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HUANG ET AL.
(C6D6, 500 MHz) δ 7.86 (d, 2, J = 8.50, Ar), 7.04 (t,
2, J = 7.00, Ar), 7.01 (m, 2, Ar), 6.51 (t, 2, J = 7.25, Ar),
2.19 (m, 4, CHMe2), 1.87 (m, 2, PdCH2), 1.56 (tt,
3, J = 7.75 and 2.25, PdCH2CH3), 1.22 (dd, 12, J = 15.75
and 8.00, CHMe2), 1.04 (dd, 12, J = 14.50 and 7.00,
CHMe2). 31P{1H} NMR (C6D6, 202 MHz) δ 37.55. 13C{1H}
NMR (C6D6, 125 MHz) δ 163.11 (t, JCP = 10.25, C),
133.48 (s, CH), 131.62 (s, CH), 121.23 (t, JCP = 18.44, C),
116.19 (t, JCP = 4.81, CH), 115.76 (t, JCP = 3.19, CH),
2.13 | Synthesis of [1a]PtnBu
The reaction was complete overnight, affording the prod-
uct as a yellow solid; yield 74%. 1H NMR (C6D6,
500 MHz) δ 7.95 (dt, 2, J = 4.25 and 2.50, Ar), 7.74 (m,
6, Ar), 7.14 (t, 4, J = 5.50, Ar), 7.00 (m, 10, Ar), 6.96 (t,
4, J = 8.00, Ar), 6.43 (t, 2, J = 7.25, Ar), 2.09 (m,
2
2, JHPt = 78.50, PtCH2), 1.55 (m, 2, CH2), 1.28 (m,
2, CH2), 0.72 (t, 3, J = 7.50, CH3). 31P{1H} NMR (C6D6,
202 MHz) δ 31.55 (1JPPt = 3126). 13C{1H} NMR (C6D6,
125 MHz) δ 162.55 (t, JCP = 10.42, C), 136.09 (s, CH),
134.20 (t, JCP = 6.90, CH), 132.93 (t, JCP = 26.86, C),
132.39 (s, CH), 130.74 (s, CH), 129.09 (t, JCP = 5.27, CH),
124.85 (t, JCP = 27.74, C), 117.73 (t, JCP = 4.39, CH),
117.15 (t, JCP = 4.39, CH), 38.27 (s, CH2), 29.04 (s, CH2),
14.71 (s, CH3), 0.17 (t, 2JCP = 5.15, 1JCPt = 619.47, PtCH2).
Anal. Calcd for C40H37NP2Pt: C, 60.91; H, 4.73; N, 1.78.
Found: C, 60.62; H, 5.02; N, 1.49.
1
2
24.88 (t, JCP = 11.19, CHMe2), 19.17 (t, JCP = 3.00,
CHMe2), 19.03 (s, PdCH2CH3), 18.25 (s, CHMe2), −6.25
2
(t, JCP
=
4.56, PdCH2CH3). Anal. Calcd for
C26H41NP2Pd: C, 58.26; H, 7.71; N, 2.61. Found: C,
58.19; H, 7.65; N, 2.50.
