W. Keim et al. / Journal of Organometallic Chemistry 662 (2002) 150Á
/
171
167
Calc. for C28H32F6N2PPdSb: C, 43.69; H, 4.19; N,
3.64%.
3.5.4. [(Acetonitrile){2,6-dimethyl-N-(2-
diphenylphosphino-cyclohexylidene)aniline-k2-
P,N}(methyl)palladium(II)]hexafluoroantimonate;
[(dppCyHexMA)Pd(CH3)(NCCH3)]SbF6 (16)
1H-NMR (CD2Cl2, 300 MHz): [ppm] dꢁ
/
0.34 (d,
1.70 (m, 2H, CH2),
2.24 (br m, 4H, CH2), 2.12,
2.16 (2*s, 2*3H, CH3), 4.39 (m, 1H, PCH), 7.01Á7.86
(m, 13H, Harom); 13C{1H}-NMR (CD2Cl2, 75 MHz):
[ppm] dꢁ 3.1 (PdCH3), 2.0 (NCCH3), 18.2, 18.9
(CH3), 26.6 (d, JC,P 6.3 Hz, CH2), 27.8 (d, JC,P 9.3
Hz, CH2), 30.6 (d, JC,P 7.0 Hz, CH2), 58.5 (d, JC,P
30.0 Hz, PCH), 119.5 (NCCH3), 124.5Á137.0 (CHarom
ipso), 145.5 (NCipso), 195.8 (d, JC,P
31P{1H}-NMR (CD2Cl2, 121 MHz): [ppm] dꢁ
IR (KBr): [cmꢂ1] nꢁ
1661.0 (m, Cꢁ
(w, CꢂN); SIMS (DTE/DTT/Sul), cation: m/z (Irel.
(%))ꢁ DTE/DTTꢂ
630 (15) [(PfflN)Pdꢀ 1]ꢀ, 492 (43)
[(PfflN)Pd(CH3)]ꢀ, 477 (22) [(PfflN)Pd]ꢀ, 372 (4)
[(PfflN)ꢀ1]ꢀ, 370 (6) [(PfflN)ꢂ1]ꢀ, 291 (11)
[PdPPh2]ꢀ, 186 (100) [(PfflN)ꢀ 1]ꢀ; SIMS
PPh2, PPh2ꢀ
235 (100)
JH,P
ꢁ
/
1.8 Hz, 3H, PdCH3), 1.48Á
/
1.73 (s, 3H, NCCH3), 2.01Á
/
Scale: 354.9 mg (0,654 mmol) (15); 230.8 mg (0.672
mmol) AgSbF6; yield: 474.7 mg (0.605 mmol, 92%)
white solid. Anal. Found: C, 44.58; H, 4.42; N, 3.61.
Calc. for C29H34F6N2PPdSb: C, 44.44; H, 4.37; N,
3.57%.
/
/
ꢂ
/
ꢁ
/
ꢁ
/
ꢁ
/
ꢁ
/
1H-NMR (CDCl3, 300 MHz): [ppm] dꢁ
JH,P 1.8 Hz, 3H, PdCH3), 1.17Á1.32 (m, 2H, CH2),
1.60Á1.83 (m, 4H, CH2), 1.74 (s, 3H, NCCH3), 2.01,
2.20 (2*s, 2*3H, CH3), 2.16Á2.40 (m, 2H, CH2), 4.00 (m,
1H, PCH), 7.00Á
7.69 (m, 13H, Harom); 13C{1H}-NMR
(CDCl3, 75 MHz): [ppm] dꢁ 3.2 (PdCH3), 1.3
(NCCH3), 17.9, 18.5 (CH3), 25.2 (d, JC,P 8.3 Hz,
CH2), 26.3 (CH2), 32.3 (d, JC,P 3.2 Hz, CH2), 32.6 (d,
JC,P 6.1 Hz, CH2), 53.8 (d, JC,P 31.2 Hz, PCH),
118.5 (NCCH3), 124.4Á135.6 (CHarom, Cipso), 144.6
(NCipso), 186.0 (d, JC,P
5.3 Hz, Cꢁ
N); 31P{1H}-
NMR (CDCl3, 121 MHz): [ppm] dꢁ52.85 (s); IR
(KBr): [cmꢂ1] nꢁ
1622.7 (m, CꢁN), 2318.2, 2289.6 (w,
CꢂN); SIMS (NBA), cation: m/z (Irel. (%))ꢁ506 (17)
[(PfflN)Pd(CH3)]ꢀ, 491 (3) [(PfflN)Pd]ꢀ, 384 (2)
[(PfflN)ꢂ1]ꢀ, 327 (4), 291 (12) [PdPPh2]ꢀ, 281 (7),
221 (6), 214 (5), 200 (100) [(PfflN)ꢀPPh2]ꢀ, 198 (13)
[CHPPh2]ꢀ, 147 (33); SIMS (NBA), anion: m/z (Irel.
