G. Ferguson et al. / Journal of Organometallic Chemistry 617–618 (2001) 671–680
679
(s at l=2.6 and 3.45), 13, 14 and carbene complex 17
4.3.6. Dichloro[(h-dimethylamino)benzylidene]-
(triphenylphosphine)platinum(II) (17)
could be detected. These resonances grew slowly when
the solution was left to stand, but initial product 11 was
still present after several days.
Similar initial clean conversion of 1 into 11 was
observed under air when dry CDCl3 was used, with the
addition of one or two small pellets of CaH2.
Carbene complex 1 (16.0 mg, 27.3 mmol) and
PhSnMe3 (9.9 mg, 41 mmol) in dry CDCl3 (1 cm3) were
allowed to sit until conversion of 1 into 11 was com-
plete. The solution was transferred to a round-bot-
tomed flask, the solvent was removed in vacuo, and the
residue was left under vacuum (ca 1 torr) overnight.
The resulting dark, gummy material was then subjected
to preparative TLC (eluant MeOH–CH2Cl2, 1:49) to
give a fraction containing 17. Recrystallization from
CH2Cl2–benzene gave pure 17 (4.2 mg, 23%) contain-
ing some water. Anal. Found: C, 48.71; H, 4.04; N,
2.02 C27H26Cl2NPPt·0.25H2O Calc.: C, 48.69; H, 4.01;
N, 2.10%. 1H-NMR l=2.98(s, 4JPtꢀH=7 Hz, 3H,
NMe), 4.14(s, 4JPtꢀH=9 Hz, 3H, NMe), 6.53(d,
4.3.4. Preparation of chloro[(h-dimethylamino)benzyl]-
(triphenylphosphine)platinum(II) (11)
Complex 1 (22.4 mg, 38.4 mmol) and PhSnMe3 (11.9
mg, 49.3 mmol) were dissolved in dry CDCl3 (1.4 cm3)
in a dry NMR tube under N2. The tube was capped
and the reaction was allowed to proceed until conver-
sion of 1 into 11 was complete (B2 h). The tube was
then opened to air and the reaction solution was
washed with water (3×2 cm3) to remove Me3SnCl and
briefly dried (Na2SO4). The resulting solution was con-
centrated in vacuo almost to dryness, and the resulting
gummy residue was triturated with pentane to precipi-
tate a white solid. This was washed with fresh pentane
and dried in vacuo to give an essentially clean sample
of 11 (22.3 mg, 92.6%). Recrystallization from CH2Cl2–
pentane, or CH2Cl2–diethylether gave 11 containing
one molar equivalent of water. Anal. Found: C, 50.40;
H, 4.40; N, 2.08. C27H27ClNPPt·H2O. Calc.: C, 50.27;
3
3JHꢀH=7.6 Hz, 2H, CꢀPh o−H), 7.14 (t, JHꢀH=7.6
3
Hz, 2H, C−Ph m−H), 7.25 (t, JHꢀH=7.6 Hz, 1H,
C−Ph p−H) 7.33(br, 6H, aromatic H) and 7.42(br,
9H, aromatic H). 31P-NMR l=7.77(1JPtꢀP=4194 Hz).
References
[1] See, for example, J.P. Collman, L.S. Hegedus, J.R. Norton R.G.
Finke, Principles and Applications of Organotransition Metal
Chemistry, University Science Books, Mill Valley, CA, 1987, pp.
379–382, 469–485, 590–591 and 783–815.
[2] See, for example (a) F.R. Hartley in: G. Wilkinson, F.G.A.
Stone, E.W. Abel (Eds.), Comprehensive Organometallic Chem-
istry, vol. 6, Pergamon Press, Oxford, 1982, pp. 502–511. (b)
R.J. Cross in: E.W. Abel, F.G.A. Stone, G. Wilkinson (Eds.),
Comprehensive Organometallic Chemistry II, vol. 9, Elsevier
Science, New York, 1995, pp. 419–426.
