The new diphosphanylphosphido complexes of tungsten(VI) and molybdenum(VI). Their synthesis, structures and properties

Article abstract of DOI:10.1039/c8dt01977k

We report on the reactivity of R₂P-P(Li)-PR′₂ (R = tBu, iPr, R′ = NEt₂, iPr) towards diimido complexes [(dippN)₂MCl₂·dme] (M = Mo, W and dipp = 2,6-iPr₂C₆H₃). A series of new complexes with diphosphanylphosphido ligands R₂P-P-PR′₂ were isolated. The solid-state structures of [(dippN)₂M(Cl)(1,2-η-iPr₂P-P-PiPr₂)] (2Mo and 2W) and [(dippN)₂M(Cl){1,2-η-tBu₂P-P-P(NEt₂)₂}] (3Mo and 3W) were established by single-crystal X-ray diffraction analysis and indicate a side-on geometry of the R₂P-P-PR′₂ moiety. 3W and 3Mo are the first triphosphorus complexes with the amido ligand NEt₂ on the P atom. [(dippN)₂M(Cl)(1,2-η-tBu₂P-P-PtBu₂)] (1Mo and 1W) and 3Mo and 3W display similar side-on geometry in solution and in the solid state. By contrast, 2Mo and 2W reveal a dynamic behavior in solution. For the first time, the reactivity of diphosphanylphosphido complexes towards different nucleophiles was studied. The complexes react with the phosphorus nucleophile Ph₂PLi, yielding phosphanylphosphinidene complexes [(dippN)₂M(Cl)(η²-P-PR₂)]^? Li⁺ (M = Mo, W) together with related diphosphanes R′₂P-PPh₂. Carbon nucleophile MeLi does not yield [(dippN)₂M(Cl)(η²-P-PR₂)]^? Li⁺ but substitutes a Cl ligand at the metal center. Moreover, we compare the coordination of the R₂P-P-PR′₂ moiety to different metal centers based on DFT methods.

