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W. Doman´ska-Babul et al. / Journal of Organometallic Chemistry 692 (2007) 3640–3648
Ph2P–P(SiMe3)2
(0.91 mmol),
[(Et3P)2PtCl2]
until the addition of the diphosphane was completed. Only
after several hours at room temperature the mixture turned
yellow and the suspension started to dissolve. After a few
days the solution was clear and turned dark orange. The
31P NMR monitoring of the reaction mixtures is presented
in Section 2.1.3. The main reaction pathway is I, but prod-
ucts formed via the paths II and III are also visible. The
resonances of (iPr2N)2PCl and (iPr2N)2P–P(NiPr2)2 are
(0.45 mmol): Ph2P–PPh2 (s), Ph2P–P(SiMe3)2 (m),
Ph2P(SiMe3) (m), P(SiMe3)3 (w), Et3P (s), [{2,3-g-
(Ph2PP@PPPh2)}Pt(PEt3)2] (m), [{(Et3P)2Pt}2P2] (s).
Ph2P–P(SiMe3)2 (0.26 mmol), [(Et2PhP)2PtCl2]
(0.26 mmol): Et2PhP (vs), Ph2P–PPh2 (w),
B (w),
[{(Et2PhP)2Pt}2P2] (w), polymer at +10 ppm (b), Ph2PCl
(m).
Ph2P–P(SiMe3)2 (0.32 mmol), [(Et2PhP)2PtCl2]
very strong. 0 In case of
a
molar ratio (iPr2N)2P–
(0.18 mmol): Et2PhP (s), Ph2P–PPh2 (w),
B
(w),
P(SiMe3)2:½ðR3PÞ2PtCl2ꢀ ðR03P ¼ Et2PhP;p-Tol3PÞ of 2:1 it
is possible to isolate the related diphosphorus Pt complexes
1 and 2 as crystals in acceptable yield. With a molar ratio
of 1:1 and R03P ¼ Et3P, the ionic complex [l2-(1,2:2-g-
P2){Pt(PEt3)2}2{Pt(PEt3)2Cl}]+Clꢁ (3) could be isolated in
a fairly good yield (Scheme 3). In the reaction solution we
have not observed any 31P NMR signals which can be attrib-
uted to 3, presumably because this compound was formed in
the final stages of reactions according to Scheme 3, or
because of dynamic equilibria which can alter the 31P
NMR spectrum of this compound.
[{(Et2PhP)2Pt}2P2] (w), Polymer at +10 ppm (b),
Ph2P(SiMe3) (w), [(2,3-g-Ph2PP@PPPh2)Pt(PPhEt2)2] (m),
Ph2P–P(SiMe3)2 (s), Ph2PCl (m).
Ph2P–P(SiMe3)2(0.22 mmol),
(0.21 mmol): EtPh2P (vs), [{(EtPh2P)2Pt}2P2] (m), polymer
at +10 ppm (b).
Ph2P–P(SiMe3)2 (0.31 mmol), [(EtPh2P)2PtCl2]
(0.16 mmol): EtPh2P (vs), [{(EtPh2P)2Pt}2P2] (m), polymer
at +10 ppm (b), Ph2P–P(SiMe3)2 (s), Ph2P(SiMe3) (m).
Ph2P–P(SiMe3)2 (0.20 mmol), [(p-Tol3P)2PtCl2]
(0.22 mmol): p-Tol3P (vs), polymer at +20 ppm (b).
Ph2P–P(SiMe3)2 (0.43 mmol), [(p-Tol3P)2PtCl2]
(23 mmol): p-Tol3P (vs), polymer at +20 ppm (b), Ph2P–
P(SiMe3)2 (s), Ph2P(SiMe3) (m).
[(EtPh2P)2PtCl2]
In the case of R0 P ¼ Et3P or Et2PhP, 31P NMR examin-
3
ations of the reaction mixtures indicated two AA0XX0 spin
systems (C and E). These reactions yield additionally some
Pt complexes with five P atoms in the molecule (D, F, G, H,
I, K) and a complex compound with four P atoms in the
molecule (L).
2.1.2. The 31P NMR studies of the mixture obtained from the
reaction of (Et2N)2P–P(SiMe3)2 with [(R03P)2PtCl2]
(iPr2N)2P–P(SiMe3)2 (0.28 mmol), [(Et3P)2PtCl2]
(0.28 mmol): (iPr2N)2PCl (vs), (iPr2N)2P–P(NiPr2)2 (s),
(iPr2N)2PH (m), [trans-(Et3P)2PtCl2] (m), [cis-(Et3P)2PtCl2]
(m), Et3P (m), C (m), D (m), (iPr2N)2P–PH–P(NiPr2)2 (m),
(Et2N)2P–P(SiMe3)2
reacts
more
slowly
with
½ðR03PÞ2PtCl2ꢀ than Ph2P–P(SiMe3)2 (about 1 day). The
31P NMR monitoring of the reaction mixtures is presented
in Section 2.1.2. The main reaction path is I.
