2746 Organometallics, Vol. 28, No. 9, 2009
Walker et al.
(26.3). Anal. Calcd for C16H31N2ISi: C: 47.28, H: 7.69, N: 6.89.
Found: C: 47.45, H: 7.66, N: 6.85.
[(CH)2 Bu2N2]SiI(CH(CH3)OCH2CH3) (5). A 100 mL round-
independently carried out by reaction of 1 with [HNEt3]I. A 100
mL round-bottom flask was charged with [HNEt3]I (148 mg, 0.646
mmol, 1.0 equiv), 1 (121 mg, 0.616 mmol, 1.0 equiv), and 15.94
g of Et3N. The flask was capped and allowed to stir overnight.
Removal of volatiles produced 239 mg of a white solid and an
amber oil (154 mg). Filtration with pentane separated the white
t
bottom flask was charged with 121 mg (0.593 mmol, 1.1 equiv) of
Ph-I and 25 mL of Et2O. A solution consisting of 103 mg (0.525
mmol, 1.0 equiv) of 1 dissolved in 10.2 mL of Et2O was transferred
to an airtight syringe. The solution containing 1 was added to the
Ph-I solution at a rate of 3.17 mL/h. After addition of 1 was
completed, volatiles were removed from the pale yellow solution.
The resulting golden oil contained a mixture of 5 (76%) and 2
(15%). Spectroscopic data were obtained on this mixture. 1H NMR
(C6D6) δ 5.78 (d, dCH, 3JH-H ) 4.4 Hz, 1H), 5.76 (d, 3JH-H ) 4.4
1
solid and amber oil. The white solid recovered was [HNEt3]I. H
NMR spectroscopy indicated that ∼30% of the amber oil was 8.
1H NMR (C6D6) δ 5.82 (s, H-CdC, 2H), 5.70 (br s, Si-H, 1H),
3
2.84 (q, JH-H ) 7.1 Hz, CH2, 4H), 1.25 (s, C(CH3)3, 18H), 0.99
3
(t, JH-H ) 7.1 Hz, CH2CH3, 6H); 13C NMR (C6D6) δ 111.8
(CHdCH-N), 51.0 (tBuC-N), 38.3 (NCH2), 30.9 (C(CH3)3), 14.8
(CH2CH3); GC-MS m/z (relative intensity) 269.30 (53.02%), 270.30
(11.27%) 72.10 (100.00%), 84.05 (24.95%), 85.05 (72.22%), 156.05
(23.21%), 183.20 (14.81%), 198.25 (24.20%), 212.25 (24.15%),
254.25 (26.04%); IR (neat on NaCl plate) 2132 cm-1 (ν Si-H).
3
Hz, 1H), 3.52 (q, JH-H ) 7.3 Hz, CH, 1H), 3.45 (m, CH2, 2H),
1.33 (d, 3JH-H ) 7.3 Hz, CHCH3, 3H), 1.32 (s, C(CH3)3, 9H), 1.26
(s, C(CH3)3, 9H), 1.10 (t, 3JH-H ) 7.0 Hz, CH2CH3, 3H); 13C NMR
(C6D6) δ 113.9 (CHdCH-N), 113.6 (CHdCH-N), 73.3 (CH3-
CH(Si)-O) [1JC-Si ) 52 Hz], 67.6 (CH3-CH2-O), 52.5 ((CH3)3-C-
N), 52.3 ((CH3)3-C-N), 30.7 (C-(CH3)3), 30.3 (C-(CH3)3), 16.9 (CH-
CH3), 15.8 (CH2-CH3); HRMS calcd (C14H29N2OSiI) 396.1094,
found 396.1089; MS (EI) m/z (relative intensity) 396.2 (100%),
157.1 (49.5%) 196.2 (35.6%), 211.0 (35.1%), 213.2 (20.4%), 267.1
(21.8%), 267.1 (21.8%), 269.0 (23.4%), 269.3 (27.5%), 283.1
(22.1%), 284.1 (22.0%).
