Journal of Inorganic and General Chemistry
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
3
300 K): δ = –1.8, –2.0, –2.1, –2.8. IR (paraffin, KBr): ν˜ = 1668 m, [pseudo-t overlap, JHH ≈ 7 Hz, 2 H, o-H(Ph)], 7.00 [m overlap, 1 H,
1595 w, 1560 m ν(C=O), ν(C=C), aryl; 1462 vs, 1377 vs. (paraffin); p-H(Ph)], 6.76 [m overlap, 2 H, m-H(Mes)], 6.74 [m overlap, 2 H(o-
3
1304 vw, 1242 m δ(CH3); 1200 vw, 1180 vw, 1156 vw, 1107 w, 1082 H(Ph)], 3.20 (d, JPH = 6.2 Hz, 2 H, CH2), 2.56 (s, 6 H, o-Me), 2.06
w, 1067 w, 1036 m ν(CC), ν(CO); 1011 m δ(CHSi2); 930 w, 843 vs,
789 w, 748 w, 733 w ρ[CH3(Si)]; 722 m (paraffin); 671 w, 615 w
ν(SiC); 573 vw, 550 vw, 521 vw, 463 w δ(CC), ν(AlC), ν(AlO), ν(PC)
cm–1. MS (EI, 20 eV, 413 K): m/z (%): 629 (8) [M – CH(SiMe3)2]+,
578 (3) [M – PhC(O)C(O)Ph]+, 563 (8) [M – PhC(O)C(O)Ph – Me]+.
(s, 3 H, p-H), 1.01 (s, 9 H, CMe3), 0.38 (s, 18 H, SiMe3), 0.25 (s, 18
2
H, SiMe3), –0.88 (s, JSiH = 10.3 Hz, 2 H, CHSi). 13C NMR
1
(101 MHz, C6D6, 300 K): δ = 207.5 (d, JPC = 14.2 Hz, C=N), 158.5
(d, 2JPC = 5.1 Hz, PC=CH), 144.8 [d, 2JPC = 15.0 Hz, o-C(Mes)], 141.1
4
[d, JPC = 1.5 Hz, p-C(Mes)], 140.6 (s very br., PC=CH), 132.4 [d,
1
3JPC = 4.9 Hz, ipso-C(Ph)], 130.7 [d, JPC = 17.6 Hz, ipso-C(Mes)],
Synthesis of Compound 7a: H8C4N–CϵN (0.056 mL, 0.56 mmol) 130.4 [o-C(Ph)], 130.0 [d, 3JPC = 5.1 Hz, m-C(Mes)], 129.6 [m-C(Ph)],
was added with a syringe to a cooled (–70 °C) solution of compound
3 (0.32 g, 0.55 mmol) in n-pentane (20 mL). The mixture was warmed CMe3), 29.2 (d, 4JPC = 2.9 Hz, CMe3), 24.5 (d, 3JPC = 13.6 Hz, o-Me),
128.0 [p-C(Ph)], 44.0 (d, 2JPC = 19.3 Hz, CH2), 36.9 (d, 3JPC = 5.4 Hz,
5
to room temperature and stirred overnight. Storing the concentrated
21.1 (p-Me), 5.4 (d, JPC = 1.8 Hz, SiMe3), 5.2 (SiMe3), 3.9 (s br.,
solution at –30 °C afforded a colorless precipitate of 7a (0.32 g, 85%).
CHSi). 31P NMR (162 MHz, C6D6, 300 K): δ = –3.7. 29Si NMR
The product was recrystallized from 1,2-difluorobenzene; the obtained (79 MHz, C6D6, 300 K): δ = –2.07, –2.11. 15N NMR (41 MHz, C6D6,
1
crystals were used for X-ray crystal structure determination, melting 300 K): δ = 235. Low temperature NMR: H NMR (400 MHz, C7D8,
point determination and microanalysis. M.p. 60 °C (dec.). 220 K): δ = 8.38 (d, JPH = 10.2 Hz, 1 H, NH), 7.00–6.97 [t overlap-
3
C34H68AlN2PSi4·(C6H4F2) (789.33): C 60.7 (calcd. 60.9); H 9.0 (9.2),
ping, 1 H, p-H(Ph)], 6.96 [pseudo-t overlap, 2 H, m-H(Ph)], 6.91 (d
overlap, JPH = 46.0 Hz, 1 H, PC=CH), 6.71 [s br., 1 H, m-H(Mes)],
1
3
3
N 3.6 (3.6)%. H NMR (400 MHz, C6D6, 300 K): δ = 6.91 (d, JPH
=
4
43.8 Hz, 1 H, PC=CH), 6.75 (d, JPH = 5.2 Hz, 1 H, m-H), 6.65 (s, 1 6.57 [d overlap, 1 H, m-H(Mes)], 6.57 [d overlap, 1 H, o-H(Ph)], 3.22,
H, m-H), 5.75 (d, 3JPH = 6.5 Hz, 1 H, NH), 3.16 (m, 1 H, NCH2), 2.83 2.82 (m, 1 H, CH2), 2.79, 2.38 (s, 3 H, o-Me), 2.07 (s, 3 H, p-Me),
(m, 2 H, NCH2), 2.77 (s, 3 H, o-Me), 2.47 (s, 3 H, o-Me), 2.10 (m, 1 1.05 (s, 9 H, CMe3), 0.55, 0.45, 0.37, 0.27 (s, 9 H, SiMe3), –0.87,
H, NCH2), 2.01 (s, 3 H, p-Me), 1.01 (s, 9 H, CMe3), 1.00, (m, 1 H, –0.75 (s, 1 H, CHSi). 31P NMR (162 MHz, C7D8, 220 K): δ = –4.9.
