10.1002/ejic.201800398
European Journal of Inorganic Chemistry
FULL PAPER
CHarom), 131.8 (d, JP,C = 2.4 Hz, CHarom), 131.7 (d, JP,C = 5.9 Hz, CHarom),
130.3 (d, JP,C = 8.6 Hz, CHarom), 128.5 (d, JP,C = 12.0 Hz, CHarom), 126.7
(d, JP,C = 69.1 Hz, Carom), 118.7 (d, JP,C = 63.5 Hz, Carom) ppm. Elemental
analysis calcd. (%) for C38H30Cl2N2O2P2Pt2: C 42.67, H 2.83, N 2.62;
found: C 42.81, H 2.90, N 2.51. HRMS (ESI): m/z 1033.0766, [M - Cl]+.
CHarom), 131.2 (d, JP,C = 1.0 Hz, CHarom), 130.9 (s, CHarom), 128.7 (d, JP,C
= 9.2 Hz, CHarom), 128.1 (d, JP,C = 9.9 Hz, CHarom), 127.5 (d, JP,C = 65.6
Hz, Carom), 127.1 (d, JP,C = 63.6 Hz, Carom), 125.6 (d, JP,C = 39.8 Hz, JPt,C
= 26.3 Hz, Carom), 8.9 (s, JPt,C = 643.7 Hz, Me), 7.8 (s, JPt,C = 535.7 Hz,
Me), 6.6 (s, JPt,C = 535.8 Hz, Me) ppm. Elemental analysis calcd. (%) for
C22H25INOPPt: C 39.30, H 3.75, N 2.08; found: C 39.41, H 3.62, N 2.15.
HRMS (ESI): m/z 533.0952, [M - I- 2Me + H2O]+.
Synthesis of (-O)-[PtMe{2-(P,N)-2-Ph2PC6H4CH=NO}]2 (7): A mixture
of [PtMe2(COD)] (6) (0.100 g, 0.300 mmol) and 2-Ph2PC6H4CH=NOH (1)
(0.091 g, 0.300 mmol) in 15 mL of dichloromethane was stirred overnight
at room temperature. The resulting solution was then concentrated under
reduced pressure to ca. 5 mL. Addition of hexanes (50 mL) led to the
precipitation of a yellow solid, which was recrystallized twice with CH2Cl2-
hexanes (5:40 mL), washed with hexanes (3 x 10 mL) and dried in vacuo.
Yield: 0.093 g (60%). IR (KBr): = 1575 (m, C=N) cm-1. 31P{1H} NMR
(CD2Cl2, 121 MHz): = 11.6 (s, JPt,P = 4412.3 Hz) ppm. 1H NMR (CD2Cl2,
300 MHz): = 8.25 (s, JPt,H = 31.8 Hz, 2 H, CH=N), 7.73-7.34 (m, 26 H,
CHarom), 7.06 (dd, JP,H = 10.2 Hz, JH,H = 8.4 Hz, 2 H, CHarom), 0.02 (d, JP,H
= 1.8 Hz, JPt,H = 64.8 Hz, 6 H, Me) ppm. 13C{1H} NMR (CD2Cl2, 100
MHz): = 143.6 (virtual t, N = 9.8 Hz, C=N), 139.6 (d, JP,C = 13.2 Hz,
Carom), 135.9 (d, JP,C = 11.5 Hz, CHarom), 134.0 (d, JP,C = 1.0 Hz, CHarom),
133.2 (d, JP,C = 2.1 Hz, CHarom), 133.1 (d, JP,C = 9.4 Hz, CHarom), 132.8 (d,
Synthesis of [PtCl2{2-(P,N)-2-Ph2PC6H4CH=NtBu}] (11): A mixture of
2-Ph2PC6H4CH=NtBu (0.145 g, 0.420 mmol) and [PtCl2(COD)] (2) (0.150
g, 0.400 mmol) and in 10 mL of dichloromethane was stirred overnight at
room temperature. The resulting solution was then concentrated under
reduced pressure to ca. 2 mL. Addition of hexanes (20 mL) led to the
precipitation of a yellow solid, which was washed with hexanes (3 x 5
mL) and dried in vacuo. Yield: 0.193 g (79%). IR (KBr): = 1612 (m,
C=N) cm-1. 31P{1H} NMR (CD2Cl2, 121 MHz): = 7.1 (s, JPt,P = 3775.3
Hz) ppm. 1H NMR (CD2Cl2, 400 MHz): = 8.37 (s, JPt,H = 99.3 Hz, 1 H,
CH=N), 7.74-7.52 (m, 13 H, CHarom), 7.88 (br s, 1 H, CHarom), 1.51 (s, 9 H,
CH3) ppm. 13C{1H} NMR (CD2Cl2, 100 MHz): = 164.8 (d, JP,C = 7.0 Hz,
C=N), 138.9 (d, JP,C = 13.0 Hz, Carom), 134.9-134.0 (m, CHarom and Carom),