[(2,3-g-{(iPr2N)2)P–P@P–P(NiPr2)2}Pt(PEt3)2]
(w),
(Et2N)2P–P(SiMe3)2 (0.19 mmol), [(Et2PhP)2PtCl2]
(0.20 mmol): Et2PhP (s), (Et2N)3P (s), [{(Et2PhP)2Pt}2P2]
(s). We were not able to resolve many weak signals in the
range from +37 to +22 ppm without Pt satellites.
(Et2N)2P–P(SiMe3)2 (0.35 mmol), [(Et2PhP)2PtCl2]
(0.19 mmol): Et2PhP (s), (Et2N)2P–P(NEt2)2 (m),
[{(Et3P)2Pt}2P2] (w). The mixture appears to be very com-
plex. We were not able to attribute many signals with Pt
satellites especially in the range of 30–0 ppm (overlaps
and higher order spectra).
(iPr2N)2P–P(SiMe3)2 (0.34 mmol), [(Et3P)2PtCl2]
(0.17 mmol): [{(Et3P)2Pt}2P2] (vs), (iPr2N)2P–P(NiPr2)2
(s), (iPr2N)2PCl (s), [(2,3-g-{(iPr2N)2)P–P@P–P(NiPr2)2}
Pt(PEt3)2] (m), (iPr2N)2P–P(SiMe3)H (w), (iPr2N)2P–PH–
P(NiPr2)2 (w), C (w), D (w).
[{(Et2PhP)2Pt}2P2]
(s),
(Et2N)2P–P(SiMe3)2
(m),
(Et2N)2P–P(SiMe3)H (m), (Et2N)3P (w). Many weak sig-
nals in the range from +37 to +24 ppm without Pt satellites
we were not able to resolve.
(Et2N)2P–P(SiMe3)2 (0.19 mmol), [(EtPh2P)2PtCl2]
(0.19 mmol): [{(EtPh2P)2Pt}2P2] (s), P(NEt2)3 (m),
PCl(NEt2)2 (w), EtPh2P (w). Many weak signals in the
range from +37 to +15 ppm without Pt satellites we were
not able to resolve.
(Et2N)2P–P(SiMe3)2 (0.32 mmol), [(EtPh2P)2PtCl2]
(0.16 mmol): [{(EtPh2P)2Pt}P2] (s), EtPh2P(w), (Et2N)2P–
P(SiMe3)2 (s), (Et2N)2P–P(SiMe3)H (m), (Et2N)2P–
P(SiMe3)–P(NEt2)2 (w), P(NEt2)3 (w). Many weak signals
in the range from +37 to +21 ppm without Pt satellites
we were not able to resolve.
(iPr2N)2P–P(SiMe3)2 (0.25 mmol), [(Et2PhP)2PtCl2]
(0.25 mmol): (iPr2N)2PCl (vs), Et2PhP (s), (iPr2N)2P–
P(NiPr2)2 (s), [{(Et2PhP)2Pt}2P2] (s), (iPr2N)2PH (m),
(iPr2N)2P–PH–P(NiPr2)2 (m), [(2,3-g-{(iPr2N)2)P–P@P–
P(NiPr2)2}Pt(PPhEt2)2] (w), E (m), F (w), G (w). We have
not resolved some signals with Pt satellites in the range
of 18–2 ppm (overlaps and higher order spectra).
(iPr2N)2P–P(SiMe3)2 (0.39 mmol), [(Et2PhP)2PtCl2]
(0.18 mmol): (iPr2N)2P–P(NiPr2)2 (vs), [{(Et2PhP)2Pt}2P2]
(m), (iPr2N)2PCl (m), (iPr2N)2PH (w), (iPr2N)2P–PH–
P(NiPr2)2 (m), (iPr2N)2P–P(SiMe3)2 (m), Et2PhP(m), (iPr2N)2
P–P(SiMe3)H (w), (iPr2N)2P–P(SiMe3)–P(NiPr2)2 (w).
(iPr2N)2P–P(SiMe3)2 (0.25 mmol), [(EtPh2P)2PtCl2]
(0.25 mmol): [{(EtPh2P)2Pt}2P2] (s), (iPr2N)2PCl (s), [cis-
(EtPh2P){(iPr2N)2PH}PtCl2] (m), [cis-(EtPh2P)2PtCl2]
(m), (iPr2N)2P–PH–P(NiPr2)2 (m), EtPh2P (m), (iPr2N)2P–
P(SiMe3)H (w), H (w).
2.1.3. The 31P NMR studies of the mixture obtained from the
reaction of (iPr2N)2P–P(SiMe3)2 with [(R0 P)2PtCl2]
3
The reactions of (iPr2N)2P–P(SiMe3)2 with ½ðR0 PÞ PtCl2ꢀ
3
2
were very slow. We did not observe any change in the mixture