NCH2CH2), 0.86 (m, 2 H, NCH2CH2), 0.72 (m, 1 H, NCH2CH2), 0.50 IR (paraffin, KBr): ν˜ = 3310 vw, 3271 m ν(NH); 2963 vs, 2918 vs,
(s, 18 H, SiMe3), 0.48, 0.43 (s, 9 H, SiMe3), –0.74, –0.79 (s, 1 H, 2901 vs, 2859 vs. (paraffin); 1653 w, 1601 m, 1551 s ν(C=N), ν(C=C),
1
CHSi). 13C NMR (101 MHz, C6D6, 300 K): δ = 179.8 (d, JPC
=
=
aryl; 1458 vs, 1373 vs. (paraffin); 1281 m, 1244 vs. δ(CH3); 1200 w,
1074 w, 1020 s ν(CC); 1009 s δ(CHSi2); 928 s, 910 s, 841 vs, 799 s,
2
2
13.2 Hz, CN2), 158.2 (d, JPC = 8.1 Hz, PC=CH), 145.2 (d, JPC
2
1
2.3 Hz, o-C), 145.0 (d, JPC = 27.5 Hz, o-C), 142.8 (s, very br., JPC 777 vs, 748 s ρ[CH3(Si)]; 727 s (paraffin); 698 s, 644 m, 613 w ν(SiC);
4
1
≈ 40 Hz, PC=CH), 140.4 (d, JPC = 1.6 Hz, p-C), 131.2 (d, JPC
=
573 vw, 548 w, 521 s, 480 m 455 w, 424 w δ(CC), ν(AlC), ν(AlN),
22.3 Hz, ipso-C), 130.0 (m-C), 129.8 (d, 3JPC = 8.0 Hz, m-C), 48.8 (d, ν(PC) cm–1. MS (EI, 20 eV, 313 K): m/z (%): 680 (2) [M – Me]+, 536
3JPC = 9.4 Hz, NCH2), 47.4 (NCH2), 36.3 (d, JPC = 4.2 Hz, CMe3), (100) [M – CH(SiMe3)2]+.
3
4
29.4 (d, JPC = 3.0 Hz, CMe3), 25.4, (NCH2CH2), 25.0 (o-Me), 23.6
(NCH2CH2), 23.4 (d, 3JPC = 27.3 Hz, o-Me), 21.0 (p-Me), 6.0, 5.7, 5.7
Synthesis of Compound 8a: tBu–NCO (0.052 mL, 0.45 mmol) was
added at –30 °C to a solution of compound 3 (0.26 g, 0.45 mmol) in
n-pentane (10 mL). The mixture was warmed to room temperature and
stirred overnight. The solvent was removed in vacuo, and the residue
(SiMe3), 5.5 (d, JPC = 3.6 Hz, SiMe3), 4.1, 3.7 (s br., CHSi). 31P
5
NMR (162 MHz, C6D6, 300 K): δ = –21.0. 29Si NMR (79 MHz, C6D6,
300 K): δ = –2.10, –2.05, –1.96, –1.93. 15N NMR (41 MHz, C6D6,
1
300 K): δ = 155 (NH). Low temperature NMR: H NMR (400 MHz, recrystallized from 1,1,1-trifluorotoluene at –30 °C to yield colorless
3
C7D8, 220 K): δ = 6.99 (d, JPH = 43.6 Hz, 1 H, PC=CH), 6.68 (d, crystals of compound 8a (0.21 g, 69%). M.p. 145 °C (dec.).