2.11 | Synthesis of [1a]PtEt
The reaction was complete in 48 h, affording the product
1
as a yellow solid; yield 94%. H NMR (C6D6, 300 MHz) δ
7.95 (d, 2, J = 8.37, Ar), 7.73 (m, 8, Ar), 7.13 (t,
2, J = 5.70, Ar), 6.99 (m, 14, Ar), 6.44 (t, 2, J = 7.14, Ar),
2.14 | Synthesis of [1a]PtnHexyl
3
2
2.12 (q, 2, JHH = 6.99, JHPt = 74.76, PtCH2), 1.36 (t,
The reaction was complete overnight, affording the prod-
uct as a yellowish orange solid; yield 75%. 1H NMR
(C6D6, 500 MHz) δ 7.94 (d, 2, J = 8.50, Ar), 7.74 (m,
8, Ar), 7.14 (m, 2, Ar), 7.00 (m, 14, Ar), 6.43 (t,
3, JHH = 7.53, JHPt = 54.03, PtCH2CH3). 31P{1H} NMR
(C6D6, 121 MHz) δ 30.85 (1JPPt = 3130). 13C{1H} NMR
(C6D6, 75 MHz) δ 162.25 (t, JCP = 10.19, C), 135.79 (t,
JCP = 9.83, CH), 133.89 (t, JCP = 6.45, CH), 132.60 (t,
JCP = 26.74, C), 132.05 (s, CH), 130.38 (s, CH), 128.79 (t,
JCP = 4.81, CH), 124.47 (t, JCP = 27.75, C), 117.38 (t,
JCP = 3.91, CH), 116.85 (t, JCP = 3.83, CH), 19.65 (s,
3
3
2
2, J = 7.00, Ar), 2.09 (m, 2, JHPt = 79.5, PtCH2), 1.55 (m,
2, CH2), 1.24 (m, 2, CH2), 1.12 (m, 2, CH2), 1.07 (q,
2, J = 7.00, CH2), 0.81 (t, 3, J = 7.25, CH3). 31P{1H} NMR
(C6D6, 202 MHz) δ 31.50 (1JPPt = 3128). 13C{1H} NMR
(C6D6, 125 MHz) δ 162.56 (t, JCP = 10.04, C), 136.11 (s,
CH), 134.20 (t, JCP = 6.53, CH), 132.96 (t, JCP = 26.86, C),
132.38 (s, CH), 130.73 (s, CH), 129.09 (t, JCP = 5.27, CH),
124.84 (t, JCP = 28.24, C), 117.73 (t, JCP = 4.39, CH),
117.16 (t, JCP = 4.77, CH), 36.01 (s, CH2), 35.96 (s, CH2),
32.67 (s, CH2), 23.45 (s, CH2), 14.80 (s, CH3), 0.59 (t,
2
1
PtCH2CH3), −8.81 (t, JCP = 4.16, JCPt = 612.67,
PtCH2CH3).
2.12 | Synthesis of [1a]PdnBu
1
The reaction was complete in 30 min, affording the prod-
uct as a yellowish brown solid; yield 90%. 1H NMR
(C6D6, 500 MHz) δ 7.92 (t, 1, J = 2.50, Ar), 7.91 (t,
1, J = 2.75, Ar), 7.67 (m, 8, Ar), 7.10 (m, 2, Ar), 7.00 (m,
14, Ar), 6.43 (t, 2, J = 7.50, Ar), 1.98 (m, 2, PdCH2), 1.51
2JCP = 5.27, JCPt = 613.82, PtCH2). Anal. Calcd for
C42H41NP2Pt: C, 61.76; H, 5.06; N, 1.71. Found: C,
61.45; H, 4.75; N, 1.49.
(m,
2,
PdCH2CH2CH2CH3),
1.24
J
(m,
7.50,
2.15 | Synthesis of [1a]PdH
2, PdCH2CH2CH2CH3), 0.69 (t, 3,
=
PdCH2CH2CH2CH3). 31P{1H} NMR (C6D6, 202 MHz) δ
27.95. 13C{1H} NMR (C6D6, 125 MHz) δ 161.85 (t,
JCP = 10.79, C), 135.96 (s, CH), 134.16 (t, JCP = 7.28, CH),
133.19 (t, JCP = 21.71, C), 132.44 (s, CH), 130.50 (s, CH),
129.21 (t, JCP = 5.40, CH), 124.45 (t, JCP = 23.59, C),
117.07 (t, JCP = 3.64, CH), 116.66 (t, JCP = 5.52, CH),
36.97 (t, JCP = 2.76, CH2), 28.37 (t, JCP = 2.64, CH2),
14.60 (s, CH3), 13.81 (t, JCP = 1.76, CH2). Anal. Calcd for
C40H37NPdP2: C, 68.62; H, 5.33; N, 2.00. Found: C,
68.37; H, 5.11; N, 1.92.
Method 1: To a C6D6 solution (0.35 ml) of [1a]PdCl
(3.4 mg, 5.0 μmol) at room temperature was added
LiHBEt3 (5.0 μl, 1.0 M in THF, 5.0 μmol). The solution
was transferred to an NMR tube, and the reaction was
1
examined in 10 min by H and 31P{1H} NMR spectros-
copy that showed quantitative formation of [1a]PdH.
Method 2: A similar reaction employing 100 equiv of
NaBH4 in THF at room temperature also afforded [1a]
PdH quantitatively in 1 h as indicated by the 31P{1H}
NMR spectrum of reaction aliquots. 1H NMR (C6D6,