Inorganic Chemistry
Article
[CH{(CH3)CN-2,6-i-Pr2C6H3}2SnP(C6H5)2] (2a). Compound 2a
was made according to the general procedure outlined for 1b using
Sn(BDI)Cl (0.300 g, 0.52 mmol) and LiPPh2 (0.101 g, 0.52 mmol).
The product was isolated as red-purple crystals from toluene. Yield
0.283 g (75%). M.pt.: 95−110 °C (decomp.). Anal. Calcd. for
C41H51N2PSn (721.54): C, 68.25; H, 7.12; N, 3.88. Found: C, 68.06;
H, 7.19; N, 3.95. 1H NMR: δ 7.14 (dd, J = 7.6, 1.6, 2H, ArH), 7.06 (t, J
= 7.6, 2H, ArH), 6.93 (dd, J = 7.6, 1.6, 2H, ArH), 6.84−6.72 (m, 10H,
PPh2), 4.71 (s, 1H, CHγ), 4.08 (d sept, J = 6.8, 1.2, 2H, CHMe2), 3.16
(sept, J = 6.8, 2H, CHMe2), 1.67 (d, J = 6.8, 6H, CHMe2), 1.52 (s, 6H,
NCMe), 1.23, 1.12, 0.96 (d, 6H, J = 6.8, CHMe2). 13C{1H} NMR: δ
167.6 (NCMe), 144.2, 143.5, 142.9 (i- and o-C6H3), 141.5 (d, JPC = 32,
C6H5), 135.1 (d, JPC = 15, C6H5), 128.4 (d, JPC = 6, C6H5), 127.0 (o-/
m C6H3), 125.8 (C6H5), 125.2, 124.9 (o-/m-C6H3), 97.3 (γ-CH), 29.2
(d, JPC = 6, CHMe2), 28.5 (JSnC = 36, CHMe2), 26.2 (JSnC = 43,
CHMe2), 25.3, 24.7 (CHMe2), 24.7 (d, JPC = 8, CHMe2), 23.5
(NCMe). 31P{1H} NMR: δ −30.7 (JSnP = 978). 119Sn{1H} NMR: δ
125 (d, JSnP = 978). IR (Nujol, v/cm−1): 1578.2 (s), 1555.3 (s), 1515.8
(b), 1317.9 (s), 1265.7 (s), 1174.3 (s), 1099.4 (s), 1018.7 (s), 935.1
(s). UV−vis (pentane), (λmax, nm, (ε, M−1 cm−1): 283.9 (14960),
354.0 (13706).
(810.03): C, 60.79; H, 6.35; N, 3.46. Found: C, 60.92; H, 6.51; N,
3.38. 1H NMR: δ 7.21 (d, J = 7.6, 2H, ArH), 7.05 (t, J = 7.6, 2H, ArH),
6.96 (d, J = 7.6, 2H, ArH), 6.86 (t, J = 7.3, 4H, C6H5), 6.75 (t, J = 7.3,
2H, C6H5), 6.53 (t, J = 7.3, 4H, C6H5), 4.59 (s, 1H, CHγ), 4.04 (sept, J
= 6.8, 2H, CHMe2), 3.06 (sept, J = 6.8, 2H, CHMe2), 1.69 (d, J = 6.8,
6H, CHMe2), 1.64 (s, 6H, NCMe), 1.29, 1.13, 0.86 (d, 6H, J = 6.8,
CHMe2). 13C{1H} NMR: δ 166.0 (NCMe), 144.6, 143.6, 143.1 (i- and
o-C6H3), 142.3 (d, JPC = 38, C6H5), 135.7 (d, JPC = 16, C6H5), *, 126.5
(o-/m C6H3), 126.4 (C6H5), 124.8, 124.6 (o-/m-C6H3), 98.6 (γ-CH),
29.0 (d, JPC = 5, CHMe2), 28.0 (JPbC = 37, CHMe2), 26.5 (CHMe2),
25.1 (d, JPC = 9, CHMe2), 25.1, 24.7 (CHMe2), 23.9 (NCMe) *
remaining C6H5 resonance obscured by solvent. 31P{1H} NMR: δ 7.3
(JPbP = 1129). 207Pb{1H} NMR: 3011 (d, JPbP = 1129). IR (Nujol, v/
cm−1): 1551.7 (s), 1512.8 (s), 1317.4 (s), 1172.7 (s), 1017.6 (s), 933.5
(s), 793.2 (s). UV−vis (pentane), (λmax, nm, (ε, M−1 cm−1): 259.1
(18623), 312.0 (17694).