(%))ꢁ
235 (100) [SbF6]ꢂ.
/
0.32 (d,
/
,
ꢁ
/
/
C
ꢁ
/
9.0 Hz, Cꢁ
/
N);
/
/
44.51 (s).
/
/
/
N), 2309.2, 2282.1
/
/
/
ꢂ
/
/
/
/
ꢁ
/
ꢁ
/
/
/
ꢁ
/
ꢁ
/
/
/
/
(DTE/DTT/Sul), Anion: m/z (Irel. (%))ꢁ
/
ꢁ
/
/
[SbF6]ꢂ.
/
/
/
/
/
3.5.3. [(Acetonitrile){2,6-diisopropyl-N-(2-
diphenylphosphino-cyclopentylidene)aniline-k2-P,N}
(methyl)palladium(II)]hexafluoroantimonate;
[(dppCyPentPA)Pd(CH3)(NCCH3)]SbF6 (13)
Scale: 464.6 mg (0.795 mmol) (12); 276.7 mg (0.805
mmol) AgSbF6; yield: 631.6 mg (0,765 mmol, 96%)
white powder. Anal. Found: C, 46.53; H, 4.92; N, 3.30.
Calc. for C32H40F6N2PPdSb: C, 46.54; H, 4.88; N,
3.39%.
/
/
/
3.5.5. [(Acetonitrile){2,6-diisopropyl-N-(2-
diphenylphosphino-cyclohexylidene)aniline-k2-
P,N}(methyl)palladium(II)]hexafluoroantimonate;
[(dppCyHexPA)Pd(CH3)(NCCH3)]SbF6 (19)
Scale: 447.3 mg (0.747 mmol) (18); 260.8 mg (0.759
mmol) AgSbF6; yield: 612.8 mg (0.730 mmol, 98%)
white powder. Anal. Found: C, 47.32; H, 5.10; N, 3.36.
Calc. for C33H42F6N2PPdSb: C, 47.20; H, 5.04; N,
3.34%.