t
[(CH)2 Bu2N2]SiI[CH(CH2CH3)N(CH2CH2CH3)2] (9). A 100
mL round-bottom flask was charged with 122 mg (0.598 mmol,
1.2 equiv) of Ph-I and 25 mL of Pr3N. A solution containing 102
mg (0.519 mmol, 1.9 equiv) of 1 dissolved in 10.4 mL of Pr3N
was transferred to an airtight syringe. The solution containing 1
was added at a rate of 3.17 mL/h to the Ph-I solution. After
addition of 1 was completed, volatiles were removed from the pale
yellow solution. The resulting golden oil was a mixture of 9 (77%),
2 (2%), and 10 (3%). Spectroscopic data were obtained on this
t
[(CH)2 Bu2N2]SiI(C4H7O2) (6). A 100 mL round-bottom flask
was charged with 120 mg (0.588 mmol, 1.1 equiv) of Ph-I and
25 mL of 1,4-dioxane. A solution consisting of 103 mg (0.525
mmol, 1.0 equiv) of 1 dissolved in 10.0 mL of 1,4-dioxane was
transferred to an airtight syringe. The solution containing 1 was
added to the Ph-I solution at a rate of 3.17 mL/h. After addition
of 1 was completed, the volatiles were removed. The resulting
golden oil contained a mixture of 6 (67%) and 2 (17%). Spectro-
scopic data were obtained on this mixture. 1H NMR (C6D6) δ 5.74
(d, 3JH-H ) 4.0 Hz, dCH, 1H), 5.68 (d, 3JH-H ) 4.0 Hz, dCH,1H),
3.96 (m, CH and CHCH2, 2H), 3.76 (pseudo t, J ) 11.2 Hz,
CHCH2, 1H), 3.48-3.38 (m, CH2CH2, 4H), 1.33 (s, 9H), 1.20 (s,
9H); 13C NMR (C6D6) δ 114.3 (CHdCH-N), 113.6 (CHdCH-N),
75.7 (O-CH2-CH(Si)-O) [1JC-Si ) 50 Hz], 69.5 (O-CH2-CH2-O),
67.9 (O-(Si)CH-CH2-O), 67.1 (O-CH2CH2-O), 52.6 (tBuC-N), 52.5
(tBuC-N), 31.1 (CH3), 30.7 (CH3); HRMS calcd (C14H27N2O2SiI)
410.0886, found 410.0883; MS (EI) m/z (relative intensity) 410.3
(100%), 105.1 (24.0%) 127.1 (26.9%), 143.1 (21.8%), 144.1
(55.9%), 161.1 (77.1%), 171.1 (56.4%), 211.0 (34.0%), 217.2
(21.2%), 273.1 (44.4%), 287.1 (22.0%), 288.1 (29.0%), 298.1
(32.8%), 354.2 (52.4%).
1
mixture. H NMR (C6D6) δ 5.83 (d,3JH-H ) 4.0 Hz, dCH, 1H),
3
5.76 (d, JH-H ) 4.0 Hz, dCH, 1H), 2.76-2.68 (m, NCH2 and
2
NCHCH2, 3H), 2.48 (m, NCH2, 2H), 2.35 (dqd, NCHCH2, JH-H
3
2
) 14.2 Hz, JH-H ) 7.2, 2.5 Hz, 1H), 1.60 (ddq, NCHCH2, JH-H
) 14.2 Hz, 3JH-H ) 9.8, 7.2 Hz, 1H), 1.50-1.33 (m, NCH2CH2CH3,
4H), 1.37 (s, C(CH3)3, 9H), 1.29 (s, C(CH3)3 9H), 1.10 (t, 3JH-H
)
7.2 Hz, CHCH2CH3, 3H), 0.81 (br t, 3JH-H ) 7.4 Hz, NCH2CH2CH3,
6H); 13C NMR (C6D6) δ 114.3 (CHdCH-N), 113.5 (CHdCH-N),
64.1 (SiCH, JC-Si ) 45 Hz), 56.2 (NCH2), 53.3 (tBuC-N), 52.6
1
(tBuC-N), 30.8 (C(CH3)3), 30.3 (C(CH3)3), 23.2 (CH2CH2CH3), 21.1
(CHCH2CH3), 16.0 (CHCH2CH3), 11.9 (CH2CH2CH3); HRMS calcd
(C19H40N3SiI) 465.2036, found 465.2046; MS (EI) m/z (relative
intensity) 196.2 (100%), 84.0 (58.1%) 84.1 (75.4%), 112.1 (48.3%),
125.1 (41.8%), 141.2 (26.2%) 142.2 (93.9%), 161.1 (%), 181.1
(33.7%), 335.3 (38.0%), 450.0 (2.2%), 465.3 (1.7%).