[CH{(CH3)CN-2,6-i-Pr2C6H3}2PbP(C6H11)2] (3b). Compound 3b
was made according to the general procedure outlined for 1b using
Pb(BDI)Cl (0.500 g, 0.79 mmol) and a suspension of LiPCy2 (0.155
g, 0.79 mmol) in toluene. The product was isolated as deep red
crystals from toluene and −30 °C. Yield 0.59 g (95%). M.pt.: 154−155
°C (decomp.). Anal. Calcd. for C41H63N2PPb (822.13): C, 59.90; H,
7.72; N, 3.41. Found: C, 60.01; H, 7.59; N, 3.29. 1H NMR: δ 7.21 (dd,
J = 7.4, 1.6, 2H, ArH), 7.05 (t, J = 7.4, 2H, ArH), 7.02 (dd, J = 7.4, 1.6,
2H, ArH), 4.61 (s, 1H, CHγ), 3.95 (d sept, J = 6.8, 0.8, 2H, CHMe2),
3.25 (sept, J = 6.8, 2H, CHMe2), 1.73 (s, 6H, NCMe), 1.69 (d, J = 6.8,
6H, CHMe2), 1.63 (br, 6H, Cy-CH and Cy‡), 1.25, 1.24, 1.18 (d, 6H, J
= 6.8, CHMe2), 1.01 (br, 8H, Cy‡) ‡ resonances for the remaining
protons of the cyclohexyl substituents appear as an ill-defined broad
feature spanning the region 0.5 and 1.9 ppm. 13C{1H} NMR: δ 166.5
(NCMe), 144.8, 144.0, 143.1 (i- and o-C6H3), 126.0, 124.6, 124.3 (m-
and p-C6H3), 97.8 (γ-CH), 39.0 (br, Cy-CH2), 34.0 (d, JPC = 34, Cy-
CH), 28.8 (d, JPC = 5, CHMe2), 28.7 (br, Cy-CH2), 27.9 (CHMe2),
26.6 (CHMe2), 26.5 (Cy-CH2), 25.5 (d, JPC =10, CHMe2), 25.1, 25.0
(CHMe2), 23.8 (NCMe). 31P{1H} NMR: δ 26.9 (JPbP = 1084).
207Pb{1H} NMR: δ 3981 (d, JPbP = 1084). IR (Nujol, v/cm−1): 1555.7
(s), 1514.57 (s), 1318.71 (s), 1172.0 (s), 934.7 (s), 788.5 (s). UV−vis
(pentane), (λmax, nm, (ε, M−1 cm−1): 280.9 (17118), 352.0 (8874).
