ACCEPTED MANUSCRIPT
room temperature for 12 h, after which it was reduced in vacuo
°C) was added. The solution was allowed to stir for approximately
2 minutes before acetonitrile (~2 mL) was added. The solution
was placed under vacuum, and the volatiles removed. The residue
was treated with n-pentane (~2 mL), which was then removed
under vacuum to afford a solid. The solid was dried in vacuo.
and hexanes were added (~20 mL). The suspension was filtered
and the solid was washed with Et2O (5 mL) and hexanes (2 x 5
mL) and dried under vacuum.
(diq)Pt(Ph)2 (9). L2
= 8-(diisopropylphosphino)quinoline.
1
Isolated 0.13 g (85%). H NMR (600 MHz, CD2Cl2) δ 8.97 (dd,
3JHH = 5 Hz, 4JHH = 2 Hz, 1H, diq), 8.46 (d, 3JHH = 8 Hz, 1H, diq),
8.06 (td, 3JHH = 7 Hz, 3JHH = 1 Hz, 1H, diq), 8.03 (d, 3JHH = 8 Hz,
[(dmpe)Pt(NCMe)(Ph)][BAr'4]
(1).
dmpe
=
(Bis-
(diphenylphosphino)methyl) methylamine. Isolated 0.13 g (93%).
1H NMR (300 MHz, CD2Cl2) δ 7.30 (m, 2H, Ho-Ph), 7.17 (t, 3JHH
= 7 Hz, 2H, Hm-Ph), 7.01 (t, 3JHH = 7 Hz, 1H, Hp-Ph), 2.31 (s, 3H,
NCMe), 1.86 (m, 4H, PCH2CH2P), 1.63 (d, 2JPH = 10 Hz, 6H, Me-
3
3
2H, Ho-Ph), 7.74 (t, JHH = 8 Hz, 1H, diq), 7.54 (t, JHH = 8 Hz,
1H, diq), 7.48 (d, 3JHH = 8 Hz, 2H, Ho-Ph), 7.32 (dd, 3JHH = 8 Hz,
3JHH = 5 Hz, 1H, diq), 7.09 (m, 2H, Hm-Ph), 6.88 (m, 3H, Hm and
Hp-Ph), 6.70 (m, 1H, Hp-Ph), 2.66 (m, 2H, CH-iPr), 1.18 (d, 3JHH
2
3
dmpe), 1.42 (d, JPH = 2 Hz, JHH = 52 Hz, 6H, Me-dmpe). 31P
1
NMR (121 MHz, CD2Cl2) δ 29.99 (s, JPtH = 1667 Hz, Pt
= 7 Hz, 3H, Me-iPr ), 1.16 (d, JHH = 7 Hz, 3H, Me-iPr), 0.96 (d,
satellites), 15.29 (s, 1JPtH = 4076 Hz, Pt satellites). 13C NMR (201
MHz, dichloromethane-d2) δ 162.23, 136.88, 135.21, 129.35,
127.03, 125.68, 125.13, 124.32, 122.97, 117.86, 29.68, 26.03,
12.78, 11.91, 3.86. Anal. calcd. for PtP2NBF24C46H36 (%): C
41.64, H 2.74, N 1.06; found: C 41.86, H 2.65, N 0.97.
3
3JHH = 7 Hz, 3H, Me-iPr), 0.93 (d, JHH = 7 Hz, 3H, Me-iPr). 31P
3
1
NMR (121 MHz, CD2Cl2) δ 41.58 (s, JPtP = 1937 Hz, Pt
satellites). 13C NMR (201 MHz, dichloromethane-d2) δ 175.75,
175.54, 155.54, 153.84, 138.83, 138.14, 137.86, 137.25, 135.74,
131.56, 130.33, 127.90, 127.78, 127.05, 123.44, 122.36, 120.69,
23.53, 23.41, 17.86, 17.35. Anal. calcd. for PtNPC27H30 (%): C
54.53, H 5.09, N 2.36; found: C 54.38, H 5.26, N 2.30.
[(dppe)Pt(NCMe)(Ph)][BAr'4]
(2).
dppe
=
1,2-
1
bis(diphenylphosphino)ethane. Isolated 0.13 g (97%). H NMR
(300 MHz, CD2Cl2) δ 7.57 (m, 32H, Ar′ and dppe), 6.90 (m, 5H,
Ph), 2.42 (m, 4H, PCH2CH2P), 2.12 (s, 3H, NCMe). 31P NMR
(bppe)Pt(Ph)2. L2
= 1,2-(bis-N-pyrrolylphosphino)ethane.
