Romeo et al.
Synthesis of Complexes. The compounds cis-[PtCl2(Me2SO)2]34
and trans-[Pt(Me)Cl(Me2SO)2]35 were synthesized by following
earlier reported procedures.
7.12-7.56 (m, 13H, H-P(Ar), H8); 3.59 (s, 3H, CH3z); 2.95 (s, 3H,
CH3A); 1.78 (s, 3H, CH3B); 1.55 (s, 3H, CH3y); 0.88 (s, 3H, CH3x);
2
0.56 (m, JPt-H ) 74 Hz, 3H, Pt-CH3). 31P NMR (CDCl3, T )
298 K): δ 5.23 (1JPt-P ) 4502 Hz).
[Pt(Me)(dmphen)(P(o-tolyl)3)]BArf (5). (63.3% yield). Anal.
Calcd for C68H48BF24N2PPt: C, 51.50; H, 3.05; N, 1.77. Found:
C, 53.01; H, 3.35; N, 1.58. 1H NMR (CDCl3, T ) 298 K): δ 8.32
[Pt(Me)Cl(dmphen)]. Upon adding a weighted amount of
dmphen (237.0 mg, 1.08 mmol) in methanol (10 mL) to a solution
of trans-[Pt(Me)Cl(Me2SO)2] (441.2 mg, 1.08 mmol) in methanol
(30 mL), a bright-yellow precipitate immediately formed, which
was filtered off, washed with methanol to eliminate traces of
dimethylsulfoxide, and air-dried (88.5% yield). Anal. Calcd for
C15H15ClN2Pt: C,39.70; H, 3.33; N, 6.17. Found: C,40.11; H, 3.23;
(d, 1H, H4); 8.22 (d, 1H, H7); 7.00-8.00 (m, 28H, H-P(Ar),, H5,6
,
H8, H3, H-BArf); 3.58 (s, 3H, CH3z); 2.91 (s, 3H, CH3A); 1.70 (s,
2
3H, CH3B); 1.52 (s, 3H, CH3y); 0.86 (s, 3H, CH3x); 0.61 (m, JPtH
) 69 Hz, 3H, Pt-CH3). 31P NMR (CDCl3, T ) 298 K): δ 5.13
1
N, 6.37. H NMR (CDCl3, T ) 298 K): δ 8.31 (d, 1H, H4); 8.28
(1JPt-P ) 4514 Hz).
(d, 1H, H7); 7.76 (s, 2H, H5,6); 7.60 (d, 1H, H3); 7.54 (d, 1H, H8);
2.95 (s, 3H, CH3A); 1.70 (s, 3H, CH3B); 1.32 (s, 2JPt-H ) 80.3 Hz,
3H, Pt-CH3).
Cyclometalated [Pt(dmphen)(P(o-tolyl)2-Ph-CH2-κC,P)]X (X
) PF6-, (6); SbF6-, (7); CF3SO3-, (8); BF4-, (9); BArf -, (10)).
In a typical procedure, a solution of 1-5 in tetrachloroethane was
warmed at 360 K for a few hours in a sealed vial. The excess solvent
was evaporated under reduced pressure, the residue was dissolved
in dichloromethane, and the products were separated out on adding
diethyl ether and cooling.
[Pt(Me)(dmphen)(P(o-tolyl)3)]X. (X ) PF6-, 1; SbF6-, 2;
CF3SO3-, 3; BF4-, 4; BArf -, 5). The typical procedure was as
follows. A known amount of [Pt(Me)Cl(dmphen)] in CH2Cl2 (15
mL) containing a few drops of methanol was dissolved by adding
slowly under stirring a solution of the stoichiometric amount of
AgX in acetone (AgPF6, for 1; AgSbF6, for 2; AgCF3SO3 for 3;
AgBF4, for 4). AgCl was separated out, the solution was filtered
on a cellulose column to remove residual AgCl, and added with
the stoichiometric amount of three-o-tolylphosphane upon cooling
under dinitrogen atmosphere. The reaction was left to go to
completion (within a couple of hours), the excess solvent was
evaporated under reduced pressure, and the residue was crystallized
in good yield from dichloromethane/diethyl ether. The synthesis
of 5 required the use of NaBArf in dichloromethane instead of a
silver salt and the elimination of solid NaCl.
[Pt(dmphen)(P(o-tolyl)2-Ph-CH2-κC,P)]PF6 (6). (81.2% yield).
Anal. Calcd for C35H32F6N2P2Pt: C, 49.36; H, 3.79; N, 3.29.
