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A. Mayr, M. Pui Yin Yu / Journal of Organometallic Chemistry 577 (1999) 223–227
123.5, 123.3, 123.2, 123.0, 122.9, 121.4, 121.3 (PPh2,
CC6H4CC, C6H4, C6H2iPr2), 91.9, 91.6, 91.3, 91.0, 89.5,
89.0 (CꢀC), 31.6, 28.8 (CH(CH3)2), 27.5, 27.4, 27.2,
27.0 (CH2PPh2), 23.5, 22.7 (CH3). 31P-NMR (CDCl3):
l 39.2 (1JWP=231 Hz). IR (CH2Cl2, cm−1): 2008 (s,
wCO), 1940 (s, wCO).
29.8 (CH(CH3)2), 27.5, 27.4, 27.1, 27.0 (CH2PPh2), 22.5
(CH3). 31P-NMR (CDCl3): l 39.2 (1JWP=231 Hz). IR
(CH2Cl2, cm−1): 2206 (w, wCC), 2120 (m, wCN), 2008 (s,
wCO), 1940 (s, wCO).
Acknowledgements
3.4. [W(CC6H4(CCC6H4NC-4)-4)Cl(CO)2(dppe)] (5)
Support for this work by the Hong Kong Research
Grants Council and the Committee on Research and
Conference Grants (CRCG) of the University of Hong
Kong is gratefully acknowledged. M. Pui Yin Yu ac-
knowledges the receipt of a Postgraduate Studentship,
administered by The University of Hong Kong.
Complex 3 (1 mmol, 0.908 g) was dissolved in
CH2Cl2 (50 ml), and 0.56 ml NEt3 was added. After
cooling to −78°C, a solution of triphosgene (C3Cl6O3)
(0.2 g) in CH2Cl2 (10 ml) was added. The resulting
mixture was allowed to warm up to 0°C, and it was
stirred at 0°C for 30 min. The solvent was then re-
moved in vacuo. The residue was washed with hexane,
then redissolved in THF (30 ml) and filtered. The
solvent was again removed in vacuo. The residue was
redissolved in CH2Cl2. After filtration, hexane was
added to the solution to afford yellow–orange crystals
References
[1] (a) E.O. Fischer, Angew. Chem. 86 (1974) 651; E.O. Fischer,
Adv. Organomet. Chem. 14 (1976) 1. (b) E.O. Fischer, U.
Schubert, J. Organomet. Chem. 100 (1975) 59. (c) R.R. Schrock,
Acc. Chem. Res. 19 (1986) 342. (d) M.A. Gallop, W.R. Roper,
Adv. Organomet. Chem. 25 (1986) 121. (e) H.P. Kim, R.J.
Angelici, Adv. Organomet. Chem. 27 (1987) 51. (f) H. Fischer, P.
Hofmann, F.R. Kreissl, R.R. Schrock, U. Schubert, K. Weiss
(Eds.), Carbyne Complexes, VCH, Weinheim, Germany, 1988.
(g) F.G.A. Stone, Adv. Organomet. Chem. 31 (1991) 53. (h) A.
Mayr, H. Hoffmeister, Adv. Organomet. Chem. 32 (1991) 227.
(i) P.F. Engel, M. Pfeffer, Chem. Rev. 95 (1995) 2281. (j) A.
Mayr, S. Ahn, Adv. Trans. Met. Coord. Chem. 1 (1996) 1. (k) L.
McElwee-White, Synlett (1996) 806.
[2] (a) N.M. Kostic´, R.F. Fenske, Organometallics 1 (1982) 489. (b)
N.M. Kostic´, R.F. Fenske, J. Am. Chem. Soc. 104 (1982) 3879.
(c) P. Hofmann in: H. Fischer, P. Hofmann, F.R. Kreissl, R.R.
Schrock, U. Schubert, K. Weiss (Eds.), Carbyne Complexes,
VCH, Weinheim, 1988.
[3] (a) T.P. Pollagi, S.J. Geib, M.D. Hopkins, J. Am. Chem. Soc.
116 (1994) 6051. (b) T.P. Pollagi, J. Manna, S.J. Geib, M.D.
Hopkins, Inorg. Chim. Acta 243 (1996) 177. (c) H.A. Brison,
T.A. Pollagi, T.C. Stoner, S.J. Geib, M.D. Hopkins, J. Chem.
Soc. Chem. Commun. (1997) 1263.