Isolated 0.17 g (72%). 1H NMR (800 MHz, acetone-d6) δ 7.31 (m,
4H, Ho-Ph), 7.01 (m, 8H, β-N-pyrrolyl), 6.90 (t, 3JHH = 8 Hz, 4H,
(121 MHz, CD2Cl2) δ 47.44 (s, JPtP = 1671 Hz, Pt satellites),
1
1
33.92 (s, JPtP = 4359 Hz, Pt satellites). 13C NMR (201 MHz,
3
4
Hm-Ph), 6.75 (tt, JHH = 8 Hz, JHH = 1 Hz, 2H, Hp-Ph), 6.30 (m,
dichloromethane-d2) δ 162.11, 151.79, 136.93, 135.11, 133.73,
133.24, 132.85, 130.07, 129.54, 129.18, 128.73, 126.96, 125.71,
125.60, 125.37, 124.76, 124.25, 117.86, 30.54, 24.87, 3.87. Anal.
calcd. for PtP2NBF24C66H44 (%): C 50.33, H 2.82, N 0.89; found:
C 50.37, H 2.99, N 1.02.
8H, β-N-pyrrole), 2.80 (d, JHH = 22 Hz, 4H, CH2-bppe). 31P
2
NMR (121 MHz, acetone-d6) δ 108.37 (1JPtP = 2123 Hz, Pt
satellites). 13C NMR (201 MHz, acetone-d6) δ 157.45 (dd, 142.01
MHz, 20.50 MHz), 137.45, 128.31, 124.48, 123.56, 113.85, 31.63
(CH2CH2). Anal. calcd. for PtN4P2C30H30 (%): C 51.20, H 4.31, N
7.96; found: C 51.35, H 4.58, N 7.57.
[(bppe)Pt(NCMe)(Ph)][BAr'4] (3). bppe
=
1,2-(bis-N-
1
pyrrolylphosphino)ethane. Isolated 0.09 g (89%). H NMR (300
MHz, CD2Cl2) δ 7.08 (m, 9H, α-N-pyrrole and Ph), 6.75 (m, 4H,
α-N-pyrrole), 6.64 (m, 4H, β- N-pyrrole), 6.48 (m, 4H, β-N-
pyrrole) 2.75 (m, 4H, CH2CH2-bppe), 2.44 (s, 3H, NCMe). 31P
(bma)Pt(Ph)2.
L2
=
(Bis-(diphenylphosphino)methyl)
methylamine. Isolated 0.62 g (91%). 1H NMR (500 MHz,
acetone-d6) δ 7.57 (m, 8H, bma), 7.36 (m, 12H, bma), 6.97 (m,
4H, Ho-Ph), 6.44 (t, 3JHH = 7 Hz, 4H, Hm-Ph), 6.31 (t, 3JHH = 7 Hz,
1
NMR (121 MHz, CD2Cl2) δ 109.56 (s, JPtP = 2539 Hz, Pt
2H, Hp-Ph), 3.59 (s, JPtH = 14 Hz Pt satellites, 4H, CH2-bma),
satellites), 80.68 (s, 1JPtP = 5599 Hz, Pt satellites). 13C NMR (201
MHz, acetonitrile-d3) δ 161.61, 147.43, 135.64, 134.67, 128.90,
128.42, 125.47, 125.14, 124.00, 123.83, 117.71, 114.76, 114.53,
32.28, 25.27. Anal. calcd. for PtN5P2BF24C58H40 (%): C 45.50, H
2.64, N 4.58; found: C 45.13, H 2.70, N 4.17.
3
2.32 (s, 3H, Me-N). 31P NMR (121 MHz, acetone-d6) δ -4.94 (s,
1JPtP = 1693 Hz, Pt satellites). 13C NMR (201 MHz, acetone-d6) δ
162.11 (dd 113.38 MHz, 15.33 MHz), 137.57, 134.43, 132.95,
130.62, 128.66, 126.92, 121.13, 60.09, 51.59. Anal. calcd. for
PtNP2C39H37 (%): C 60.30, H 4.81, N 1.80; found: C 60.45, H
4.73, N 1.92.
[(dppp)Pt(NCMe)(Ph)][BAr'4]
bis(diphenylphosphino)propane. Isolated 0.09 g (91%). H NMR
(4).
dppp
=
1,3-
1
(DtBuC)Pt(Ph)2.
