Chemistry Letters 2002
1) -H elimination
73
ingly no chemical reactions of these complexes are reported.2
a) V. S. Reddy, K. V. Katti, and C. L. Barnes, Inorg. Chim.
Acta, 240, 367 (1995). b) G. F. Nieckarz, T. J. R. Weakley,
W. K. Miller, B. E. Miller, D. K. Lyon, and D. R. Tyler,
Inorg. Chem., 35, 1721 (1996). c) V. S. Reddy, D. E. Berning,
K. V. Katti, C. L. Barnes, W. A. Volkert, and A. R. Ketring,
Inorg. Chem., 35, 1753 (1996). d) V. S. Reddy, K. V. Katti,
and C. L. Barnes, J. Chem. Soc., Dalton Trans., 1996, 1301. e)
D. E. Berning, K. V. Katti, C. L. Barnes, W. A. Volkert, and
A. R. Ketring, Inorg. Chem., 36, 2765 (1997).
7
2) reductive
elimination
CH2=CH2 + CH3CH3
PtEt2L2
hydrolysis
2 CH3CH3
8
a) J. Chatt, G. J. Leigh, and R. M. Slade, J. Chem. Soc.,
Dalton Trans., 1973, 2021. b) K. N. Harrison, P. A. T. Hoye,
A. G. Orpen, P. G. Pringle, and M. B. Smith, J. Chem. Soc.,
Chem. Commun., 1989, 1096. c) P. G. Pringle and M. B.
Smith, Platinum Metals Rev., 34, 74 (1990). d) E. Costa, M.
Martin, P. G. Pringle, and M. B. Smith, Inorg. Chim Acta,
213, 25 (1993). e) D. E. Berning, K. V. Katti, L. J. Barbour,
and W. A. Volkert, Inorg. Chem., 37, 334 (1998). f) L.
Higham, A. K. Powell, M. K. Whittlesey, S. Wocadlo, and
P. T. Wood, Chem. Commun., 1998, 1107.
L2 = DHMPE (1b), 2 THMP (2b)
Scheme 2.
reaction such as ꢀ-hydrogen elimination even in water, and
suggest that such organometallic intermediates should be taken
into account in transition metal mediated organic transformations
and catalyses in water as well as in biphasic water/organic
solvents.
3
9
1a: Yield 72%. 1H NMR (D2O): ꢂ 0.50 (t, JH-P ¼ 7 Hz,
This work was supported by New Energy and Industrial
Technology Development Organization (NEDO) and Japan
Chemical Innovation Institute (JCII) through the R&D program
for the Next-Generation Chemical Process Technologies.
2JH-Pt ¼ 69 Hz, 6H, Pt-Me), 1.96 (m, 4H, PC2H4), 4.14 (dd,
2
2JH-H ¼ 14 Hz, JH-P ¼ 2:1 Hz, 4H, PCH2OH), 4.25 (d,
1
3
2JH-H ¼ 14 Hz, JH-Pt ¼ 12 Hz, 4H, PCH2OH). 31Pf Hg
1
NMR (D2O): ꢂ 49.3 (s, JP-Pt ¼ 1640 Hz). Anal. Calcd for
References and Notes
C8H22O4P2Pt: C, 21.87;H, 5.05%. Found: C, 21.05;H,
4.66%.
1
‘‘Aqueous-Phase Organometallic Catalysis. Concepts and
Applications,’’ ed. by B. Cornils and W. A. Herrmann,
Wiley-VCH (1998) and references cited therein.
J. E. Ellis, K. N. Harrison, P. A. T. Hoye, A. G. Orpen, P. G.
Pringle, and M. B. Smith, Inorg. Chem., 31, 3026 (1992).
D. P. Aterniti and J. D. Atwood, Chem. Commun., 1997,
1665.
Catalysis in biphasic media: a) J. P. Arhancet, M. E. Davis, J.
Merola, and B. E. Hanson, J. Catal., 121, 327 (1990). b) T.
Bartik, B. B. Bunn, B. Bartik, and B. E. Hanson, Inorg.
Chem., 33, 164 (1994). c) A. Fukuoka, W. Kosugi, F.
Morishita, M. Hirano, L. McCaffrey, W. Henderson, and S.
Komiya, Chem. Commun., 1999, 489.