1
of 5 (0.266 g, 30%), m.p. 135–138°C (dec.). H-NMR
(CDCl3): l 7.75–7.13 (24H, PPh2, C6H4NC), 7.10 (d,
J=8.30 Hz, 2H, C6H4CC), 6.46 (d, J=8.31 Hz, 2H,
C6H4CC), 2.96–2.88 (m, 2H, CH2PPh2), 2.71–2.63 (m,
2H, CH2PPh2). 13C-NMR (CDCl3): l 264.6 (WꢀC),
1
cis
1
212.3 (CO, J =6 Hz, JtPrCans=46 Hz), 165.9 (NꢀC),
PC
149.2, 135.9, 135.3, 133.0, 132.8, 132.7, 132.5, 132.4,
132.1, 131.0, 130.7, 130.3, 130.1, 129.8, 129.7, 129.5,
129.2, 128.6, 128.5, 128.4, 128.3, 128.1, 126.5, 126.2,
125.9, 124.7, 121.1, 120.7 (PPh2, C6H4NC, C6H4CC),
92.6, 89.8 (CꢀC), 27.6, 27.4, 27.2, 27.0 (CH2PPh2).
31P-NMR (CDCl3):
l
38.5 (1JWP=231 Hz). IR
(CH2Cl2, cm−1): 2214 (w, wCC), 2125 (m, wCN), 2006 (s,
wCO), 1940 (s, wCO). Anal. Found: C, 58.48; H, 3.31; N,
1.68. C44H32ClNO2P2W·1/4CH2Cl2. Calc. C, 58.45; H,
3.60; N, 1.54%.
3.5. [W(CC6H4(CCC6H4(CCC6H2iPr2-
3,5-NC-4)-4)-4)Cl(CO)2(dppe)] (6)
[4] (a) E.C. Constable, Prog. Inorg. Chem. 42 (1994) 67. (b) M.D.
Ward, Chem. Soc. Rev. 24 (1995) 121.
[5] (a) L. Malatesta, F. Bonati (Eds.), Isocyanide Complexes of
Transition Metals, Wiley, New York, 1969. (b) P.M. Treichel,
Adv. Organomet. Chem. 11 (1973) 21. (c) S.J. Lippard, Prog.
Inorg. Chem. 21 (1976) 91. (d) Y. Yamamoto, Coord. Chem.
Rev. 32 (1980) 193. (e) E. Singleton, H.E. Oosthuizen, Adv.
Organomet. Chem. 22 (1983) 209. (f) W.P. Fehlhammer, M.
Fritz, Chem. Rev. 93 (1993) 1243. (g) F.E. Hahn, Angew. Chem.
105 (1993) 681; Angew. Chem. Int. Ed. Engl. 32 (1993) 650. (h)
D. Lentz, Angew. Chem. 106 (1994) 1377; Angew. Chem. Int.
Ed. Engl. 33 (1994) 1315.
[6] (a) L.-F. Mao, A. Mayr, Inorg. Chem. 35 (1995) 3183. (b) J.
Guo, A. Mayr, Inorg. Chim. Acta 261 (1997) 141. (c) M.E.
Squires, A. Mayr, Inorg. Chim. Acta 1264 (1997) 161. (d) K.Y.
Lau, A. Mayr, K.-K. Cheung, Inorg. Chim. Acta (in press). (e)
A. Mayr, L.-F. Mao, Inorg. Chem. (in press). (f) A. Mayr, J.
Guo, Inorg. Chem. (in press).
The synthesis follows the procedure described for 5,
whereby 4 (0.27 g) was used. (Amounts of solvent and
reagents same as described for 5). Yellow micro-crys-
1
tals. Yield: 0.10 g, 27%, m.p. 125–128°C (dec.). H-
NMR (CDCl3): l 7.73–7.67 (8H, PPh2), 7.52 (d,
J=8.34 Hz, 2H, C6H4), 7.48 (d, J=8.38 Hz, 2H,
C6H4), 7.40–7.21(14H, PPh2, C6H2iPr2), 7.10 (d, J=
8.24 Hz, 2H, CC6H4), 6.46 (d, J=8.23 Hz, 2H,
CC6H4), 3.41–3.35 (m, 2H, CH(CH3)2), 3.00–2.88 (m,
2H, CH2PPh2), 2.71–2.59 (m, 2H, CH2PPh2), 1.30 (d,
12H, CH3). 13C-NMR (CDCl3): l 265.0 (WꢀC), 212.3
1
cis
1
(CO, J =8 Hz, JtPrCans=46 Hz), 170.0 (NꢀC), 148.9,
PC
145.3, 135.8, 135.2, 132.9, 132.8, 132.7, 132.5, 132.1,
131.6, 131.5, 130.6, 130.3, 130.1, 129.4, 128.8, 128.6,
128.5, 126.7, 124.1, 124.0, 123.4, 122.6, 121.2 (PPh2,
CC6H4CC, C6H4, C6H2iPr2), 92.0, 91.2, 90.7 (CꢀC),
[7] M.P.Y. Yu, A. Mayr, K.-K. Cheung, J. Chem. Soc. Dalton
Trans. (1998) 475.
[8] M.P.Y. Yu, K.-K. Cheung, A. Mayr, J. Chem. Soc. Dalton
Trans. (1998) 2373.