1
Found: C, 47.96; H, 3.63; N, 2.99. H NMR (C2D2Cl4, T ) 233
K): δ 9.65 (br, 1H, H-P(Ar)); 8.52 (d, 3JHH ) 8.8 Hz, 1H, H4); 8.30
3
3
(d, JHH ) 8.8 Hz, 1H, H7); 7.94 (s, 1H, H-P(Ar)); 7.90 (d, JHH
)
8.8 Hz, 2H, H5,6); 7.86 (s, 1H, H-P(Ar)); 7.61 (br, 1H, H-P(Ar)); 7.50
3
(br, 1H, H-P(Ar)); 7.33 (br, 3H, H-P(Ar)); 7.19 (d, JHH ) 8.8 Hz,
3
1H, H3); 7.13 (s, 2H, H-P(Ar)); 7.06 (d, JHH ) 8.8 Hz, 1H, H8);
6.98 (br, 1H, H-P(Ar)); 6.92 (br, 1H, H-P(Ar)); 4.14 (br, 1H, CH2a′);
3.83 (br, 1H, CH2a); 3.12 (s, 3H, CH3A); 2.31 (br, 3H, CH3y); 1.95
(s, 3H, CH3B); 1.60 (br, 3H, CH3x). 31P NMR (C2D2Cl4, T ) 233
K): δ 30.3 (1JPtPav ) 4413 Hz).
[Pt(Me)(dmphen)(P(o-tolyl)3)]PF6 (1). (87.2% yield) Anal.
Calcd for C36H36F6N2P2Pt: C, 49.83; H, 4.18; N, 3.23. Found: C,
49.68; H, 4.22; N, 2.97. 1H NMR (CDCl3, T ) 298 K): δ 8.55 (d,
1H, H4); 8.40 (d, 1H, H7); 8.00 (s, 2H, H5,6); 7.76 (d, 1H, H3);
7.01-7.43 (m, 13H, H-P(Ar), H8); 3.58 (s, 3H, CH3z); 2.95 (s, 3H,
CH3A); 1.78 (s, 3H, CH3B); 1.50 (s, 3H, CH3y); 0.85 (s, 3H, CH3x);
0.59 (m, 2JPtH ) 68 Hz, 3H, Pt-CH3). 31P NMR (CDCl3, T ) 298
K): δ 5.20 (1JPtP ) 4514 Hz).
[Pt(dmphen)(P(o-tolyl)2-Ph-CH2-κC,P)]SbF6 (7). (85.4% yield).
Anal. Calcd for C35H32F6N2PPtSb: C, 44.60; H, 3.42; N, 2.97.
1
Found: C, 44.82; H, 3.63; N, 2.98. H NMR (C2D2Cl4, T ) 233
K): δ 9.65 (br, 1H, H-P(Ar)); 8.52 (d, 3JHH ) 8.8 Hz, 1H, H4); 8.31
3
3
(d, JHH ) 8.8 Hz, 1H, H7); 7.94 (s, 1H, H-P(Ar)); 7.90 (d, JHH
)
8.8 Hz, 2H, H5,6); 7.87 (s, 1H, H-P(Ar)); 7.61 (br, 1H, H-P(Ar)); 7.50
3
(br, 1H, H-P(Ar)); 7.33 (br, 3H, H-P(Ar)); 7.20 (d, JHH ) 8.8 Hz,
[Pt(Me)(dmphen)(P(o-tolyl)3)]SbF6 (2). (67.3% yield). Anal.
Calcd for C36H36F6N2PPtSb: C, 45.11; H, 3.79; N, 2.92. Found:
C, 46.00; H, 3.90; N, 2.64. 1H NMR (CDCl3, T ) 298 K): δ 8.54
(d, 1H, H4); 8.39 (d, 1H, H7); 7.96 (s, 2H, H5,6); 7.85 (d, 1H, H3);
7.01-7.67 (m, 12H, H-P(Ar),); 6.87 (d, 1H, H8); 3.58 (s, 3H, CH3z);
2.95 (s, 3H, CH3A); 1.78 (s, 3H, CH3B); 1.50 (s, 3H, CH3y); 0.85
3
1H, H3); 7.14 (s, 2H, H-P(Ar)); 7.06 (d, JHH ) 8.8 Hz, 1H, H8);
6.99 (br, 1H, H-P(Ar)); 6.91 (br, 1H, H-P(Ar)); 4.15 (br, 1H, CH2a′);
3.83 (br, 1H, CH2a); 3.13 (s, 3H, CH3A); 2.31 (br, 3H, CH3y); 1.95
(s, 3H, CH3B); 1.60 (br, 3H, CH3x). 31P NMR (C2D2Cl4, T ) 233
K): δ 30.3 (1JPtPav ) 4413 Hz).