L2
=
1,1'-methylene-3,3'-di-tert-
(800 MHz, CD2Cl2) δ 7.58 (m, 8H, dppp), 7.34 (m, 8H, dppp),
3
4
3
butylimidazol-2,2'-diylidine. The synthesis of this complex was
taken from a reported preparation for the bis-methyl Pt(II)
equivalent.41 Ag2O (0.370 g, 1.60 mmol) and DtBuC (0.169 g,
0.40 mmol) were mixed in DCM at room temperature. After 45
min, [Pt(Ph)2(ꢀ-SEt2)]2 (0.176 g, 0.20 mmol) was added to the
solution and allowed to stir for 2 h. The mixture was passed
through celite and the volatiles were removed in vacuo to afford a
7.23 (td, JHH = 8 Hz, JHH = 3 Hz, 4H, dppp), 6.93 (t, JHH = 7
Hz, 2H, Ho-Ph), 6.69 (t, 3JHH = 7 Hz, 2H, Hm-Ph), 6.64 (t, 3JHH = 7
Hz, 1H, Hp-Ph), 2.74 (m, 2H), 2.66 (m, 2H), 1.99 (m, 2H), 1.70 (s,
3H, NCMe). 31P NMR (121 MHz, CD2Cl2) δ -0.06 (d, JPP = 26
2
Hz), -4.20 (d, 2JPP = 26 Hz). Pt coupling not resolved due to poor
signal intensity. 13C NMR (201 MHz, dichloromethane-d2) δ
162.17, 152.10, 136.29, 135.22, 133.45, 133.16, 132.15, 131.97,
129.82, 129.29, 128.98, 128.43, 127.35, 127.04, 125.67, 124.33,
124.25, 117.84, 24.84, 22.77, 18.79, 2.95. Anal. calcd. for
PtP2NBF24C67H46 (%): C 50.64, H 2.92, N 0.88; found: C 50.84,
H 2.92, N 0.81.
1
white solid (0.139 g, 57%). H NMR (300 MHz, acetone-d6) δ
7.51 (d, JHH = 7.90 Hz, JPtH = 28.83 Hz, 4 H, o-phenyl), 7.45 (m,
2 H, NCH=CHN), 7.17 (d, JHH = 1.87 Hz, 2 H, NCH=CHN), 6.99
(d, JHH = 12.46 Hz, 1 H, NCH2N), 6.67 (t, JHH = 7.49 Hz, 4 H, m-
phenyl), 6.47 (t, JHH = 7.09 Hz, 2 H, p-phenyl), 6.08 (d, JHH
=
[(dppf)Pt(NCMe)(Ph)][BAr'4]
(5).
dppf
=
1,1ˈ-
12.48 Hz, 1 H, NCH2N), 1.40 (s, 18 H, tBu). 13C NMR (150 MHz,
acetone-d6) δ 181.77 (s, carbene C), 140.37 (s, 2JPtC = 17.4 Hz, m-
bis(diphenylphosphino)ferrocene. Isolated 0.07 g (88%). 1H NMR
(300 MHz, CD3CN) δ 7.90 (m, 4H, dppf), 7.57 (m, 17H, Ar′ and
dppf), 7.41 (m, 7H, Ho-Ph and dppf), 7.20 (m, 4H, dppf), 6.96 (m,
2H, Hm-Ph), 6.62 (m, 3H, Hp-Ph and dppf), 4.79 (m, 2H, Cp-
dppf), 4.62 (s, 2H, Cp-dppf), 4.36 (s, 2H, Cp-dppf), 3.90 (m, 2H,
Cp-dppf). Coordinated NCMe not observed due to rapid exchange
with CD3CN. 31P NMR 121 MHz, CD3CN) δ 18.95 (d, 2JPP = 17
1
phenyl), 126.42 (s, JPtC = 31.8 Hz, o-phenyl), 120.47 (s, p-
phenyl), 119.65 (s, 2JPtC = 9.4 Hz, NCH=CHN), 118.38 (s, 2JPtC
=
12.4 Hz, NCH=CHN), 65.09 (s, CH2), 58.79 (s, C(CH3)3), 30.99
(s, C(CH3)3), i-phenyl not observed. Anal. Calcd. for PtN4C27H34
(%): C 53.19, H 5.62, N 9.19; found: C 52.22, H 5.72, N 9.19.
1
2
Hz, JPtP = 1717 Hz, Pt satellites), 11.00 (d, JPP = 17 Hz, 1JPtP
=
General
procedure
for
the
synthesis
of
[(L~L)Pt(NCMe)(Ph)][BAr'4] complexes.
A
suspension of
4674 Hz, Pt satellites). 13C NMR (201 MHz, acetonitrile-d3) δ
162.56, 150.38, 136.62, 135.60, 135.20, 135.03, 132.59, 132.25,
130.78, 130.18, 129.83, 129.07, 128.71, 126.07, 124.72, 124.45,
(L~L)Pt(Ph)2 in THF (30 mL) was cooled to -70 °C. One
equivalent of [H(Et2O)2][BAr'4] dissolved in THF (~10 mL, -70
6