FULL PAPER
2
1
11), 156.77 (d, J = 10.6 Hz, C-14), 172.55 (d, J = 54.4 Hz, C-2)
ppm. 31P{1H} NMR (CDCl3): δ = 52.5 ppm.
Crystal Structure Analyses: A crystal of 4 was mounted on a glass
fibre in inert oil. The data were recorded at low temperature with
an Oxford Diffraction Xcalibur Nova diffractometer by using Cu-
Kα radiation (λ = 1.54184 Å). The structure was solved by direct
methods and refined by full-matrix least-squares on F2.[18] Hydro-
gen atoms were included by using a riding model or rigid methyl
groups. The crystal data are compiled in Table 1.
2,6-Bis(5-methyl-1,3-benzazaphosphol-2-yl)pyridine (7) and 2-(5-
Methyl-1,3-benzazaphosphol-2-yl)-6-(4-tolylaminomethyl)pyridine
(8): Pyridine-2,6-dicarbaldehyde (0.91 g, 6.73 mmol), 1 (1.86 g,
13.4 mmol) and ClSiMe3 (0.34 mL, 20 mol-%) in toluene (10 mL)
were heated to reflux for 24 h and worked up with degassed 5%
aq. NaOH/diethyl ether solution as described above. The resulting
yellow oil displayed strong 31P NMR signals at δ = 82.7 (br) and
79.2 ppm (intensity ratio 64:36) and three trace signals in the same
region. An attempt at purification by column chromatography un-
der inert conditions was made with dry 30% Et2O/n-hexane. The
main fraction gave a yellow solid (403 mg); however, this was still
a mixture of two 1,3-benzazaphospholes, 7 and 8, pMe ratio
28:36:36 (by 1H NMR integration), molar ratio ca. 30:70. 31P
NMR ([D6]DMSO): δ = 79.4 (s, 7), 77.3 (s, 8) ppm; intensity ratio
ca. 40:60.
CCDC-928891 (for 4) contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge from
The Cambridge Crystallographic Data Centre via www.ccdc.cam.
ac.uk/data_request/cif.
Supporting Information (see footnote on the first page of this arti-
cle): Procedure for the reaction of 1 with glyoxal, NMR spectra of
the new compounds.
Acknowledgments
1
3
7: H NMR ([D6]DMSO): δ = 2.43 (s, 6 H, 5-Me), 7.29 (br. d, J
= 8.3 Hz, 2 H, 6-H), 7.50–8.02 (superimposed m, aryl-H), 12.78
(br. s, 2 H, NH) ppm. 13C NMR ([D6]DMSO): δ = 20.04 (s, CH3),
114.68 (s, C-7), 120.15 (dd, 3J = 13.3, 5J = 2.8 Hz, C-3Ј, C-5Ј),
127.16 (d, 4J ≈ 3 Hz, C-6), 127.51 (d, 2J = 21.2 Hz, C-4), 129.06
Financial support and a fellowship from the Higher Education
Commission, Pakistan (HEC) and Deutscher Akademischer Aus-
tausch Dienst (DAAD) are gratefully acknowledged. The authors
thank G. Thede and M. Steinich for NMR and LRMS measure-
ments and Dr. H. Frauendorf and G. Sommer-Udvarnoki (Georg
August University, Göttingen, Institut für Organische und Biomo-
lekulare Chemie) for HRMS measurements.
3
2
(d, J = 13.3 Hz, C-5), 138.86 (s, C-4Ј), 141.38 (d, J = 6.6 Hz, C-
7a), 141.95 (d, 1J = 39.8 Hz, C-3a), 151.21 (d, 2J = 20 Hz, C-2Ј, C-
1
6Ј), 170.53 (d, J = 49.1 Hz, C-2) ppm. HRMS (ESI, MeOH/FA):
calcd. for C21H17N3P2 [M + H]+ 374.0970; found 374.0971.
1
8: H NMR ([D6]DMSO): δ = 2.13 (s, 3 H, p-Me), 2.40 (s, 3 H, 5-
[1] a) Multiple Bonds and Low Coordination in Phosphorus Chemis-
try (Eds.: M. Regitz, O. J. Scherer), Thieme, Stuttgart, Ger-
many, 1990; b) Phosphorus: The Carbon Copy (Eds.: K. B.
Dillon, F. Mathey, J. F. Nixon), Wiley, New York, 1998; c)
Phosphorus-Carbon Heterocyclic Chemistry: The Rise of a New
Domain (Ed.: F. Mathey), Pergamon, Amsterdam, 2001.
[2] a) C. Müller, L. E. E. Broeckx, I. de Krom, J. J. M. Weemers,
Eur. J. Inorg. Chem. 2013, 187–202; b) L. Kollar, G. Keglevich,
Chem. Rev. 2010, 110, 4257–4302; c) C. Müller, D. Vogt, Dalton
Trans. 2007, 5505–5523; d) P. Le Floch, Coord. Chem. Rev.
2006, 250, 627–681.
3
Me), 4.44 (br. s, 2 H, NCH2), 6.32 (v br, 1 H, NH), 6.57 (mAAЈ, J
3
= 8.1 Hz, 2 H, H-o), 6.90 (mBBЈ, J = 8.1 Hz, 2 H, H-m), 7.21 (br.
3
3
d, J = 8.3 Hz, 1 H, 6-H), 7.31 (d, J = 7.6 Hz, 1 H, 5Ј-H), 7.50–
8.02 (superimposed m, aryl-H), 12.73 (br. s, 1 H, ring NH) ppm.
