N.J. Korte et al. / Journal of Organometallic Chemistry 745-746 (2013) 356e362
361
3
4
(dd, 1H, JHH ¼ 8.2, JHP ¼ 4.1, H(3) arom.). 13C{1H} NMR (
d
, ppm):
(d,1H, J ¼ 4.6, H(6) of Py). 13C{1H} NMR (
d
, ppm): 42.8 (d, 3JCP ¼ 21.8,
15.4 (s, CH3), 36.3 (s, CH2), 126.2 (d, 3JCP ¼ 12.6, C(6) arom.), 128.6 (d,
CH2), 121.0 (s, C(5) of Py), 123.6 (d, 2JCP ¼ 2.3, C(6) of C6H4), 126.9 (s,
C(4) of C6H4), 128.5 (d, 3JCP ¼ 7.1, m-PPh), 128.6 (s, p-PPh), 129.1 (s,
2JCP ¼ 11.9, m-PPh), 130.7 (br s, C(3) arom.), 131.1 (d, 1JCP ¼ 10.4, C(5)
2
4
3
arom.), 131.5 (d, JCP ¼ 7.9, C(2) arom.), 131.9 (d, JCP ¼ 2.8, p-PPh),
132.0 (d, 3JCP ¼ 9.7, o-PPh), 132.4 (d, 1JCP ¼ 37.7, ipso-PPh), 133.3 (s,
C(3) of Py), 130.3 (d, JCP ¼ 4.8, C(3) of C6H4), 133.8 (s, C(4) of Py),
133.9 (d, 2JCP ¼ 19.7, o-PPh), 136.1 (s, C(5) of C6H4), 136.2, 136.6 and
144.1 (three d, 2JCP ¼ 11.3, 1JCP ¼ 26.3, 1JCP ¼ 10.3, respectively, C(1)
of C6H4, PC(2) of C6H4 and ipso-PPh2), 149.1 (s, C(6) of Py), 160.5 (s,
C(4) arom.), 133.5 (d, 1JCP ¼ 12.9, C(1) arom.). 31P{1H} NMR (
d, ppm):
16.9. HRMS: [M þ H]þ calcd for C20H20PSO 339.0977, found
339.0969.
C(2) of Py). 31P{1H} NMR (
d
, ppm): ꢁ29.4. HRMS [M þ H]þ calcd for
C24H21NP 354.14116, found 354.14506.
4.5.5. [2-(Diphenylphosphoryl)benzyl]diphenylphosphine oxide
(14)
4.5.8. 20-(Diphenylphosphino)-N,N-dimethylbiphenyl-2-amine (20)
The compound was synthesized from CPC 19 (21.1 mg) as a
white solid in 47% yield (11.2 mg) using the procedure described for
(S)-6. The eluent used for the preparative TLC was benzene. Rf 0.77
(benzene). The 1H and 13C{1H} NMR spectra matched the literature
The dioxide was obtained from CPC 12 (25.0 mg) as a white solid
in 35% yield (9.9 mg) following the procedure described for (S)-6. In
the end of the reaction, air was bubbled through the mixture for 1 h
to ensure the oxidation of the product. The eluent used for the
preparative TLC was a 3:1 benzeneeacetone mixture. Rf 0.57 (3:1
data [46]. 31P{1H} NMR (
d
, ppm): ꢁ29.4 (lit. data: ꢁ13.9 ppm
benzeneeacetone); m.p. 172e175 ꢀC, dec.; 1H NMR (
d
, ppm): 3.36
relative to 85% H3PO4 in CDCl3 [46]).
2
4
3
(dd, 2H, JHP ¼ 10.7, JHP ¼ 5.4, CH2), 6.74 (dd, 1H, JHH ¼ 7.9,
4
3JHP ¼ 10.4, H(3) arom.), 7.00 (br t, 1H, 3J ¼ 6.4, JHP ¼ 6.0, H(6)
4.5.9. [2,6-Bis(methylthiomethyl)phenyl]diphenylphosphine (23)
The highest yield of compound 23, 49%, was obtained from CPC
22 and KPPh2 in hexane using 1.2 equiv. of KPPh2 and the CPC
concentration of 3 mg/mL. The solvent used for preparative TLC was
benzene. Disulfidophosphine 23 was obtained as a pale yellow
arom.), 7.20 (t, 1H, 3J ¼ 8.0, H(4) arom.), 7.31 (t, 1H, 3J ¼ 7.4, H(5)
arom.), 7.38 (m, 4H, m-PPh1), 7.46 (m, 2H, p-PPh1), 7.51 (m, 4H, m-
PPh2), 7.59 (m, 2H, p-PPh2), 7.73 (br. m, 8H, o-PPh1 and o-PPh2). 13
C
1
3
NMR (
d
, ppm): 33.5 (dd, JCP ¼ 27.4, JCP ¼ 15.8, CH2), 125.5 (dd,
1JCP ¼ 51.3, 3JCP ¼ 11.5, C(2) arom.), 127.9 (d, 1JCP ¼ 58.9, ipso-PPh1),
128.2 (d, 1JCP ¼ 56.4, ipso-PPh2), 128.4 (dd, 3JCP ¼ 8.9, 5JCP ¼ 3.1, C(4)
arom.), 128.7 (d, 3JCP ¼ 11.6, m-PPh2), 129.0 (d, 3JCP ¼ 11.9, m-PPh1),
131.8 (d, 4JCP ¼ 2.6, p-PPh2), 132.0 (m, C(5) and C(6) arom.), 132.1 (d,
4JCP ¼ 2.3, p-PPh1), 133.5 (d, 2JCP ¼ 10.6, o-PPh2), 134.0 (d, 3JCP ¼ 5.2,
syrup with an unpleasant odor. Rf 0.68 (benzene); 1H NMR (
d, ppm):
1.81 (s, 6H, 2 CH3), 3.77 (s, 4H, 2 CH2), 7.27e7.34, 7.45e7.48 (three
m,13H, PPh2 and C6H3). 13C{1H} NMR (
d, ppm): 15.4 (s, CH3), 38.9 (d,
3JCP ¼ 18.6, CH2), 127.7 (s, p-PPh), 128.5 (d, 3JCP ¼ 5.5, m-PPh), 129.3
3
(d, JCP ¼ 3.9, C(3) and C(5) arom.), 130.4 (s, C(4) arom.), 131.4 (d,
C(3) arom.), 134.8 (d, JCP ¼ 11.7, o-PPh1), 137.3 (dd, JCP ¼ 11.8,
2JCP ¼ 17.5, o-PPh), 132.9 (d, JCP ¼ 21.1, C(1) arom.), 136.1 (d,
2
2
1
2JCP ¼ 2.3, C(1) arom.). 31P{1H} NMR (
d
, ppm): 35.4 and 8.9 (two d,
2JCP ¼ 15.1, C(2) and C(6) arom.), 146.1 (d, 1JCP ¼ 14.5, 2C, ipso-PPh).