133.3 (d, JP,C = 7.7 Hz, CHarom), 132.3 (d, JP,C = 1.7 Hz, CHarom), 132.2 (d,
JP,C = 2.4 Hz, CHarom), 130.8 (d, JP,C = 63.7 Hz, Carom), 130.5 (d, JP,C
=
JP,C = 8.4 Hz, CHarom), 131.5 (d, JP,C = 4.2 Hz, CHarom), 122.9 (d, JP,C =
8.4 Hz, CHarom), 130.1 (d, JP,C = 11.3 Hz, CHarom), 124.0 (d, JP,C = 60.6
Hz, Carom), -10.2 (d, JP,C = 5.8 Hz, Me) ppm. Elemental analysis calcd.
(%) for C40H36N2O2P2Pt2: C 46.70, H 3.53, N 2.72; found: C 46.77, H 3.62,
N 2.84. HRMS (ESI): m/z 1029.1573, [M + H]+.
61.4 Hz, Carom), 69.8 (s, C(CH3)3), 31.9 (s, C(CH3)3) ppm. Elemental
analysis calcd. (%) for C23H24Cl2NPPt: C 45.18, H 3.96, N 2.29; found: C
45.23, H 4.01, N 2.37.
General procedure for the catalytic cross dehydrogenative coupling
of hydrosilanes with alcohols: The corresponding hydrosilane (1
mmol), alcohol (1 mL) and platinum catalyst (0.0005 or 0.01 mmol; 0.1-1
mol%) were introduced into a Teflon-capped sealed tube, and the
reaction mixture stirred at room temperature for the indicated time (see
Table 1 and Scheme 9). The course of the reaction was monitored
regularly taking samples of ca. 10 L which, after dilution with CH2Cl2,
were analyzed by GC. The identity of the alkoxysilanes formed was
assessed by comparison of their NMR data with those reported in the
literature (copies of the 1H and 13C{1H} NMR spectra of the products
obtained after purification by flash chromatography are included in the
Supporting Information).
Synthesis of [Pt({2-(P,N)-2-Ph2PC6H4CH=NO}2H)][Cl] (8): A solution
of [Pt{2-(P,N)-2-Ph2PC6H4CH=NOH}2][Cl]2 (4) (0.150 g, 0.171 mmol) in
10 mL of dichloromethane was treated at r.t. with Na2CO3 (0.181 g, 1.710
mmol) for 20 h. The resulting suspension was then filtered through
Kieselguhr, and the filtrate concentrated under vacuum to ca. 2 mL.
Addition of hexanes (30 mL) led to the precipitation of a yellow solid,
which was recrystallized twice with CH2Cl2-hexanes (2:30 mL), washed
with hexanes (2 x 5 mL) and dried in vacuo. Yield: 0.105 g (73%). IR
(KBr): = 1741 (s, O-H-O), 1630 (m, C=N) cm-1. 31P{1H} NMR (CD2Cl2,
121 MHz): = 5.6 (s, JPt,P = 3273.6 Hz) ppm. 1H NMR (CD2Cl2, 400
MHz): = 8.18 (d, JP,H = 8.4 Hz, JPt,H = 56.0 Hz, 2 H, CH=N), 7.65-7.30
(m, 26 H, CHarom), 6.85 (dd, JH,H = 7.8 Hz, JP,H = 6.0 Hz, 2 H, CHarom
)
ppm; O-H-O signal not observed. 13C{1H} NMR (CD2Cl2, 100 MHz): =
150.1 (br s, C=N), 134.2 (virtual t, N = 10.2 Hz, CHarom), 134.0 (virtual t, N
= 25.8 Hz, Carom), 133.6 (virtual t, N = 9.2 Hz, CHarom),132.8 (s, CHarom),
132.7 (s, CHarom), 133.2 (virtual t, N = 3.6 Hz, CHarom), 131.9 (virtual t, N
X-Ray crystal structure determination of complexes 3, 4, 7 and 10:
Crystals of 3, 4, 7 and 10 suitable for X-ray diffraction analysis were
obtained in all the cases by slow diffusion of hexanes into a saturated
solution of the complex in a dichloromethane/methanol mixture (3:1 v/v).