1
4
H, 4.53; N, 2.17%. H-NMR l=2.63 (d, JPꢀH=5.6
3
4
Hz, JPtꢀH=18 Hz, 3H, NMe), 3.10(d, JPꢀH=4.8 Hz,
3JPtꢀH=24 Hz, 3H, NMe), 4.19 (d, 3JPꢀH=5.6 Hz,
2JPtꢀH=80 Hz, 1H, CHPh), 6.9−7.2(m, 3H, CHPh),
7.25(br, 11H, aromatic H) and 7.49(br, 6H, aromatic
H). 31P-NMR l=23.67(1JPtꢀP=5526 Hz).
[3] R.A. Michelin, R. Bertani, M. Mozzon, G. Bombieri, F. Bene-
tollo, M. de Fatima, C. Guedes da Silva, A.J.L. Pombiero,
Organometallics 12 (1993) 2372 and references therein.
[4] For a recent summary, see D. Bourissou, O. Guerret, F.P.
Gaba¨ı, G. Bertrand, Chem. Rev. 90 (2000) 76.
[5] (a)R. McCrindle, A.J. McAlees, Organometallics 12 (1993) 2445.
(b) P. Bergamini, E. Costa, A.G. Orpen, P.G. Pringle, M.B.
Smith, Organometallics 14 (1995) 3178.
[6] (a)Z. Lu, W.M. Jones, W.R. Winchester, Organometallics 12
(1993) 1344. (b) G.W.V. Cave, A.J. Hallett, W. Errington, J.P.
Rourke, Angew. Chem. Int. Ed. Engl. 37 (1998) 3270.
[7] M.H. Chisholm, H.C. Clark, W.S. Johns, J.E.H. Ward, K.
Yasufuku, Inorg. Chem. 14 (1975) 900.
[8] G.L. Casty, J.M. Stryker, Organometallics 16 (1997) 3083.
[9] (a) E.K. Barefield, A.M. Carrier, D.J. Sepelak, D.G. Van
Derveer, Organometallics 1 (1982) 103. (b) G. Ferguson, Y. Li,
A.J. McAlees, R. McCrindle, K. Xiang, Organometallics 18
(1999) 2428.
4.3.5. Dichloro[(h-dimethylammonio)benzyl]-
(triphenylphosphine)platinum(II) (12)
Excess acetyl chloride (three to four equivalents) was
added to a solution of 11 (15.5 mg, 24.0 mmol) in
1
CDCl3 (1 cm3). Monitoring by H-NMR spectrometry
showed consumption of 11 and formation of 12 along
with additional minor products. During this time, a
white, crystalline solid began to deposit. The sample
was left in the refrigerator overnight, the crystals were
recovered and washed with CDCl3 to give 12 (9.7 mg,
61%). Recrystallization from CH2Cl2–CHCl3 gave ma-
terial containing CHCl3. Anal. Found: C, 45.14; H,
3.87; N, 1.96. C27H29Cl2NPPt·0.6CHCl3 Calc.: C, 45.10;
H, 3.92; N, 1.91%. 1H-NMR (CD2Cl2) l=2.24.(d,
3
3JHꢀH=5.6 Hz, 3H, NMe), 3.23(d, JHꢀH=5.2 Hz, 3H,
NMe), 3.29 (t, 3JHꢀH=3JPꢀH=7.8 Hz, 1H, CHPh),
7.15(br m, 3H, CHPh), 7.38(m, 7H, aromatic H), 7.50
(m, 10H, aromatic H) and 8.75(br, 1H, NH). A 2D
COSY spectrum showed that the resonance at l=8.75
was coupled to those at l=2.24, 3.23 and 3.29. 31P-
NMR (CDCl3) l=13.13 (1JPtꢀP=4710 Hz).
[10] See Ref. [2a] pp. 508–509.
[11] For Pt(IV) a-aminoalkyl derivatives, see C.R. Baar, L.P. Car-
bray, M.C. Jennings, R.J. Puddephatt, J. Am. Chem. Soc. 122
(2000) 176.
[12] R. McCrindle, G.J. Arsenault, R. Farwaha, M.J. Hampden-
Smith, R.E. Rice, A. McAlees, J. Chem. Soc. Dalton
Trans.(1988) 1773.
On standing, solution 12 decomposed to give mainly
benzaldehyde and 14 along with a trace of 13.
[13] R. McCrindle, G. Ferguson, G.J. Arsenault, A.J. McAlees, B.L.
Ruhl, D.W. Sneddon, Organometallics 5 (1986) 1171.