.88 (AA′XX′, 4H, m-H), 3.77 (AA′XX′, 4H, o-H), 1.71
(s, 6H, CH3), −2.57 (s, 2H, SH).
Ru(TPP)(p-ClC6H4SH)2. 1H NMR: TPP, δ 8.58 (s, 8H, β-pyrrole),
8.11−8.09 (m, 8H, o-Ph), 7.57−7.47 (m, 8H, m- + p-Ph); p-
ClC6H4SH, δ 5.98 (AA′XX′, 4H, m-H), 3.50 (AA′XX′, 4H, o-H),
−2.72 (s, 2H, SH).
2.3.3. Ru(T-p-MePP)(RSH)2 (R = Me, Et, nPr, iPr, nBu, tBu, nHex, Bn,
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Ph, p-MeOC6H4). The RSH complexes with R = Me, Et, Pr, Pr, Bu,
Bn, and Ph were described previously, including isolaton of the tBuSH
complex, which confirmed the general formulation of the in situ
species.13a
Ru(TPP)(p-BrC6H4SH)2. 1H NMR: TPP, δ 8.58 (s, 8H, β-pyrrole),
8.11−8.09 (m, 8H, o-Ph), 7.57−7.47 (m, 8H, m- + p-Ph); p-
BrC6H4SH, δ 5.98 (AA′XX′, 4H, m-H), 3.49 (AA′XX′, 4H, o-H),
−2.72 (s, 2H, SH).
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Ru(T-p-MePP)(nBuSH)2. H NMR: T-p-MePP, δ 8.81 (s, 8H, β-
pyrrole), 8.21 (AA′BB′, 8H, o-C 6H4Me), 7.29 (AA′BB′, 8H, m-
C6H4Me), 2.39 (s, 12H, CH3); nBuSH, δ −0.07 (t, 6H, 3JHH = 7.28, C4
H3), −0.28 to −0.40 (m, 4H, C3H2), −1.25 to −1.35 (m, 4H, C2H2),
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2.3.5. Ru(T-p-FPP)(RSH)2 (R = Me, Et, Pr, Pr, Bu, Bu, Hex, Bn,
Ph, p-MeOC6H4). The porp m-H signals are partially hidden by the
residual solvent resonance.
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−2.06 to −2.14 (m, 4H, C1H2), −4.07 (t, 2H, JHH = 6.99, SH).
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Ru(T-p-MePP)(nHexSH)2. H NMR: T-p-MePP, δ 8.81 (s, 8H, β-
Ru(T-p-FPP)(MeSH)2. 1H NMR: T-p-FPP, δ 8.56 (s, 8H, β-
pyrrole), 8.21 (AA′BB′, 8H, o-C6H4Me), 7.30 (AA′BB′, 8H, m-
pyrrole), 7.94 (AA′BB′, 8H, o-C6H4F); MeSH, δ −2.61 (d, 6H, 3JHH
=
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C6H4Me), 2.39 (s, 12H, CH3); HexSH, δ 0.68−0.59 (m, 4H, C5H2),
7.82, CH 3), −4.36 (q, 2H, 3JHH = 7.82, SH). 19F{1H} NMR: δ −38.5
(s, p-F).
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0.56 (t, 6H, JHH = 6.90, C6H3), 0.28−0.18 (m, 4H, C4H2), −0.28 to
−0.38 (m, 4H, C3H2), −1.18 to −1.28 (m, 4H, C2H2), −2.03 to −2.11
Ru(T-p-FPP)(EtSH)2. 1H NMR: T-p-FPP, δ 8.59 (s, 8H, β-
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(m, 4H, C1H2), −4.05 (t, 2H, JHH = 7.30, SH).
pyrrole), 7.98 (AA′BB′, 8H, o-C6H4F); EtSH, δ −1.49 (t, 6H, JHH
=
=
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Ru(T-p-MePP)(p-MeOC6H4SH)2. H NMR: T-p-MePP, δ 8.73 (s,
7.23, C2H3), −2.12 to −2.23 (m, 4H, C1H2), −4.20 (t, 2H, JHH
6.97, SH). 19F{1H} NMR: δ −38.5 (s, p-F).