The most relevant crystal and refinement data are collected in Table 2. In
all the cases, data collection was performed with a Rigaku-Oxford
Diffraction Xcalibur Onyx Nova single crystal diffractometer using Cu-K
radiation ( = 1.5418 Å). Images were collected at a fixed crystal-detector
distance of 62 mm, using the oscillation method with 1.30º oscillation for
3 and 10 and 1.10º for 4 and 7, and 2.00-4.00 s variable exposure time
per image for 3, 3.50-7.00 s for 4, 2.00-5.00 s for 7 and 4.00-12.50 s for
10. Data collection strategy was calculated with the program
= 9 Hz, CHarom), 129.3 (virtual t, N = 11.6 Hz, CHarom), 124.9 (d, JP,C
=
68.6 Hz, Carom), 121.7 (d, JP,C = 62.4 Hz, Carom) ppm. Elemental analysis
calcd. (%) for C38H31N2O2P2ClPt: C 54.33, H 3.72, N 3.33; found: C 54.25,
H 3.80, N 3.42. HRMS (ESI): m/z 804.1483, [M]+.
Synthesis of fac-[PtIMe3{2-(P,N)-2-Ph2PC6H4CH=NOH}] (10):
A
mixture of 2-Ph2PC6H4CH=NOH (1) (0.125 g, 0.410 mmol) and [PtMe3I]4
(9) (0.150 g, 0.102 mmol) and in 30 mL of dichloromethane was stirred
overnight at room temperature. The resulting solution was then
concentrated under reduced pressure to ca. 5 mL. Addition of hexanes
(30 mL) led to the precipitation of a yellow solid, which was recrystallized
twice with CH2Cl2-hexanes (5:30 mL), washed with hexanes (2 x 10 mL)
and dried in vacuo. Yield: 0.228 g (83%). IR (KBr): = 3484 (br, OH),
CrysAlisPro [41]
with the program CrysAlisPro [41]
applied using the SCALE3 ABSPACK algorithm as implemented in the
program CrysAlisPro [41]
All the structures were solved by Patterson
.
Data reduction and cell refinement were also performed
An empirical absorption correction was
.
.
interpretation and phase expansion using DIRDIF2008.[42] Isotropic least-
squares refinements on F2 using SHELXL2014[43] were performed.
During the final stages of the refinements, all the positional and
anisotropic displacement parameters of all non-H atoms were refined
(except C18 in complex 3).
1625 (m, C=N) cm-1. 31P{1H} NMR (CD2Cl2, 121 MHz): = -0.2 (s, JPt,P
=
1208.9 Hz) ppm. 1H NMR (CD2Cl2, 400 MHz): = 13.05 (br s, 1 H, OH),
8.29 (s, JPt,H = 19.2 Hz, 1 H, CH=N), 7.62-7.24 (m, 13 H, CHarom), 7.06 (br
s, 1 H, CHarom), 1.52 (s, JPt,H = 59.6 Hz, 3 H, Me), 1.33 (s, JPt,H = 80.4 Hz,
3 H, Me), 1.06 (s, JPt,H = 64.8 Hz, 3 H, Me) ppm. 13C{1H} NMR (CD2Cl2,
100 MHz): = 151.5 (s, C=N), 135.5 (d, JP,C = 9.7 Hz, CHarom), 134.5 (s,
CHarom), 134.1 (d, JP,C = 8.6 Hz, CHarom), 133.9 (d, JP,C = 20.8 Hz, Carom),
133.6 (d, JP,C = 9.5 Hz, CHarom), 132.2 (d, JP,C = 5.8 Hz, CHarom), 131.5 (s,
For 3, hydrogen atoms bonded to C1 and O1 were unequivocally
located using a difference electron density Fourier synthesis and their
coordinates and isotropic displacement parameters were freely refined.
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