room temperature. Evaporation to dryness gave 3a as an orange
residue (0.082 g, 58% yield).
Complex 3b was prepared as an oil following an iden-
tical procedure, using (NBu4)(CN) (0.034 g, 0.128 mmol)
and [cis-Pt(C6F5)2(PPh2C≡CC6H4C≡CBut)(tht)] 2b (0.126 g,
0.128 mmol).
Complex 3c was prepared as a white solid following a
similar procedure by treating (NBu4)(CN) (0.147 g, 0.546 mmol)
and [cis-Pt(C6F5)2(PPh2C≡CPh)(tht)] (0.493 g, 0.546 mmol) in
CH2Cl2 (20 cm3), and treating the residue with cold i-PrOH
(5 cm3) (0.551 g, 93% yield).
Data for 4a: (Found: C, 62.72; H, 3.02%; M 1302.
C68F10H38P2Pt requires C, 62.73; H, 2.94%); m˜max/cm−1 (C≡C)
2212vw and 2179vs; (X-sens. C6F5) 799vs (br) (Nujol); dH
(CDCl3) 7.70 (8H, m), 7.54 (6H, m), 7.34 (22H, m) and 6.84
[2H, d, J(HH) 8.2] (aromatics, Ph, C6H4); dC (CDCl3) 145.1 [d,
1
1
br, J(CF) 229, C6F5], 136.9 [d, br, J(CF) 225, C6F5], 132.7
2
4
[AXXꢀ, J(CP) + J(CP) 12.3, Co, PPh2], 131.5 (s, C2), 131.4
(C8), 130.9 (s, C3), 130.6 (s, Cp, PPh2), 130.3 [AXXꢀ, four lines
are observed, J(CP) + J(CP) 65.8, Ci, PPh2], 128.5 (s, C10),
1
3
128.2 (s, C9), 128.0 [AXXꢀ, J(CP) + J(CP) 11.6, Cm, PPh2],
124.8, 122.3 (s, C7, C4), 119.5 (s, br, C1), 107.3 [AXXꢀ, 2J(CP) +
4J(CP) 15, Cb], 92.3, 88.2 (s, C6, C5) and 81.9 [d, AXXꢀ, 1J(CP) +
3
5
Data for 3a: (Found: C, 57.18; H, 5.09; N 2.46%; M 1184.
C57F10H55N2PPt requires C, 57.82; H, 4.68; N, 2.37%); m˜max/cm−1
(C≡C) 2216vw and 2177m; (CN) 2121m; (X-sens. C6F5) 799w
(br) (Nujol); dH (CDCl3) 7.91 (4H, m), 7.47 (m), 7.36 (15H,
m) (aromatics), 3.06 (8H, m, NCH2, NBu4), 1.51 (8H, m, CH2,
NBu4), 1.34 (8H, m, CH2, NBu4) and 0.94 (12H, t, CH3, NBu4);
3J(CP) 101.3, J(CaPt) ≈ 17, Ca]; dF (CDCl3) −117.7 [4Fo, m,
2
3J(PtFo) ≈ 315], −162.5 (2Fp, t) and −163.8 (4Fm, m); dP (CDCl3)
−5.69 [s, 1J(PtP) 2392]; m/z (%) FAB(+): 1303 ([M + H]+ 21),
1135 ([M − C6F5]+ 53) and 967 ([M − 2C6F5]+ 70).
Data for 4b: (Found: C, 60.60; H, 3.51%; M 1262.
C64F10H46P2Pt requires C, 60.91; H, 3.67%); m˜max/cm−1 (C≡C)
2233w and 2180s; (X-sens. C6F5) 796s and 783s (Nujol); dH
(CDCl3) 7.66 (8H, m, Ph), 7.31 (12H, m, Ph), 7.15 [d, J(HH)
8.08], 6.73 [d, J(HH) 8.08] (C6H4) and 1.31 (18H, s, C(CH3)3);
3
dF (CDCl3) −116.0 [2Fo, m, J(PtFo) ≈ 385], −117.3 [2Fo, m,
3J(PtFo) ≈ 350], −164.3 (1Fp, t), −165.1 (1Fp + 2Fm, m) and
1
−165.8 (2Fm, m); dP (CDCl3) −7.35 [s, J(PtP) 2493]; m/z (%)
ES(−): 1084 ([M − C≡CPh + H]− 100) and 941 ([M − NBu4 −
H]− 100). KM: 105 X−1 cm2 mol−1.