8H, β-pyrrole), 8.11 (AA′BB′, 8H, o-C6H4Me), 7.34 (AA′BB′, 8H, m-
C6H4Me), 2.43 (s, 12H, CH3); p-MeOC6H4SH, δ 5.73 (AA′XX′, 4H,
m-H), 3.82 (AA′XX′, 4H, o-H), 3.05 (s, 6H, OCH3), −2.49 (s, 2H,
SH).
Ru(T-p-FPP)(nPrSH)2. 1H NMR: T-p-FPP, δ 8.59 (s, 8H, β-
pyrrole), 8.00 (AA′BB′, 8H, o-C6H4F); nPrSH, δ −0.69 (t, 6H, 3JHH
=
7.32, C3H3), −1.22 to −1.34 (m, 4H, C2H2), −2.16 to −2.23 (m, 4H,
C1H2), −4.19 (t, 2H, 3JHH = 7.00, SH). 19F{1H} NMR: δ −38.5 (s, p-
F).
2.3.4. Ru(TPP)(RSH)2 (R = Me, Et, nPr, iPr, nBu, tBu, nHex, Bn, Ph, p-
MeOC6H4, p-MeC6H4, p-ClC6H4, p-BrC6H4). The ortho and meta
positions in p-XC6H4SH are relative to the SH.
Ru(T-p-FPP)(iPrSH)2. 1H NMR: T-p-FPP, δ 8.57 (s, 8H, β-
Ru(TPP)(MeSH)2. 1H NMR: TPP, δ 8.65 (s, 8H, β-pyrrole),
8.20−8.17 (m, 8H, o-Ph), 7.47−7.45 (m, 8H, m- + p-Ph); MeSH, δ
pyrrole), 7.98 (AA′BB′, 8H, o-C6H4F); iPrSH, δ −1.46 (d, 12H, 3JHH
=
6.48, C2H3), −1.74 to −1.84 (m, 2H, C1H), −4.13 (d, 2H, 3JHH = 2.75,
SH). 19F{1H} NMR: δ −38.5 (s, p-F).
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−2.59 (d, 6H, JHH = 7.51, CH3), −4.32 (q, 2H, JHH = 7.51, SH).
Ru(TPP)(EtSH)2. 1H NMR: TPP, δ 8.68 (s, 8H, β-pyrrole), 8.24−
8.21 (m, 8H, o-Ph), 7.48−7.43 (m, 8H, m- + p-Ph); EtSH, δ −1.49 (t,
6H, 3JHH = 7.41, C2H3), −2.09 to −2.18 (m, 4H, C1H2), −4.15 (t, 2H,
3JHH = 6.94, SH).
Ru(T-p-FPP)(nBuSH)2. 1H NMR: T-p-FPP, δ 8.60 (s, 8H, β-
pyrrole), 8.01 (AA′BB′, 8H, o-C6H4F); nBuSH, δ −0.11 (t, 6H, 3JHH
=
7.36, C4H3), −0.34 to −0.41 (m, 4H, C3H2), −1.26 to −1.36 (m, 4H,
C2H2), −2.13 to −2.21 (m, 4H, C1H2), −4.17 (t, 2H, JHH = 7.24,
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Ru(TPP)(nPrSH)2. 1H NMR: TPP, δ 8.68 (s, 8H, β-pyrrole), 8.25−
8.22 (m, 8H, o-Ph), 7.48−7.43 (m, 8H, m- + p-Ph); nPrSH, δ −0.68 (t,
SH). 19F{1H} NMR: δ −38.5 (s, p-F).
Ru(T-p-FPP)(tBuSH)2. 1H NMR: T-p-FPP, δ 8.60 (s, 8H, β-
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6H, JHH = 7.32, C3H3), −1.24 to −1.31 (m, 4H, C2H2), −2.12 to
t
pyrrole), 8.02 (AA′BB′, 8H, o-C6H4F); BuSH, δ −1.54 (s, 18H,
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−2.19 (m, 4H, C1H2), −4.14 (t, 2H, JHH = 6.99, SH).