13C NMR ([D6]DMSO): δ = 20.88 (br. s, Me-5, Me-p), 48.68 (s,
NCH2), 112.59 (s, C-o), 115.10 (s, C-7), 118.60 (d, 3J = 13.3 Hz,
5
4
C-3Ј), 120.56 (d, J = 3 Hz, C-5Ј), 124.51 (s, C-p), 127.74 (d, J =
2.7 Hz, C-6), 127.90 (d, 2J = 21.2 Hz, C-4), 129.36 (d, 3J = 13.3 Hz,
2
C-5), 129.38 (s, C-m), 137.84 (s, C-4Ј), 141.81 (d, J = 7 Hz, C-7a),
142.05 (d, 1J = 39.8 Hz, C-3a), 146.10 (s, C-6Ј), 151.46 (d, 2J =
[3] a) S. Ito, K. Nishide, M. Yoshifuji, Organometallics 2006, 25,
1424–1430; b) M. Freytag, S. Ito, M. Yoshifuji, Chem. Asian J.
2006, 1, 693–700; c) L. Weber, Angew. Chem. 2002, 114, 583;
Angew. Chem. Int. Ed. 2002, 41, 563–572.
1
18.6 Hz, C-2Ј), 159.53 (s, C-i), 171.46 (d, J = 49.1 Hz, C-2) ppm.
HRMS (ESI, MeOH/FA): calcd. for C21H20N3P [M + H]+
346.14676; found 346.14.
[4] a) R. K. Bansal, J. Heinicke, Chem. Rev. 2001, 101, 3549–3578;
b) J. Heinicke, Trends Organomet. Chem. 1994, 1, 307–322; c)
J. Heinicke, Tetrahedron Lett. 1986, 27, 5699–5702; d) K.
Issleib, R. Vollmer, Z. Anorg. Allg. Chem. 1981, 481, 22–32.
[5] a) M. S. S. Adam, P. G. Jones, J. W. Heinicke, Eur. J. Inorg.
Chem. 2010, 3307–3316; b) B. R. Aluri, M. K. Kindermann,
P. G. Jones, I. Dix, J. W. Heinicke, Inorg. Chem. 2008, 47, 6900–
6912; c) B. R. Aluri, M. K. Kindermann, P. G. Jones, J. W. Hei-
nicke, Chem. Eur. J. 2008, 14, 4328–4335.
[6] a) B. Niaz, M. Ghalib, P. G. Jones, J. W. Heinicke, Dalton
Trans. 2013, 42, 9523–9532; b) M. Ghalib, B. Niaz, P. G. Jones,
J. W. Heinicke, Tetrahedron Lett. 2012, 53, 5012–5014; c) B. R.
Aluri, B. Niaz, M. K. Kindermann, P. G. Jones, J. Heinicke,
Dalton Trans. 2011, 40, 211–224.
Detection of (3-Methyl-isoindolino[2,1-a][1,3]benzazaphosphole-P)-
(pentacarbonyl)tungsten(0) (9): W(CO)5(THF), prepared from
W(CO)6 (291 mg, 0.83 mmol) by UV irradiation in THF (100 mL),
was stirred with 7 (180 mg, 0.80 mmol) for 24 h at room temp. Re-
moval of the solvent and excess W(CO)6 under vacuum (10–1 to
10–5 Torr) provided solid 9 (398 mg, ca. 80%), contaminated by
residual W(CO)6 and a minor side product. The compound was
identified by characteristic NMR spectroscopic data. 1H NMR
4
(CDCl3): δ = 2.51 (s, 3 H, CH3), 5.30 (d, JP,H = 11.0 Hz, 2 H,
3
NCH2), 7.29 (partly resolved dt, J = 8.7 Hz, 1 H, 6-H), 7.45 (dt,
4
3J = 7.6, J = JP,H = 1.3 Hz, 1 H, aryl), 7.47–7.57 (m, 3 H, aryl),
3
7.72 (dm, 3J = 8.7 Hz, 1 H, 7-H), 7.98 (br. d, J = 7.7 Hz, 1 H, 13-
H) ppm. 13C{1H} NMR and DEPT135 (CDCl3): δ = 21.31 (s,
[7] a) L. Nyulászi, Chem. Rev. 2001, 101, 1229–1246; b) T.
Veszprémi, L. Nyulászi, J. Reffy, J. Heinicke, J. Phys. Chem.
1992, 96, 623–626.
3
3
CH3), 54.21 (s, NCH2), 109.17 (d, J = 2.6 Hz, C-7), 122.30 (d, J
= 2.6 Hz, C-13), 124.41 (s, C-10), 127.71 (d, 2J = 14.6 Hz, C-4),
128.80 (d, J = 4.0 Hz, C-6), 129.40 (d, J = 3.9 Hz, C-11), 129.76
(d, J = 2.6 Hz, C-12), 131.99 (d, J = 15.6 Hz, C-5), 135.94 (d, J
[8] K. Issleib, H.-U. Brünner, H. Oehme, Organomet. Chem. Synth.
1970/71, 1, 161–168.
4
5
4
3
3
[9] D. Gelman, L. Jiang, S. L. Buchwald, Org. Lett. 2003, 5, 2315–
2
= 9.3 Hz, C-9), 139.15 (br, C-7a), 141.52 (d, J = 10.6 Hz, C-14),
2318.
142.34 (d, 1J = 20 Hz, C-3a), 172.5 (d, 1J = 20 Hz, C-2), 195.67 (d,
2JP,C = 7.9 Hz, 4 CO-cis), 200.45 (d, 2JP,C = 28 Hz, CO-trans) ppm.
[10] J. Heinicke, N. Gupta, A. Surana, N. Peulecke, B. Witt, K.
Steinhauser, R. K. Bansal, P. G. Jones, Tetrahedron 2001, 57,
9963–9972.
31P{1H} NMR (CDCl3): δ = 2.0 ppm (satellites, JP,W = 242 Hz).
1
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