10 2a: Yield 82% (by NMR). 1H NMR (D2O): ꢂ 0.49 (brs,
2JH-H ¼ 66 Hz, 6H, Pt-Me), 4.29 (br, 12H, PCH2OH).
1
31Pf Hg NMR (D2O): ꢂ 13.2 (s, 1JP-Pt ¼ 1700 Hz).
2
3
4
11 1c: Yield 64%. 1H NMR (D2O): ꢂ 2.10 (m, 4H, PC2H4), 4.11
(m, 8H, PCH2OH), 6.85 (t, 3JH-H ¼ 7 Hz, 2H, p-Ph), 7.08 (t,
3
4
3JH-H ¼ 7 Hz, 4H, m-Ph), 7.46 (t, JH-H ¼ JH-P ¼ 7 Hz,
1
3JH-Pt ¼ 52 Hz, o-Ph). 31Pf Hg NMR (D2O): ꢂ 43.9 (s,
1JP-Pt ¼ 1600 Hz). Anal. Calcd for C18H26O4P2Pt: C, 38.37;
H, 4.65%. Found: C, 38.38;H, 4.81%.
1
3
12 2c: Yield 58%. H NMR (D2O): ꢂ 4.06 (s, JH-Pt ¼ 11 Hz,
3
12H, PCH2OH), 6.79 (t, JH-H ¼ 7 Hz, 2H, p-Ph), 7.01 (t,
3
3
3JH-H ¼ 7 Hz, 4H, m-Ph), 7.41 (d, JH-H ¼ 7 Hz, JH-Pt
¼
¼
1
57 Hz, 4H, o-Ph). 31Pf Hg NMR (D2O): ꢂ 4.5 (s, JP-Pt
1
5
Catalysis in water: a) G. Papadogianakis and R. A. Sheldon,
New J. Chem., 20, 175 (1996). b) B. Cornils and E. Wiebus,
Chemtech, 1995, 33. c) F. Gassner and W. Leitner, Chem.
Commun., 1993, 1465. d) J. Kovacs, T. D. Todd, J. H.
Reibenspies, F. Joo, and D. J. Darensbourg, Organometallics,
19, 3963 (2000). e) C. S. Chin, W.-T. Chang, S. Yang, and K.-
S. Joo, Bull. Korean Chem. Soc., 18, 324 (1997). f) J. Cermak,
M. Kvicalova, V. Blechta, Collect. Czech. Chem. Commun.,
62, 355 (1997). g) P. T. Hoye, P. G. Pringle, M. B. Smith, and
K. Worboys, J. Chem. Soc., Dalton Trans., 1993, 269. h) A. E.
Shilov, in‘‘Activation and Functionarization of Alkanes,’’ ed.
by C. L. Hill, John-Wiley & Sons, New York (1989).
1660 Hz). Anal. Calcd for C18H28O6P2Pt: C, 36.19;H,
4.72%. Found: C, 36.46;H, 4.50%.
13 1b: Yield 86% (by NMR). 1H NMR (D2O): ꢂ 1.25 (q,
2
3JH-H ¼ 8 Hz, JH-Pt ¼ 71 Hz, 4H, Pt-CH2CH3), 1.26 (m,
2
6H, Pt-CH2CH3), 1.88 (m, 4H, PC2H4), 4.09 (dd, JH-H
14 Hz, 2JH-P ¼ 3 Hz, 4H, PCH2OH), 4.22 (d, 2JH-H ¼ 14 Hz,
¼
1
3JH-Pt ¼ 11 Hz, 4H, PCH2OH). 31Pf Hg NMR (D2O): ꢂ 48.3
(s, 1JP-Pt ¼ 1460 Hz).
14 2b: Yield 89% (by NMR). 1H NMR (D2O): ꢂ 1.14 (m, 6H, Pt-
3
2
CH2CH3), 1.2 (q, 4H, JH-H ¼ 8 Hz, JH-Pt ¼ 129 Hz, Pt-
1
CH2CH3) 4.33 (brs, 12H, PCH2OH). 31Pf Hg NMR (D2O): ꢂ
1
8.9 (s, 1JP-Pt ¼ 1470 Hz).
6
These compounds were characterized only by 31Pf Hg- and
1
13Cf Hg NMR spectra of the phosphorus ligands and no
15 Pt products were not characterized.
distinct evidence for Pt-Me moiety are described. Accord-