C2H3), −3.96 (s, 2H, SH). 19F{1H} NMR: δ −38.5 (s, p-F).
Ru(T-p-FPP)(nHexSH)2. 1H NMR: T-p-FPP, δ 8.61 (s, 8H, β-
pyrrole), 8.03 (AA′BB′, 8H, o-C6H4F); nHexSH, δ 0.66−0.50 (m,
10H, C6H3 + C5H2), 0.24−0.14 (m, 4H, C4H2), −0.31 to −0.41 (m,
4H, C3H2), −1.19 to −1.29 (m, 4H, C2H2), −2.09 to −2.18 (m, 4H,
C1H2), −4.15 (t, 2H, 3JHH = 6.86, SH). 19F{1H} NMR: δ −38.4 (s, p-
F).
Ru(TPP)(iPrSH)2. 1H NMR: TPP, δ 8.66 (s, 8H, β-pyrrole), 8.23−
8.20 (m, 8H, o-Ph), 7.48−7.44 (m, 8H, m- + p-Ph); iPrSH, δ −1.45 (d,
12H, 3JHH = 6.63, C2H3), −1.67 to −1.81 (m, 2H, C1H), −4.07 (d, 2H,
3JHH = 3.00, SH).
Ru(TPP)(nBuSH)2. 1H NMR: TPP, δ 8.69 (s, 8H, β-pyrrole),
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8.27−8.24 (m, 8H, o-Ph), 7.48−7.44 (m, 8H, m- + p-Ph); BuSH, δ
Ru(T-p-FPP)(BnSH)2. 1H NMR: T-p-FPP, δ 8.63 (s, 8H, β-
pyrrole), 7.95 (AA′BB′, 8H, o-C6H4F); BnSH, δ 6.44−6.39 (m, 2H, p-
Ph), 6.34−6.29 (m, 4H, m-Ph), 5.15−5.12 (m, 4H, o-Ph), −1.02 (d,
4H, 3JHH = 7.43, CH2), −3.84 (t, 2H, 3JHH = 7.43, SH). 19F{1H} NMR:
δ −38.4 (s, p-F).
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−0.10 (t, 6H, JHH = 7.28, C4H3), −0.32 to −0.40 (m, 4H, C3H2),
−1.26 to −1.36 (m, 4H, C2H2), −2.09 to −2.16 (m, 4H, C1H2), −4.12
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(t, 2H, JHH = 6.97, SH).
Ru(TPP)(tBuSH)2. 1H NMR: TPP, δ 8.68 (s, 8H, β-pyrrole), 8.27−
8.24 (m, 8H, o-Ph), 7.48−7.44 (m, 8H, m- + p-Ph); tBuSH, δ −1.52 (s,
18H, C2H3), −3.89 (s, 2H, SH).
Ru(T-p-FPP)(PhSH)2. 1H NMR: T-p-FPP, δ 8.51 (s, 8H, β-
pyrrole), 7.90 (AA′BB′, 8H, o-C6H4F); PhSH, δ 6.40−6.35 (m, 2H, p-
Ph), 6.03−5.98 (m, 4H, m-Ph), 3.76−3.73 (m, 4H, o-Ph), −2.60 (s,
2H, SH). 19F{1H} NMR: δ −38.7 (s, p-F).
Ru(TPP)(nHexSH)2. 1H NMR: TPP, δ 8.69 (s, 8H, β-pyrrole),
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8.28−8.24 (m, 8H, o-Ph), 7.48−7.44 (m, 8H, m- + p-Ph); HexSH, δ
0.65−0.52 (m, 10H, C6H3 + C5H2), 0.26−0.16 (m, 4H, C4H2), −0.29
to −0.39 (m, 4H, C3H2), −1.19 to −1.29 (m, 4H, C2H2), −2.06 to
Ru(T-p-FPP)(p-MeOC6H4SH)2. 1H NMR: T-p-FPP, δ 8.53 (s, 8H,
β-pyrrole), 7.93 (AA′BB′, 8H, o-C6H4F); p-MeOC6H4SH, δ 5.70
(AA′XX′, 4H, m-H), 3.74 (AA′XX′, 4H, o-H), 2.98 (s, 6H, OCH3),
−2.58 (s, 2H, SH). 19F{1H} NMR: δ −38.8 (s, p-F).
