Dinuclear Olefin and Alkyne Complexes of Platinum(II)
1
which was filtered off, washed with diethyl ether (2ϫ2 mL), and
Reaction with tBuCϵCtBu: H NMR (200 MHz, 300 K, CD2Cl2):
dried in vacuo.
δ = 1.48 [s, 36 H, C(CH3)3, 12], 1.51 [s, 36 H, C(CH3)3, 12], 1.47
[s, 9 H, C(CH3)3, 9], 4.55 (s, d, 2JPt,H = 55 Hz, 4 H, =CH2, 9), 4.70
R/RЈ = Me/Me (4): Yield 52 mg, 81%. 1H NMR (200 MHz, 300 K,
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(s, d, JPt,H = 56 Hz, 8 H, =CH2, 10) ppm. 13C NMR (50.3 MHz,
CD2Cl2): δ = 1.61 (s, d, JPt,H = 18.7 Hz, 12 H, CH3) ppm. 13C
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300 K, CDCl3): δ = 27.9 [s, C(CH3)3], 30.4 [s, C(CH3)3, 12], 31.4
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NMR (50.29 MHz, 300 K, CDCl3): δ = 8.8 (s, d, JPt,C = 15 Hz,
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[s, C(CH3)3, 12], 31.7 [s, C(CH3)3, 9], 80.4 (s, d, JPt,C = 138 Hz,
CH3), 104.1 (s, d, 1JPt,C = 145 Hz, C4) ppm. 195Pt NMR (107 MHz,
300 K, CDCl3): δ = –3168 (s) ppm. C8H12Cl2Pt (374.17): calcd. C
25.68, H 3.23, Cl 18.95; found C 25.56, H 3.52, Cl 19.02.
1
1
=CH2, 9), 80.7 (s, d, JPt,C = 221 Hz, ϵC, 12), 80.6 (s, d, JPt,C
=
1
231 Hz, ϵC, 12), 84.3 (s, 10, =CH2), 85.9 (s, d, JPt,C = 151 Hz,
ϵC, 9) ppm. 195Pt NMR (86.0 MHz, 300 K, CD2Cl2): δ = –1958
(s, 12), –1995 (s, 12), –3143 (s, 9) ppm.
1
R/RЈ = Et/Et (5): Yield 56 mg, 76%. H NMR (200 MHz, 300 K,
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CD2Cl2): δ = 1.28 (t, JH,H = 7.47 Hz, 12 H, CH2CH3), 2.01 (q,
Synthesis of [{PtCl2(RCϵCtBu)}2] (R = Me, 11; R = tBu, 12): The
requisite alkyne (0.76 mmol) was added at room temperature to
a suspension of [{PtCl2(H2C=CH2)}2] (1, 186 mg, 0.316 mmol) in
CHCl3 (3 mL), resulting in a deep red solution. After having been
stirred at room temperature for 24 h, the solution was reduced to
1 mL and layered with diethyl ether (1 mL)/n-pentane (2–3 mL),
resulting in precipitation of the requisite complex, which was fil-
tered off, washed with small amounts of n-pentane, and dried in
vacuo.
3JH,H = 7.47 Hz, 8 H, CH2CH3) ppm. 13C NMR (50.29 MHz,
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300 K, CDCl3): δ = 10.9 (s, d, JPt,C = 14.9 Hz, CH2CH3), 18.1 (s,
2
1
d, JPt,C = 12.6 Hz, CH2CH3), 106.3 (s, d, JPt,C = 150 Hz, C4)
ppm. 195Pt NMR (107 MHz, 300 K, CDCl3): δ = –3265 (s) ppm.
C12H20Cl2Pt (430.27): calcd. C 33.49, H 4.68, Cl 16.48; found C
33.00, H 4.84, Cl 16.43.