2
(s, 3H, CH3x); 0.60 (m, JPt-H ) 69 Hz, 3H, Pt-CH3). 31P NMR
[Pt(dmphen)(P(o-tolyl)2-Ph-CH2-κC,P)]CF3SO3 (8). (91.2%
yield). Anal. Calcd for C36H32F3N2O3PPtS: C, 50.53; H, 3.77; N,
(CDCl3, T ) 298 K): δ 5.20 (1JPtP ) 4507 Hz).
1
3.27. Found: C, 49.20; H, 3.63; N, 3.12 H NMR (C2D2Cl4, T )
[Pt(Me)(dmphen)(P(o-tolyl)3)]CF3SO3 (3). (78.1% yield). Anal.
Calcd for C37H36F3N2O3PPtS: C, 50.97; H, 4.16; N, 3.21. Found:
C, 49.42; H, 4.10; N, 2.99. 1H NMR (CDCl3, T ) 298 K): δ 8.67
(d, 1H, H4); 8.55 (d, 1H, H7); 8.40 (s, 2H, H5,6); 7.80 (d, 1H, H3);
7.00-7.60 (m, 13H, H-P(Ar), H8); 3.59 (s, 3H, CH3z); 2.95 (s, 3H,
CH3A); 1.82 (s, 3H, CH3B); 1.50 (s, 3H, CH3y); 0.85 (s, 3H, CH3x);
0.60 (m, 2JPtH ) 71 Hz, 3H, Pt-CH3). 31P NMR (CDCl3, T ) 298
K): δ 5.21 (1JPtP ) 4507 Hz).
[Pt(Me)(dmphen)(P(o-tolyl)3)]BF4 (4). (88.2% yield). Anal.
Calcd for C36H36BF4N2PPt: C, 53.41; H, 4.48; N, 3.46. Found: C,
53.20; H, 4.35; N, 3.40. 1H NMR (CDCl3, T ) 298 K): δ 8.70 (d,
1H, H4); 8.50 (d, 1H, H7); 8.00 (s, 2H, H5,6); 7.90 (d, 1H, H3);
233 K): δ 9.64 (br, 1H, H-P(Ar)); 8.52 (d, 3JHH ) 8.8 Hz, 1H, H4);
3
8.30 (d, JHH ) 8.8 Hz, 1H, H7); 7.93 (s, 1H, H-P(Ar)); 7.89 (d,
3JHH ) 8.8 Hz, 2H, H5,6); 7.85 (s, 1H, H-P(Ar)); 7.61 (br, 1H, H-P(Ar));
3
7.49 (br, 1H, H-P(Ar)); 7.32 (br, 3H, H-P(Ar)); 7.19 (d, JHH ) 8.8
3
Hz, 1H, H3); 7.13 (s, 2H, H-P(Ar)); 7.05 (d, JHH ) 8.8 Hz, 1H,
H8); 6.98 (br, 1H, H-P(Ar)); 6.91 (br, 1H, H-P(Ar)); 4.14 (br, 1H,
CH2a′); 3.83 (br, 1H, CH2a); 3.11 (s, 3H, CH3A); 2.30 (br, 3H, CH3y);
1.94 (s, 3H, CH3B); 1.59 (br, 3H, CH3x). 31P NMR (C2D2Cl4, T )
233 K): δ 30.3 (1JPtPav ) 4413 Hz).
[Pt(dmphen)(P(o-tolyl)2-Ph-CH2-κC,P)]BF4 (9). (78.2% yield).
Anal. Calcd for C35H32BF4N2PPt: C, 52.98; H, 4.06; N, 3.53.
1
Found: C, 53.12; H, 3.93; N, 3.42 H NMR (C2D2Cl4, T ) 233
K): δ 9.63 (br, 1H, H-P(Ar)); 8.52 (d, 3JHH ) 8.8 Hz, 1H, H4); 8.30
(33) Brookhart, M.; Grant, B.; Volpe, A. F. Organometallics 1992, 11,
3920-3922.
3
3
(d, JHH ) 8.8 Hz, 1H, H7); 7.93 (s, 1H, H-P(Ar)); 7.90 (d, JHH
)
(34) Price, J. H.; Williamson, A. N.; Schramm, R. F.; Wayland, B. B. Inorg.
Chem. 1972, 11, 1280-1284.
8.8 Hz, 2H, H5,6); 7.86 (s, 1H, H-P(Ar)); 7.59 (br, 1H, H-P(Ar)); 7.48
3
(br, 1H, H-P(Ar)); 7.31 (br, 3H, H-P(Ar)); 7.17 (d, JHH ) 8.8 Hz,
(35) Eaborn, C.; Kundu, K.; Pidcock, A. J. Chem. Soc., Dalton Trans. 1981,
933-938.
3
1H, H3); 7.12 (s, 2H, H-P(Ar)); 7.04 (d, JHH ) 8.8 Hz, 1H, H8);
10690 Inorganic Chemistry, Vol. 46, No. 25, 2007