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−2.13 (m, 4H, C1H2), −4.09 (t, 2H, JHH = 7.21, SH).
Ru(TPP)(BnSH)2. 1H NMR: TPP, δ 8.71 (s, 8H, β-pyrrole), 8.21−
8.18 (m, 8H, o-Ph), 7.46−7.41 (m, 8H, m- + p-Ph); BnSH, δ 6.43−
6.38 (m, 2H, p-Ph), 6.32−6.27 (m, 4H, m-Ph), 5.15−5.13 (m, 4H, o-
Ph), −0.98 (d, 4H, 3JHH = 7.83, CH2), −3.79 (t, 2H, 3JHH = 7.83, SH).
Ru(TPP)(PhSH)2. 1H NMR: TPP, δ 8.61 (s, 8H, β-pyrrole), 8.15−
8.12 (m, 8H, o-Ph), 7.53−7.48 (m, 8H, m- + p-Ph); PhSH, δ 6.41−
6.35 (m, 2H, p-Ph), 6.06−6.00 (m, 4H, m-Ph), 3.82−3.79 (m, 4H, o-
Ph), −2.56 (s, 2H, SH).
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2.3.6. Ru(T-p-ClPP)(RSH)2 (R = Me, Et, Pr, Pr, Bu, Bu, Hex, Bn,
Ph, p-MeOC6H4). Ru(T-p-ClPP)(MeSH)2. 1H NMR: T-p-ClPP, δ 8.52
(s, 8H, β-pyrrole), 7.87 (AA′BB′, 8H, o-C6H4Cl), 7.41 (AA′BB′, 8H,
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m-C6H4Cl); MeSH, δ −2.66 (d, 6H, JHH = 7.65, CH ), 4.41 (q, 2H,
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3JHH = 7.65, SH).
Ru(T-p-ClPP)(EtSH)2. 1H NMR: T-p-ClPP, δ 8.55 (s, 8H, β-
pyrrole), 7.92 (AA′BB′, 8H, o-C6H4Cl), 7.41 (AA′BB′, 8H, m-
Ru(TPP)(p-MeOC6H4SH)2. 1H NMR: TPP, δ 8.62 (s, 8H, β-
pyrrole), 8.18−8.15 (m, 8H, o-Ph), 7.52−7.48 (m, 8H, m- + p-Ph); p-
MeOC6H4SH, δ 5.71 (AA′XX′, 4H, m-H), 3.79 (AA′XX′, 4H, o-H),
3.03 (s, 6H, OCH3), −2.54 (s, 2H, SH).
C6H4Cl); EtSH, δ −1.51 (t, 6H, JHH = 7.25, C2H3), − 2.16 to −2.23
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(m, 4H, C1H2), −4.23 (t, 2H, JHH = 7.49, SH).
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Ru(T-p-ClPP)(nPrSH)2. 1H NMR: T-p-ClPP, δ 8.56 (s, 8H, β-
pyrrole), 7.93 (AA′BB′, 8H, o-C6H4Cl), 7.40 (AA′BB′, 8H, m-
Ru(TPP)(p-MeC6H4SH)2. 1H NMR: TPP, δ 8.61 (s, 8H, β-
pyrrole), 8.13−8.11 (m, 8H, o-Ph), 7.53−7.48 (m, 8H, m- + p-Ph); p-
C6H4Cl); PrSH, δ −0.70 (t, 6H, 3JHH = 7.18, C3H3), −1.27 to −1.35
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dx.doi.org/10.1021/ic302401m | Inorg. Chem. XXXX, XXX, XXX−XXX