Paper
Dalton Transactions
18.3 (s, PCH(CH3)2), 18.4 (d, JC–P = 5.2 Hz, PCH(CH3)2), 19.3 (d,
JC–P = 5.2 Hz, PCH(CH3)2), 20.8 (s, CH3), 28.3 (d, JC–P = 16.0 Hz,
PCH(CH3)2), 29.1 (d, JC–P = 21.5 Hz, PCH(CH3)2), 107.8 (d, JC–P
= 13.4 Hz, Ni-ArCS-meta), 116.8 (d, JC–P = 12.4 Hz, Ni-ArCO-meta),
128.0 (s, Ni-ArCpara), 128.7 (s, S-ArCmeta), 132.9 (s, S-ArCpara),
134.9 (s, S-ArCortho), 142.7 (s, S-ArCipso), 149.1 (s, Ni-ArCS-otho),
155.5 (s, Ni-ArCO-ortho), 167.5 (s, Ni-ArCipso). 31P{1H} NMR (THF-
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2
2
d8, 121 MHz, δ): 107.2 (d, JP–P = 314 Hz), 180.1 (d, JP–P = 314
Hz). Anal. Calcd for C25H38NiOP2S2: C, 55.67; H, 7.10; S, 11.89.
Found: C, 55.90; H, 7.120; S, 12.68. MS (CI positive, isobutane):
m/z = 538 [M]+, 415 [M − SC6H4-p-CH3].
[
iPrPSCSPiPr]NiSC6H4CH3 (6). iPrPSCSPiPr]NiSC6H4CH3 (6)
[
was prepared in 59% yield by a procedure similar to that used
for 4. Crystallisation from an n-hexane solution layered with
acetonitrile at −30 °C yielded crystals suitable for X-ray ana-
1
lysis. H NMR (THF-d8, 300 MHz, δ): 1.25–1.52 (m, PCH(CH3)2,
3
24H), 2.20 (s, CH3, 3H), 2.29–2.44 (sept, JH–H = 7.0 Hz,
3
PCH(CH3)2, 4H), 6.69 (t, JH–H = 7.6 Hz, Ni-ArHpara, 1H), 6.84
3
3
(d, JH–H = 7.6 Hz, S-ArHmeta, 2H), 6.88 (d, JH–H = 7.6 Hz, Ni-
ArHmeta, 2H), 7.34 (d, JH–H = 7.6 Hz, S-ArHortho, 2H). 13C{1H}
3
NMR (THF-d8, 100 MHz, δ): 18.3 (s, PCH(CH3)2), 19.7 (s, PCH
(CH3)2), 20.7 (s, CH3), 28.5 (t, JC–P = 9.7 Hz, PCH(CH3)2), 119.2
(t, JC–P = 6.0 Hz, Ni-ArCmeta), 126.5 (s, Ni-ArCpara), 128.9 (s,
S-ArCmeta), 132.8 (s, S-ArCpara), 134.4 (s, S-ArCortho), 141.3 (s,
S-ArCipso), 155.5 (s, Ni-ArCortho), 164.7 (s, Ni-ArCipso). 31P{1H}
NMR (THF-d8, 121 MHz, δ): 96.38 (s). Anal. Calcd For
C25H38NiP2S3: C, 54.06; H, 6.90; S, 17.32. Found: C, 54.04; H,
7.20; S, 17.56 (determined by at least two measurements). MS
(CI positive, isobutane): m/z = 554 [M]+, 431 [M − SC6H4-p-
CH3].
Crystallographic details
X-ray analysis was performed using a Bruker Kappa APEX II
Duo diffractometer with Mo-Kα radiation. The structure was
solved by direct methods (SHELXS-97)16 and refined by full-
matrix least square procedures on F2 (SHELXL-2014).17
Diamond was used for graphical representations.18 CCDC
1893578 contains the supplementary crystallographic data for
this paper.†
Pincer-Metal
Platform:
Coordination
Chemistry
&
Conflicts of interest
Applications, ed. G. van Koten and R. A. Gossage, Springer
International Publishing, Cham, 2016, p. 239.
There are no conflicts to declare.
4 (a) J. I. van der Vlugt and J. N. H. Reek, Angew. Chem., Int.
Ed., 2009, 48, 8832–8846, (Angew. Chem., 2009, 121, 8990–
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A. S. Goldman, Chem. Rev., 2011, 111, 1761–1779;
(c) M. Albrecht and M. M. Lindner, Dalton Trans., 2011, 40,
8733–8744; (d) G. van Koten and D. Milstein,
Organometallic Pincer Chemistry, Springer, Berlin, 2013, vol.
40; (e) K. J. Szabo and O. F. Wendt, Pincer and Pincer-Type
Complexes: Applications in Organic Synthesis and Catalysis,
Wiley-VCH, Weinheim, 2014.
Acknowledgements
We thank our technical and analytical staff, in particular
Benjamin Andres. Financial support by the DFG (grant no. BE
4370/5-1) is gratefully acknowledged.
Notes and references
5 (a) V. Pandarus and D. Zargarian, Organometallics, 2007,
26, 4321–4334; (b) B. Vabre, F. Lindeperg and D. Zargarian,
Green Chem., 2013, 15, 3188–3194.
1 C. J. Moulton and B. L. Shaw, J. Chem. Soc., Dalton Trans.,
1976, 1020–1024.
16328 | Dalton Trans., 2019, 48, 16322–16329
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