4JPP ¼ 6.4). IR (
n
, cmꢁ1, CH2Cl2): 1266 s (P]O), 1225 s (CH2P¼O).
31P{1H} NMR (
C22H24PS2 383.10625, found 383.10845.
d
, ppm, CDCl3): ꢁ34.7. HRMS: [M þ H]þ calcd for
HRMS [M þ Na]þ calcd for C31H26O2NaP2 515.13002, found
515.13159.
Acknowledgment
4.5.6. Chloro-{2-[(diphenylphosphino)methyl]phenyl-
C,P}(tetraphenyldiphosphine oxide-P)palladium(II) (16)
The authors acknowledge financial support from ND EPSCoR
through NSF grant No. EPS-0-0184442.
The complex was isolated as a yellow powder in 13% yield from
the reaction of CPC 12 with KPPh2 (see the preparation of com-
pound 14). Rf 0.26 (5:1 benzeneeacetone); 1H NMR (
d, ppm): 3.27
Appendix A. Supplementary data
(dd, 2H, 2JHP ¼ 10.1, 4JHP ¼ 5.6, CH2), 6.7 (m, 2H, H(3) arom. and H(6)
arom.), 7.07 (m, 2H, H(4) arom. and H(5) arom.), 7.16e7.24 (br. m,
10H, m-PPh1, m-PPh2, and p-PPh1), 7.35 (m, 2H, p-PPh2), 7.46 (m,
Supplementary data related to this article can be found at http://
4H, m-PPh3), 7.51 (m, 2H, p-PPh3), 7.67e7.60 (br. m, 12H, o-PPh1, o-
PPh2, and o-PPh3). 13C NMR (
d
, ppm): 38.5 (dd, JCP ¼ 25.5,
1
2JCP ¼ 17.5, CH2), 127.0, (d, JCP ¼ 10.8, m-PPh1), 127.7, 130.7, 131.6
and 133.1 (four m, C(3), C(4), C(5) and C(6) arom.), 128.0 (d,
2JCP ¼ 11.4, m-PPh2), 128.1 (m, ipso-PPh1), 128.2 (m, ipso-PPh2),
128.8 (d, 4JCP ¼ 2.8, p-PPh1), 128.9 (d, 2JCP ¼ 10.7, m-PPh3), 130.7 (m,
C(5) arom.), 130.8 (d, 4JCP ¼ 2.4, p-PPh2), 131.0 (d, 4JCP ¼ 2.4, p-PPh3),
131.1 (d, 1JCP ¼ 12.3, ipso-PPh3), 131.5 (d, 3JCP ¼ 10.3, m-PPh1), 133.9
References
2
3
3
(d, JCP ¼ 11.1, o-PPh2), 134.8 (d, JCP ¼ 11.9, o-PPh3), 137.9 (dd,
3
2JCP ¼ 16.3, JCP ¼ 4.0, C(2) arom.), 141.5 (m, C(1) arom.). 31P{1H}
, ppm): 49.4 (dd, 1JPP ¼ 449, 3JPP ¼ 15.5, P(O)Ph2), 31.4 (dd,
NMR (
d
3
2
2JPP ¼ 61.1, JPP ¼ 15.5, CH2PPh2), ꢁ7.2 (dd, 1JPP ¼ 449, JPP ¼ 61.1,
PdPPh2).
4.5.7. 2-[2-(Diphenylphosphino)benzyl]pyridine (18)
The compound was synthesized from CPC 17 (19.7 mg) as a pale
yellow syrup in 47% yield (10.7 mg) using the procedure described
for (S)-6. The eluent used for the preparative TLC was a 10:1 ben-
zeneeacetone mixture. Rf 0.69 (10:1 benzeneeacetone); 1H NMR
(d, ppm): 4.45 (s, 2H, CH2), 6.93 (m, 2H, H(4) of Py and H(6) of C6H4),
6.91 (m,1H, H(6) of C6H4), 7.00 (br dd,1H, J ¼ 8.3, J ¼ 6.2, H(5) of Py),
7.14 (br t, 1H, 3J ¼ 6.8, H(4) of C6H4), 7.20e7.32 (m, 12H, PPh, H(3) of
Py and H(3) of C6H4), 7.39 (td, 1H, J ¼ 8.0, J ¼ 1.7, H(5) of C6H4), 8.46