dC (CDCl3) 145.1 [dd, J(CF) 202, J(CF) 18, C6F5], 136.6 [d,
1
2
Data for 3b (oily product): m˜max/cm−1 (C≡C) 2236w and 2175s;
(CN) 2127s; (X-sens. C6F5) 793m and 782m (Nujol); dH (CDCl3)
7.89 (4H, m), 7.35–7.26 (10H, m) (aromatics), 2.99 (8H, m,
NCH2, NBu4), 1.45 (8H, m, CH2, NBu4), 1.28 (17H, m, CH2,
NBu4 + C(CH3)3) and 0.88 (12H, t, CH3, NBu4); dC (CDCl3)
146.8 [dt, br, 1J(CF) 227.3, C6F5], 136.1 [d, br, 1J(CF) 237,
C6F5], 133.0 [d, 2J(CP) 12.9, Co, PPh2], 131.9 [d, 1J(CP) 60.5, Ci,
br, J(CF) 290, C6F5], 132.7 [AXXꢀ, J(CP) + J(CP) 12.4, Co,
1
2
4
PPh2], 131.3 (s, C2), 130.8 (s, C3), 130.5 (s, Cp, PPh2), 129.4
[AXXꢀ, 1J(CP) + J(CP) 65.7, Ci, PPh2], 127.9 [AXXꢀ, 3J(CP) +
3
5J(CP) 11.5, Cm, PPh2], 125.8 (s, C4), 118.7 [d, J(CP) ≈ 1,
3
C1], 107.5 [AXXꢀ, J(CP) + J(CP) 15.1, Cb], 101.6 (s, C6,5),
2
4
81.3 [d, AXXꢀ, J(CP) + J(CP) 102, Ca], 78.2 (s, C5,6), 30.5
(s, C(CH3)3) and 27.7 (s, C(CH3)3); dF (CDCl3) −117.8 [4Fo,
m, 3J(PtFo) 327], −162.7 (2Fp, t) and −164.0 (4Fm, m); dP
(CDCl3) −5.90 [s, 1J(PtP) 2395]; m/z (%) FAB(+): 1260 ([M −
2H]+ 26), 1095 ([M − C6F5]+ 5), 926 ([M − 2C6F5 − 2H]+
31), 745 ([Pt(PPh2C≡CC6H4C≡CBut)(PPh2) − H]+ 13), 560
([Pt(PPh2C≡CC6H4C≡CBut) − H]+ 45) and 379 ([Pt(PPh2) −
H]+ 100).
1
3
4
4
PPh2], 131.3 [d, J(CP) 1.1, C2], 131.0 (s, C3), 130.0 [d, J(CP)
1.8, Cp, PPh2], 127.8 [d, J(CP) 11.3, Cm, PPh2], 125.4 (s, C4),
3
119.7 [d, J(CP) 3.0, C1], 106.4 [d, J(CP) 13.7, Cb], 103.8 (s,
CN), 101.3 (s, C5,6), 82.0 [d, 1J(CP) 96.4, Ca], 78.3 (s, C5,6), 58.3
(s, NCH2, NBu4), 30.5 (s, C(CH3)3), 27.7 (s, C(CH3)3), 23.4 (s,
CH2, NBu4), 19.2 (s, CH2, NBu4) and 13.1 (s, CH3, NBu4); dF
3
2
3
(CDCl3) −116.05 [2Fo, m, J(PtFo) ≈ 395], −117.32 [2Fo, m,
3J(PtFo) ≈ 350], −164.36 (1Fp, t), −165.0 (1Fp, t), 165.2 (2Fm,
m) and −165.8 (2Fm, m); dP (CDCl3) −7.49 [s, 1J(PtP) 2477].
Data for 3c: (Found: C, 54.52; H, 4.57; N 3.00%; M 1084.
C49F10H51N2PPt requires C, 54.29; H, 4.74; N, 2.58%); m˜max/cm−1
(C≡C) 2177vs; (CN) 2117vs; (X-sens. C6F5) 793vs and 785vs
(Nujol); dH (CDCl3) 7.94 (4H, m), 7.33 (11H, m) (Ph), 2.97 (8H,
m, NCH2, NBu4), 1.42 (8H, m, CH2, NBu4), 1.25 (8H, m, CH2,
NBu4) and 0.91 (12H, t, CH3, NBu4); dC (CDCl3) 146.8 [dt,
Synthesis of [(C6F5)2Pt(l-tht)(l-1jP:2g2-Ca,Cb-PPh2C≡
CC6H4C≡CR)Pt(C6F5)2] (R = Ph 5a, But 5b)
A light orange solution of [cis-Pt(C6F5)2(PPh2C≡CC6H4C≡
CPh)(tht)] 2a (0.101 g, 0.100 mmol) in CH2Cl2 (20 cm3) was
treated with [cis-Pt(C6F5)2(thf)2] (0.067 g, 0.100 mmol), and the
mixture was stirred for 1 h. By concentration to small volume
(≈ 3 cm3) and addition of cold n-hexane (5 cm3) complex 5a
precipitates as a white solid (0.071 g, 46% yield).