4JPH = 4.3 Hz, 1 H, m-H), 6.53 (s, 1 H, m-H), 5.70 (d, JPH = 6.0 Hz,
C34H69AlNOPSi4 (678.22): C 59.8 (calcd. 60.2); H 10.1 (10.3), N 1.9
3
3
1 H, NH), 3.13 (m, 1 H, NCH2), 2.81 (s, 3 H, o-Me), 2.78, 2.68 (m,
1 H, NCH2), 2.54 (s, 3 H, o-Me), 2.00 (m, 1 H, NCH2), 2.02 (s, 3 H, 45.7 Hz, 1 H, PC=CH), 6.69 (d, JPH = 2.1 Hz, 2 H, m-H), 5.58 (s, 1
(2.1)%. 1H NMR (400 MHz, C6D6, 300 K): δ = 6.81 (d, JPH
=
4
p-Me), 1.05 (s, 9 H, CMe3), 1.09, (m overlap, 1 H, NCH2CH2), 0.83
H, NH), 2.53 (s, 6 H, o-Me), 1.97 (s, 3 H, p-Me), 0.99 (s, 9 H, CCMe3),
2
(m, 2 H, NCH2CH2), 0.63–0.43 (m overlap, 1 H, NCH2CH2), 0.58, 0.92 (s, 9 H, NCMe3), 0.53, 0.48 (s, JSiH = 6.0 Hz, 18 H, SiMe3),
0.58, 0.57, 0.51 (s, 9 H, SiMe3), –0.70, –0.70 (s, 1 H, CHSi). 31P
–0.72 (s, 2 H, CHSi2). 13C NMR (101 MHz, C6D6, 300 K): δ = 195.1
NMR (162 MHz, C7D8, 220 K): δ = –22.1. IR (paraffin, KBr): ν˜ = (d, 1JPC = 12.3 Hz, NCO), 156.3 (d, 2JPC = 5.9 Hz, PC=CH), 141.6 (d,
1
3450 vw, 3372 vw ν(NH); 2953 vs, 2926 vs, 2853 vs. (paraffin); 1629
w, 1603 w, 1528 s, 1508 m ν(C=N), ν(C=C), aryl; 1458 vs, 1377 s
(paraffin); 1294 w, 1269 w, 1244 m δ(CH3); 1198 w, 1153 vw, 1099 5.2 Hz, CMe3), 29.3 (d, JPC = 3.4 Hz, CMe3), 28.7 (d, JPC = 0.7 Hz,
4JPC = 1.8 Hz, p-C), 139.5 (PC=CH), 132.1 (d, JPC = 29.3 Hz, ipso-
3
3
C), 130.0 (d, JPC = 1.8 Hz, m-C), 54.7 (NCMe3), 36.9 (d, JPC
=
4
4
w, 1080 w ν(CC), ν(CN); 1020 m δ(CHSi2); 928 w, 916 w, 840 vs,
797 w, 777 w, 750 m ρ[CH3(Si)]; 718 w (paraffin); 667 w, 613 vw
ν(SiC); 521 w, 463 w δ(CC), ν(AlC), ν(AlN), ν(PC). cm–1. MS
NCMe3), 24.3 (s br., o-Me), 21.0 (p-Me), 5.6 (d, 5JPC = 0.8 Hz, SiMe3),
5
5.4 (d, JPC = 1.2 Hz, SiMe3), 4.3 (s br., CHSi2); the resonance of o-
C Mes was not found. 31P NMR (162 MHz, C6D6, 300 K): δ = –15.7.
(EI, 20 eV, 323 K): m/z (%): 659 (1) [M – Me]+, 515 (100) 29Si NMR (79 MHz, C6D6, 300 K): δ = –1.8, –2.2. Low temperature
[M – CH(SiMe3)2]+.
NMR: 1H NMR (400 MHz, C7D8, 220 K): δ = 6.89 (d, 3JPH = 45.5 Hz,
4
1 H, PC=CH), 6.58, (d, JPH = 5.2 Hz, 1 H, m-H), 6.52 (s, 1 H, m-H),
Synthesis of Compound 7b: PhCH2–CN (0.068 mL, 0.59 mmol) was
5.58 (s, 1 H, NH), 2.70, 2.37 (s, 3 H, o-Me), 1.96 (s, 3 H, p-Me), 1.03
added at –78 °C to a solution of compound 3 (0.35 g, 0.60 mmol) in (s, 9 H, CCMe3), 0.82 (s, 9 H, NCMe3), 0.61, 0.61, 0.56, 0.54 (s, 9 H,
n-pentane (20 mL). The mixture was warmed to room temperature and
SiMe3), –0.99, –0.53 (s, 1 H, CHSi2). 31P NMR (162 MHz, C7D8,
stirred for 2 d. The solvent was removed in vacuo, and the solid residue 220 K): δ = –18.1. IR (paraffin, KBr): ν˜ = 3370 vw ν(NH); 2951 vs,
was recrystallized from a concentrated solution in n-pentane at –30 °C 2922 vs, 2853 vs. (paraffin); 1688 vw, 1655 vw, 1547 m, 1518 m,
yielding colorless crystals of compound 7b (0.31 g, 74%). M.p. 145 °C 1510 sh ν(CO), ν(C=C), aryl; 1460 vs, 1377 vs. (paraffin); 1273 w,
(dec.). C37H67AlNPSi4 (696.25): C 63.8 (calcd. 63.8); H 9.7 (9.7), N
1244 s δ(CH3); 1209 w, 1155 vw, 1082 vw, 1026 w ν(CC), ν(CN);
1007 w δ(CHSi2); 934 w, 922 w, 841 vs, 777 w, 748 w ρ[CH3(Si)];
723 w (paraffin); 673 w, 610 vw ν(SiC); 519 w, 506 w, 479 w, 463 w
1
3
2.3 (2.0)%. H NMR (400 MHz, C6D6, 300 K): δ = 8.46 (d, JPH
=
3
10.2 Hz, 1 H, NH), 6.82 (d, JPH = 46.4 Hz, 1 H, PC=CH), 7.04
Z. Anorg. Allg. Chem. 2017, 1978–1990
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