[CH{(CH3)CN-2,6-i-Pr2C6H3}2PbP{Si(CH3)3}2], (3c). Pb(BDI)Cl
(0.24 g, 0.369 mmol) was dissolved in toluene (20 mL) and added
directly to LiP(TMS)2 (0.07 g, 0.369 mmol). The reaction mixture was
stirred at room temperature for 4 h. The red solution was filtered
through a pad of Celite. The volatiles were evaporated under vacuum,
and the solid was dissolved n-hexane for recrystallization at −35 °C
[CH{(CH3)CN-2,6-i-Pr2C6H3}2SnP(C6H11)2] (2b). Compound 2b
was made according to the general procedure outlined for 1b using
Sn(BDI)Cl (0.380 g, 0.66 mmol) and a suspension of LiPCy2 (0.135 g,
0.66 mmol) in toluene. The product was isolated as purple crystals
from toluene at −30 °C. Yield 0.423 g (87%). M.pt.: 205−207 °C
(decomp.). Anal. Calcd. for C41H63N2PSn (733.64): C, 67.12; H, 8.66;
N, 3.82. Found: C, 67.03; H, 8.60; N, 3.75. 1H NMR: δ 7.17 (dd, 2H, J
= 7.7, 1.4, ArH), 7.08 (t, 2H, J = 7.7, ArH), 7.02 (dd, 2H, J = 7.7, 1.4,
ArH), 4.72 (s, 1H, CHγ), 3.99 (d sept, 2H, J = 6.8, 1.6, CHMe2), 3.32
(sept, 2H, J = 6.8, CHMe2), 1.67 (d, 6H, J = 6.8, CHMe2), 1.59 (s, 6H,
NCMe), 1.54 (br, 6H, Cy‡), 1.31, 1.21, 1.15 (d, 6H, J = 6.8, CHMe2),
1.00 (br, 8H, Cy‡). ‡ resonances for the remaining protons of the
cyclohexyl substituents appear as an ill-defined broad feature spanning
the region 0.6 and 2.1 ppm. 13C{1H} NMR: δ 167.9 (NCMe), 144.4,
144.1, 143.2 (i- and o-C6H3), 126.6, 124.9, 124.8 (m- and p-C6H3),
96.6 (γ-CH), 36.0 (br, Cy-CH2), 32.8 (d, JPC = 29, Cy-CH), 29.0 (d,
JPC = 7, CHMe2), 28.5 (br, Cy-CH2), 28.4 (CHMe2), 26.6 (Cy-CH2),
26.3, 25.3, 25.0 (CHMe2), 24.8 (d, JPC =10, CHMe2), 23.6 (NCMe).
31P{1H} NMR: δ −15.4 (JSnP = 953§) § coupling to 117Sn and 119Sn
not resolved, therefore average coupling observed. 119Sn{1H} NMR: δ
358 (d, JSnP = 964). IR (Nujol, v/cm−1): 1552.6 (s), 1517.6 (s), 1318.9
(s), 1173.8 (s), 1019.1 (s), 763.9 (s), 751.1 (s), 515.8 (s). UV−vis
(pentane), λmax, nm (ε, M−1 cm−1): 284.0 (19409), 365.0 (10939).
[CH{(CH3)CN-2,6-i-Pr2C6H3}2SnP{Si(CH3)3}2] (2c). Compound 2c
was made according to the general procedure outlined for 1b using
Sn(BDI)Cl (0.436 g, 0.76 mmol) and a suspension of LiP{SiMe3}2
(0.140 g, 0.76 mmol) in toluene. The product was isolated as yellow
crystals from pentane at −30 °C. Yield 0.503 g (93%). M.p.: 192−194
°C (decomp.). Anal. Calcd. for C35H59N2PSi2Sn (713.71): C, 58.90;
1
(0.27 g, 91%). H NMR (499.91 MHz, C6D6, 303 K): δ 7.22 (dd, J =
7.5, 2.0, 2H, m-H), 7.12 (t, J = 7.5, 2H, p-H), 7.09 (dd, J = 7.5, 2.0, 2H,
m-H), 4.75 (s, 1H, γ-CH), 3.92 (d sept, J = 7.0, 1.0, 2H, CHMe2), 3.29
(sept, J = 6.5, 2H, CHMe2), 1.64 (s, 6H, NCMe), 1.52 (d, J = 6.5, 6H,
CHMe2), 1.31 (d, J = 7.0, 6H, CHMe2), 1.26 (d, J = 6.5, 6H, CHMe2),
1.16 (d, J = 7.0, 6H, CHMe2), 0.30 (d, J = 4.0, 18H, SiMe3). 13C{1H}
NMR (100.46 MHz, C6D6, 303 K): δ 166.2 (NCMe), 145.5 (ipso-C),
144.7 (o-C), 143.6 (o-C), 127.0 (m-H), 125.6 (m-H), 124.4 (p-H),
103.0 (γ-CH), 29.0 (CHMe2), 28.4 (d, JPC = 6.3, CHMe2), 28.2 (d, JPC
= 5.0, CHMe2), 26.1 (CHMe2), 25.1 (CHMe2), 25.1 (CHMe2), 25.0
(NCMe), 7.5 (d, JSiC = 9.8, SiMe3). 31P{1H} NMR (161.72 MHz,
C6D6, 303 K): δ −116.6 (JPbP = 2874). 29Si{1H} NMR (79.37 MHz,
C6D6, 303 K): δ 7.2 (d, JPSi = 36). UV−vis (pentane) λmax, nm (ε, M−1
cm−1): 382.0 (7900).