Complex 5b was prepared as a white solid following a similar
procedure, using [cis-Pt(C6F5)2(PPh2C≡CC6H4C≡CBut)(tht)]
2b (0.150 g, 0.152 mmol) and [cis-Pt(C6F5)2(thf)2] (0.103 g,
0.152 mmol). The mixture was reacted for 5 h and the complex
was precipitated with cold EtOH absolute (≈ 5 cm3) (0.065 g,
28% yield). From the filtrate, a mixture of starting material and
5b was isolated. Attempts to recrystallize were unsuccessful.
Longer reaction times do not improve the yield.
1
1
br, J(CF) 225, C6F5], 137.7 [dm, J(CF) 244, C6F5], 133.0 [d,
2J(CP) 12.9, J(CPt) 18, Co, PPh2], 132.1 [d, J(CP) 60.4, Ci,
3
1
4
4
PPh2], 131.6 [d, J(CP) 1.3, Co, Ph], 130.0 [d, J(CP) 2.2, Cp,
3
Ph], 129.4 (s, Cp, Ph), 128.0 (s, Cm, Ph), 127.8 [d, J(CP) 11.3,
3
2
Cm, PPh2], 121.0 [d, J(CP) 2.9, Ci, Ph], 106.7 [d, J(CP) 13.8,
3J(CPt) 18, Cb], 80.8 [d, 1J(CP) 97.3, 2J(CPt) 28.1, Ca], 58.3 (s,
NCH2, NBu4), 23.3 (s, CH2, NBu4), 19.2 (s, CH2, NBu4) and
3
13.0 (s, CH3, NBu4); dF (CDCl3) −116.1 [2Fo, m, J(PtFo) ≈
400], −117.3 [2Fo, dm, 3J(PtFo) ≈ 345], −164.4 (1Fp, t), −165.2
(1Fp + 2Fm, m) and −165.9 (2Fm, m); dP (CDCl3) −7.53 [s, br,
1J(PtP) 2505]; m/z (%) ES(+): 841 ([M − NBu4]+ 100). KM: 85
X−1 cm2 mol−1.
Data for 5a: (Found: C, 43.71; H, 1.63; S, 1.99%; M
1533. C56F20H27PPt2S requires C, 43.88; H, 1.78; S, 2.09%);
m˜max/cm−1 (C≡C) 2215m, 2173w, 2036 (sh) and 2000s (br);
(X-sens. C6F5) 803vs and 787m (Nujol); dH (CDCl3) 7.71–
7.38 (19H, aromatics, Ph, C6H4), 3.84 (2H, br s, a-CH2,
C4H8S), 3.67 (2H, br s, a-CH2, C4H8S), 1.67 (2H, br s, b-
CH2, C4H8S) and 1.54 (2H, br s, b-CH2, C4H8S); The low
solubility in CDCl3 and the low stability in CD3COCD3
precluded their characterisation by 13C NMR spectroscopy; dF
Synthesis of [cis-Pt(C6F5)2(PPh2C≡CC6H4C≡CR)2] (R = Ph
4a, But 4b)
A mixture of PPh2C≡CC6H4C≡CPh (0.250 g, 0.647 mmol) and
[{Pt(C6F5)2(tht)}2] (0.200 g, 0.162 mmol) (4 : 1 molar ratio)
in CH2Cl2 (20 cm3) was stirred for 14 h at room temperature.
Evaporation to small volume and addition of cold EtOH (≈
5 cm3), afforded [cis-Pt(C6F5)2(PPh2C≡CC6H4C≡CPh)2] 4a as
a yellow solid (0.257 g, 61% yield).
Complex 4b was prepared as a white solid following a
similar procedure, using PPh2C≡CC6H4C≡CBut 1b (0.436 g,
1.191 mmol) and [{Pt(C6F5)2(tht)}2] (0.367 g, 0.298 mmol) after
2 h of stirring (0.364 g, 48% yield).
3
(CDCl3) −117.7 [2Fo, m, J(PtFo) ≈ 405], −118.3 (2Fo, m),
3
−118.5 (2Fo, m), −119.1 [2Fo, m br, J(PtFo) ≈ 350], −156.4
(1Fp, t), −157.4 (1Fp, t), −158.5 (1Fp, t), −160.8 (1Fp + 4Fm, m)
and −163.0 (4Fm, m); dP (CDCl3) 24.46 [s, 1J(PtP) 2356]; m/z (%)
FAB(+): 1134 ([Pt(C6F5)(PPh2C≡CC6H4C≡CPh)2]+ 18), 967
([Pt(PPh2C≡CC6H4C≡CPh)2]+ 23), 915 ([Pt(C6F5)2(PPh2C≡
CC6H4C≡CPh) − H]+ 14), 836 ([Pt(C6F5)(SC4H8)(PPh2C≡
CC6H4C≡CPh) − H]+ 16), 748 ([Pt(C6F5)(PPh2C≡CC6H4C≡
3 8 6 0
D a l t o n T r a n s . , 2 0 0 4 , 3 8 5 4 – 3 8 6 3