R/RЈ = Me/nPr (6): Yield 51 mg, 73%. 1H NMR (200 MHz, 300 K,
CD2Cl2): δ = 0.98 (t, 3JH,H = 7.32 Hz, 6 H, CH2CH3), 0.99 (t, 3JH,H
= 7.32 Hz, 6 H, CH2CH3), 1.62 (s, 6 H, CH3), 1.63 (s, 6 H, CH3),
1.66 (m, 8 H, CH2CH3), 1.90 (m, 8 H, CH2CH2) ppm. 13C NMR
(50.29 MHz, 300 K, CDCl3): δ = 9.26 (s, d, 3JPt,C = 12.8 Hz, CH3),
R/RЈ = Me/tBu (11): Yield 206 mg, 90%. 1H NMR (200 MHz,
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300 K, CD2Cl2): δ = 1.61 [s, 18 H, C(CH3)3], 2.26 (s, d, JPt,H
=
32 Hz, 6 H, CH3) ppm. 13C NMR (50.29 MHz, 300 K, CDCl3): δ
= 7.9 (s, d, JPt,C = 22 Hz, CH3), 26.9 [s, C(CH3)3], 30.0 [s,
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9.38 (s, d, JPt,C = 14.4 Hz, CH3), 14.41 (s, CH3), 14.49 (s, CH3),
2
3
3
19.48 (s, d, JPt,C = 16.0 Hz, CH2), 19.78 (s, d, JPt,C = 15.3 Hz,
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C(CH3)3], 69.4 (s, ϵC), 69.7 (s, ϵC), 70.0 (s, d, JPt,C = 190 Hz,
2
2
CH2), 25.86 (s, d, JPt,C = 11.6 Hz, CH2), 26.18 (s, d, JPt,C
=
ϵC), 79.4 (s, ϵC), 79.5 (s, d, 1JPt,C = 228 Hz, ϵC), 79.7 (s, d, 1JPt,C
= 224 Hz, ϵC) ppm. 195Pt NMR (107 MHz, 300 K, CD2Cl2): δ =
–1971 (s), –1960 (s), –1955 (s) ppm. C14H24Cl4Pt2 (724.31): calcd.
C 23.21, H 3.34; found C 23.63, H 3.58.
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11.6 Hz, CH2), 99.2 (s, C4), 102.8 (s, d, JPt,C = 148 Hz, C4), 103.3
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1
(s, d, JPt,C = 159 Hz, C4), 106.9 (s, d, JPt,C = 158 Hz, C4) ppm.
195Pt NMR (107 MHz, 300 K, CDCl3): δ = –3180 (s), –3186 (s)
ppm. C12H20Cl2Pt (430.27): calcd. C 33.49, H 4.68, Cl 16.48; found
C 33.13, H 4.89, Cl 16.45.
R/RЈ = tBu/tBu (12): Yield 242 mg, 95%. 1H NMR (200 MHz,
300 K, CD2Cl2): δ = 1.48 [s, 36 H, C(CH3)3], 1.51 [s, 36 H,
C(CH3)3] ppm. 13C NMR (50.29 MHz, 300 K, CDCl3): δ = 29.8 [s,
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R/RЈ = Me/Ph (7): Yield 51 mg, 60%. H NMR (200 MHz, 300 K,
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2
3
CD2Cl2): δ = 1.90 (s, d, JPt,H = 20 Hz, 12 H, CH3), 7.30–7.49 (m,
C(CH3)3], 29.9 [s, d, JPt,C = 21 Hz, C(CH3)3], 30.3 [s, d, JPt,C
=
12 H, m-H/p-H), 7.53–7.77 (m, 8 H, o-H) ppm. 13C NMR
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21 Hz, C(CH3)3], 30.4 [s, C(CH3)3], 81.1 (s, d, JPt,C = 230.8 Hz,
ϵC), 81.2 (s, ϵC) ppm. 195Pt NMR (107 MHz, 300 K, CDCl3): δ
= –1968 (s), –2005 (s) ppm. C20H36Cl4Pt2 (808.47): calcd. C 29.71,
H 4.49; found C 29.76, H 4.81.
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(50.29 MHz, 300 K, CDCl3): δ = 3.1 (s, d, JPt,C = 16 Hz, CH3),
1
1
101.5 (s, d, JPt,C = 150 Hz, C4), 110.0 (s, d, JPt,C = 156 Hz, C4),
131.9 (s, d, 2JPt,C = 21 Hz, i-C), 135.9 (s, m-C), 136.8 (s, d, JPt,C
=
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21 Hz, o-C), 138.7 (s, p-C) ppm. 195Pt NMR (107 MHz, 300 K,
CDCl3): δ = –1672 (s) ppm.