1
H, 8.33; N, 3.93. Found: C, 58.94; H, 8.28; N, 3.88. H NMR: δ 7.22
(dd, J = 7.7, 1.6, 2H, ArH), 7.16 (t, J = 7.6, 2H, ArH), 7.09 (dd, J = 7.6,
1.6, 2H, ArH), 4.95 (s, 1H, CHγ), 3.97 (d sept, J = 6.8, 1.6, 2H,
CHMe2), 3.38 (sept, J = 6.8, 2H, CHMe2), 1.61 (s, 6H, NCMe), 1.48,
1.32, 1.28, 1.12 (d, J = 6.8, 6H, CHMe2), 0.46 (d, JSnH = 124, JPH = 4.4,
JSiH = 11.2, 18H, SiMe3). 13C{1H} NMR: δ 167.1 (NCMe), 146.3,
143.6, 142.7 (i- and o-C6H3), 127.2, 125.5, 124.3 (m- and p-C6H3),
101.2 (γ-CH), 29.5 (d, JPC = 5, CHMe2), 29.3 (JSnC = 21, CHMe2),
27.8 (d, JPC = 5, CHMe2), 25.1, 25.0, 24.7 (CHMe2), 24.5 (NCMe), 6.0
(d, JPC = 10, JSnC = 60, SiMe3). 31P{1H} NMR: δ −183.5 (s, JPSi = 17,
JSnP = 2427). 119Sn{1H} NMR: δ 39 (d, JSnP = 2427). 29Si{1H} NMR: δ
4.0 (d, JPSi = 17). IR (Nujol, v/cm−1): 1551.4 (s), 1521.0 (s), 1314.4
(s), 1239.1 (s), 1167.6 (s), 1020.4 (s), 935.2 (s), 831.3 (b), 794.8 (s),
757.2 (s), 628.1 (s). UV−vis (pentane), λmax, nm (ε, M−1 cm−1): 231.0
(34501), 373.1 (13015). MS m/z (EI): 713, 537, 403, 202, 160, 73, 46.
[CH{(CH3)CN-2,6-i-Pr2C6H3}2PbP(C6H5)2] (3a). Compound 3a
was made according to the general procedure outlined for 1b using
Pb(BDI)Cl (0.250 g, 0.38 mmol) and LiPPh2 (0.073 g, 0.38 mmol).
The product was isolated as red crystals from hexane. Yield 0.189 g,
(61%). M.pt.: 265−266 °C (decomp.). Anal. Calcd. for C41H51N2PPb
ASSOCIATED CONTENT
■
S
* Supporting Information
Thermal ellipsoid plots of 1b, 2a−2c, 3a−3b; selected solution-
and solid-state NMR data; crystal structure data for
polymorphic Sn(BDI)Cl (II′) and Ph2P-PPh2.. This material
K
dx.doi.org/10.1021/ic301208d | Inorg. Chem. XXXX, XXX, XXX−XXX