1H-NMR (CDCl3, 300 MHz): [ppm] dꢁ
JH,P 2.1 Hz, 3H, PdCH3), 0.95, 1.16, 1.21, 1.40 (4*d,
Jꢁ 1.76 (m, 2H, CH2), 1.71
6.9 Hz, 4*3H, CHi3Pr), 1.49Á
(s, 3H, NCCH3), 1.98Á2.30 (m, 4H, CH2), 2.89 (hept.,
Jꢁ 6.9 Hz, 1H,
6.9 Hz, 1H, CHiPr), 2.96 (hept., Jꢁ
CHiPr), 4.67 (dt, JH,H
7.8 Hz, JH,P 11.4 Hz, 1H,
PCH), 7.13Á
7.85 (m, 13H, Harom); 13C{1H}-NMR
(CDCl3, 75 MHz): [ppm] dꢁ 3.2 (d, JC,P 2.1 Hz,
PdCH3), 1.3 (NCCH3), 23.5, 23.7, 23.8, 24.5 (CHi3Pr),
25.9 (d, JC,P 6.6 Hz, CH2), 27.0 (d, JC,P 9.4 Hz,
CH2), 28.2, 28.3 (CHiPr), 30.9 (d, JC,P
7.0 Hz, CH2),
57.1 (d, JC,P 30.0 Hz, PCH), 119.0 (NCCH3), 124.9Á
138.6 (CHarom, Cipso), 142.2 (NCipso), 195.7 (d, JC,P
8.7 Hz, Cꢁ
N); 31P{1H}-NMR (CDCl3, 121 MHz):
[ppm] dꢁ 1653.4 (s,
45.07 (s); IR (KBr): [cmꢂ1] nꢁ
CꢁN), 2317.6, 2289.7 (w, CꢂN); SIMS (DTE/DTT/Sul),
cation: m/z (Irel. (%))ꢁ DTE/
686 (7) [(PfflN)Pdꢀ
DTTꢂ
1]ꢀ, 548 (37) [(PfflN)Pd(CH3)]ꢀ, 533 (22)
[(PfflN)Pd]ꢀ, 346 (12) [C17H22NPd]ꢀ, 291 (4)
/
0.33 (d,
ꢁ
/
/
/
/
/
/
ꢁ
/
ꢁ
/
/
/
ꢂ
/
ꢁ
/
1H-NMR (CDCl3, 300 MHz): [ppm] dꢁ
JH,P 1.5 Hz, 3H, PdCH3), 1.08, 1.09, 1.16 (3*d, Jꢁ
6.9 Hz, 3*3H, CHi3Pr), 1.16Á
1.30 (m, 2H, CH2), 1.39 (d,
Jꢁ 1.96
6.9 Hz, 3H, CHi3Pr), 1.69 (s, 3H, NCCH3), 1.68Á
(m, 4H, CH2), 2.20 (m, 1H, CH2), 2.44 (m, 1H, CH2),
2.63 (hept., Jꢁ 6.9
6.9 Hz, 1H, CHiPr), 2.90 (hept., Jꢁ
Hz, 1H, CHiPr), 4.07 (m, 1H, PCH), 7.13Á
7.71 (m, 13H,
arom); 13C{1H}-NMR (CDCl3, 75 MHz): [ppm] dꢁ
3.6 (PdCH3), 1.1 (NCCH3), 23.4, 23.5, 23.7, 23.8
(CHi3Pr), 24.8 (d, JC,P
8.1 Hz, CH2), 25.3 (CH2),
28.0, 28.3 (CHiPr), 31.5 (d, JC,P
3.5 Hz, CH2), 33.3
(d, JC,P 5.9 Hz, CH2), 53.5 (d, JC,P 30.7 Hz, PCH),
118.8 (NCCH3), 123.7Á138.9 (CHarom, Cipso), 141.8
(NCipso), 185.5 (d, JC,P
6.3 Hz, Cꢁ
N); 31P{1H}-
NMR (CDCl3, 121 MHz): [ppm] dꢁ53.41 (s); IR
(KBr): [cmꢂ1] nꢁ
1620.8 (m, CꢁN), 2319.4, 2291.6 (w,
CꢂN); SIMS (DTE/DTT/Sul), cation: m/z (Irel. (%))ꢁ
/0.29 (d,
ꢁ
/
/
ꢁ
/
ꢁ
/
/
ꢁ
/
/
/
ꢁ
/
/
ꢁ
/
/
/
/
/
/
/
H
/
ꢂ
/
/
/
/
/
ꢁ
/
/
ꢁ
/
ꢁ
/
ꢁ
/
[PdPPh2]ꢀ, 242 (58) [(PfflN)ꢀ
/
PPh2]ꢀ, 240 (27)
/
[C17H22N]ꢀ, 238 (7), 226 (6) [(CH2)2CHPPh2]ꢀ, 147
(19), 109 (26), 97 (13), 95 (40), 93 (16), 83 (25), 81 (95),
69 (100), 67 (31); SIMS (DTE/DTT/Sul), Anion: m/z
ꢁ
/
/
/
/
/
(Irel. (%))ꢁ
/
235 (100) [SbF6]ꢂ.
/
/