Reaction between [{PtCl2(H2C=CH2)}2] (1) and But-2-yne in CDCl3:
[{PtCl2(H2C=CH2)}2] (1, 18 mg, 0.03 mmol) was placed in an
NMR tube and dissolved in CDCl3 (0.7 mL), and but-2-yne (6 mg,
0.12 mmol) was added. The course of the reaction was monitored
for up to several days by 1H and 13C NMR spectroscopic measure-
ments and showed the formation of [PtCl2(C4Me4)] (4) as main
product, and hexamethylbenzene and [PtCl2(H2C=CH2)2] (10) as
Reaction between [{PtCl2(H2C=CH2)}2] (1) and RCϵCtBu (R =
Me, tBu): A solution of the requisite alkyne (0.36 mmol) in CD2Cl2
(0.7 mL) was added at –80 °C to [{PtCl2(H2C=CH2)}2] (1, 97 mg,
0.165 mmol) and benzene (5 μL) as standard in an NMR tube. The
NMR tube was then sealed by melting and allowed to warm to
room temperature. The courses of the reactions were monitored for
up to several months by means of 1H and 13C NMR spectroscopic
measurements showing the formation of [PtCl2(H2C=CH2)-
(RCϵCtBu)] (R = Me, 8; tBu, 9) as the main products and of
[PtCl2(H2C=CH2)2] (10) as well as [{PtCl2(tBuCϵCtBu)}2] (12)
and [PtCl2(C4Me2tBu2)] (16), respectively, as sideproducts.
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sideproducts. H NMR (200 MHz, 300 K, CDCl3): δ = 1.63 (s, d,
3JPt,H = 20 Hz, 12 H, CH3, 4), 2.22 [s, 18 H, C6(CH3)6], 4.70 (s, d,
2JPt,H = 56.0 Hz, 8 H, 10), 5.07 (br., =CH2) ppm. 13C NMR
(50.3 MHz, 300 K, CDCl3, after two weeks): δ = 8.9 (s, CH3, 4),
16.2 [s, C6(CH3)6], 84.3 (s, =CH2, 10), 104.1 (s, C4, 4) ppm.
Reaction between [{PtCl2(H2C=CH2)}2] (1) and Acetone:
[{PtCl2(H2C=CH2)}2] (1, 18 mg, 0.03 mmol) was placed in an
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Reaction with MeCϵCtBu: H NMR (200 MHz, 300 K, CD2Cl2):
δ = 1.39 [s, C(CH3)3, 18 H, 16], 1.47 [s, 9 H, C(CH3)3, 8], 1.77 (s, NMR tube and dissolved in [D6]acetone (0.7 mL). The course of
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d, JPt,H = 21 Hz, 6 H, CH3, 16), 2.26 (s, d, JPt,H = 31 Hz, 3 H,
the reaction was monitored for up to several days by 13C and 195Pt
NMR spectroscopic measurements and showed the formation of
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CH3, 8), 4.47–4.56 (m, dm, JPt,H = 60 Hz, 4 H, =CH2, 8), 4.70 (s,
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d, JPt,H = 56 Hz, 8 H, =CH2, 10) ppm. 13C NMR (50.3 MHz, [PtCl2(Me2CO)(H2C=CH2)] (18) as main product and of 4-hy-
3
300 K, CDCl3): δ = 8.5 (s, d, JPt,C = 24 Hz, ϵCCH3, 8), 11.0 (s,
droxy-4-methylpentan-2-one, 4-methylpent-3-en-2-one, and higher
2
CH3, 16), 28.2 [s C(CH3)3, 16], 30.6 [s, d, JPt,C = 28 Hz, condensation products of acetone containing Me–(MeC=CH)n–
C(CH3)3, 8], 31.1 [s, d, 3JPt,C = 17 Hz, C(CH3)3, 8], 74.9 (s, d, 1JPt,C
C(O)Me (n = 5–7) units, as side products, as well as an unidentified
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= 115 Hz, ϵC, 8), 80.2 (s, d, JPt,C = 141 Hz, =CH2, 8), 84.3 (s, d,
platinum complex. 13C NMR [50.3 MHz, 300 K, (CD3)2CO]: δ =
1JPt,C = 131 Hz, =CH2, 10), 84.8 (s, d, JPt,C = 156 Hz, ϵC), 98.7 20.6 (s, =CCH3), 27.6 (s, =CCH3), 29.3 [s, =C(CH3)2OH], 31.6 (s,
1
1
1
(s, d, JPt,C = 132 Hz, =CtBu, 16), 107.8 (s, d, JPt,C = 153 Hz,
H3CCO), 31.8 (s, H3CCO), 54.6 (s, CH2), 69.3 (s, CMe2OH), 89.0
=CMe, 16) ppm. 195Pt NMR (86.0 MHz, 300 K, CD2Cl2): δ = (br., =CH2, 18), 124.8 (s, =CHCO), 154.3 (s, =CMe2), 198.3 (s,
–3145 (s, 8), –3642 (s, 10) ppm.
Eur. J. Inorg. Chem. 2012, 5881–5895
=CHCO), 210.0 (s, CH2CO) ppm. 195Pt NMR [86 MHz, 300 K,
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
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