t
[(CH)2 Bu2N2]SiH[N(CH2CH2CH3)2] (10). This product is
present in ∼3% yield as indicated by 1H NMR spectroscopy using
the reaction conditions given for compound 9. Synthesis of 10 was
independently carried out by reaction of 1 with [HNPr3]I. A 100
mL round-bottom flask was charged with 140 mg (0.516 mmol,
1.0 equiv) of [HNPr3]I, 98 mg (0.499 mmol, 1 equiv) of 1, and 15
mL of Pr3N. The solution was allowed to stir for 24 h. Removal of
volatiles afforded a white solid with a goldish-colored oil. The white
solid was removed via filtration with pentane. Then 148 mg of a
t
[(CH)2 Bu2N2]SiI[CH(CH3)N(CH2CH3)2] (7). A 100 mL round-
bottom flask was charged with 119 mg (0.583 mmol, 1.1 equiv) of
Ph-I and 25 mL of Et3N. A solution consisting of 102 mg (0.519
mmol, 1.0 equiv) of 1 dissolved in 9.6 mL of Et3N was transferred
to an airtight syringe. The solution containing 1 was added to the
Ph-I solution at a rate of 3.17 mL/h. After addition of 1 was
completed, volatiles were removed. The resulting golden semisolid
contained a mixture of 7 (80%), 2 (10%), and 8 (10%). Spectro-
scopic data were obtained on this mixture. 1H NMR (C6D6) δ 5.88
1
goldish-colored oil was recovered, by H NMR; 23% of the oil
was 10. The white solid remaining after filtration was 114 mg of
[HNPr3]I (81% recovery). 1H NMR (C6D6) δ 5.83 (s, H-CdC, 2H),
5.73 (br s, Si-H, 1H), 2.77 (m, N-CH2, 4H), 1.49 (m, CH2-CH3,
4H), 1.27 (s, C(CH3)3, 18H), 0.79 (t, 3J ) 7.2 Hz CH2-CH3), 6H);
13C NMR (C6D6) δ 111.9 (CHdCH-N), 51.0 (tBuC-N), 47.9
(NCH2), 30.9 (C(CH3)3), 23.2 (CH2CH2CH3), 12.1 (CH2CH3); GC-
MS m/z (relative intensity) 297.35 (49.34%), 298.35 (11.70%),
84.00 (36.55%), 85.00 (100.00%), 86.00 (17.03%), 100.10 (91.56%),
184.20 (25.25%), 240.25 (20.03%), 282.30 (18.75%); IR (neat on
NaCl plate) 2199 cm-1 (ν Si-H).
3
3
(d, JH-H ) 4.4 Hz, dCH, 1H), 5.77 (d, JH-H ) 4.4 Hz, dCH,
3
2
1H), 3.14 (q, JH-H ) 7.3 Hz, CH, 1H), 2.63 (qd, JHH) 13.0 Hz,
3JH-H ) 7.2 Hz, CH2, 2H), 2.26 (qd, 2JH-H ) 13.0 Hz, 3JH-H ) 7.2
Hz, CH2, 2H), 1.38 (s, CH3, 9H), 1.29 (d, 3JH-H ) 7.3 Hz, CHCH3,
3
3H) 1.28 (s, CH3, 9H), 0.90 (br t, JH-H ) 7.2 Hz, CH2CH3, 6H);
13C NMR (C6D6) δ 114.5 (CHdCH-N), 113.0 (CHdCH-N), 58.2
(CH, JC-Si ) 48 Hz), 52.9 (tBuC-N), 52.3 (tBuC-N), 47.0
1
[(CH)2 Bu2N2]SiI[CH2N(CH3)tBu] (11). A two-neck 100 mL
t
(CH3CH2N), 30.9 (C-(CH3)3), 30.2 (C-(CH3)3), 14.8 (CH2CH3), 8.0
(CHCH3); HRMS calcd (C16H34N3SiI) 423.1567, found 423.1578;
MS (EI) m/z (relative intensity) 100.1 (100%), 125.0 (6.5%) 127.9
(6.7%), 196.1 (7.3%), 210.9 (7.1%), 423.1 (5.1%).
round-bottom flask was charged with 254 mg (1.24 mmol, 1.2
equiv) of Ph-I and 7.750 g of Me2NtBu. A solution containing
200 mg (1.02 mmol, 1 equiv) of 1 in 4 mL of Me2NtBu was
transferred to an airtight syringe. The solution containing 1 was
added to the Ph-I solution at a rate of 1.19 mL/h. After addition
of 1 was completed, the solution was stirred for 16 h, after which
t
[(CH)2 Bu2N2]SiH[N(CH2CH3)2] (8). This product is present in
∼10% yield as indicated by 1H NMR spectroscopy using the
reaction conditions given for compound 7. Synthesis of 8 was