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The new diphosphanylphosphido complexes of tungsten(VI) and
molybdenum(VI). Their synthesis, structures and properties.
A. Wiśniewska a†,R. Grubba a, Ł. Ponikiewski a , M. Zauliczny a and J. Pikies a
Received 00th January 20xx,
Accepted 00th January 20xx
We report on a reactivity of R2P–P(Li)–PR’2 (R = tBu, iPr, R’ = NEt2, iPr) towards diimido complexes [(dippN)2MCl2·dme] (M =
Mo, W and dipp = 2,6-iPr2C6H3). A series of new complexes with diphosphanylphosphido ligands R2P-P-PR’2 were isolated.
The solid-state stuctures of [(dippN)2M(Cl)(1,2-η-iPr2P-P-PiPr2)] (2Mo and 2W) and [(dippN)2M(Cl){1,2-η- tBu 2P-P-P(NEt2)2}]
(3Mo and 3W) were established by single-crystal X-ray diffraction analysis and indicate a side-on geometry of R2P-P-PR’2
moiety. 3W and 3Mo are the first triphosphorus complexes with amido ligand NEt2 on P atom. [(dippN)2M(Cl)(1,2-η-tBu2P-
P-PtBu2)] (1Mo and 1W) and 3Mo, 3W display similar side-on geometry in the solution and in the solid-state. By contrast
2Mo and 2W reveal dynamic behavior in the solution. For the first time the reactivity of diphosphanylphosphido
complexes towards different nucleophiles was studied. The complexes react with phosphorus nucleophile Ph2PLi, yielding
phosphanylphosphinidene complexes [(dippN)2M(Cl)(η2-P-PR2)]– Li+ (M = Mo, W) together with related diphosphanes
R’2P–PPh2. Carbon nucleophile MeLi does not yield [(dippN)2M(Cl)(η2-P-PR2)]– Li+ but substitutes Cl ligand at metal center.
Moreover, we compare the coordination of R2P-P-PR’2 moiety to different metal centers based on DFT methods.
DOI: 10.1039/x0xx00000x
www.rsc.org/
reverse metathesis of [Cp*(CO)3M]Li (M = Mo, W) with tBu2P-
PCl2 leading to dimeric [Cp*(CO)3M(η2-tBu2P-P)]2 with tBu2P=P-
P=PtBu2 ligand of a diphosphenium-dication structure.12
Introduction
During our investigations on the synthesis of transition metal
complexes with low valent di-, tri- and polyphosphorus ligands
we have exploited metathesis reactions of phosphorus
nucleophiles R2P-P(SiMe3)Li or R2P-P(Li)-PR2 with halogen-
substituted transition metal complexes. We have found that
[(dippN)2MCl2·DME] (M = W, Mo) reacts with R2P-P(SiMe3)Li
yielding related anionic phosphanylphosphinidene complexes
[(dippN)2MCl(η2-P-PtBu2)]– (dipp = 2,6-iPr2-C6H3).1,2 These com-
pounds display moderate nucleophilicity and low phospha-
Wittig ability.3,4 They react with phosphorus electrophiles
R’2PX (X = hal) yielding [(dippN)2M(Cl)(1,2-η-R2P-P-PR’2)] (Chart
1A) and react with R’PX2 forming [(dippN)2M(Cl)(η2-R2P-P)-PR’-
(η2-P-PR2)(Cl)M(dippN)2]. [(dippN)2M(Cl)(1,2-η-tBu2P-P-PtBu2)]
is alternatively accessible via metathesis of tBu2P-P(Li)-PtBu2
with [(dippN)2MCl2] (M = Mo, W) (Chart 1A).2 Starting imido
complexes [(RN)2MCl2·dme], M = Mo or W, i.e. R = dipp,5,6 R =
tBu,7 R = electron withdrawing aryl groups,8 and R = tBu and
2,6-Mes2C6H3 (Dmp)9 were studied by Schrock et al as
important species in synthesis of catalysts for carbine-
metathesis. The reactions of tBu2P–P(Li)–PtBu2 with dichlorido
complexes of metals of nickel triad also lead to nearly planar
A
B
P Bu
t
PtBu2
2
tBu2P
P
tBu2P
P
W
Mo
Cl
dippN
Ndipp
dippN
Ndipp
Cl
1W
1Mo
PPh2
tBu2P
P
W
dippN
Ndipp
Cl
6W
PiPr2
PiPr2
Pr P
2
P
i
iPr2P
P
W
Mo
dippN
Ndipp
dippN
Ndipp
Cl
Cl
2W
2Mo
P(Et2N)2
P(Et2N)2
tBu2P
P
Bu P
2
P
t
W
Mo
Cl
dippN
Ndipp
dippN
Ndipp
Cl
3W
3Mo
PiPr2
PtBu2
tBu2P
P
isomers of [L(Cl)M(1,2-η-tBu2P–P–PtBu2)] (L
=
tertiary
iPr2P
P
phosphine).10,11 Another way to polyhosphorus ligands is a
W
W
dippN
Ndipp
dippN
Ndipp
Cl
Cl
4W
4W'
a.
Department of Inorganic Chemistry, Chemical Faculty, Gdansk University of
Technology,Narutowicza 11/12, 80-233 Gdańsk, Poland
† alewisni3@pg.edu.pl
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
Chart 1. The structure of diphosphanylphosphido complexes of Mo(VI) and W(VI), A)
other work2,3, B) this work
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Table 1. Synthesis of diphosphanylphosphido complexes of tungsten(VI) and molybdenum(VI)
[(dippN)2MCl2·dme] (m)
M= Mo (0.455 g/ 0.75 mmol)
M= Mo (0.562 g/ 1.0 mmol)
M= Mo (0.562 g/ 1.0 mmol)
M= W (0.521 g/ 0.75 mmol)
M= W (0.695 g/ 1.0 mmol)
M= W (0.695g / 1.0 mmol)
R2-PLi-PR’2 (m)
[(dippN)2M(Cl)(1,2-η-R2P-P-PR’2)]
R= tBu, R’=tBu (1Mo)
R= iPr, R’= iPr (2Mo)
Yield %
62 2
51
1
2
3
4
5
6
R= tBu, R’=tBu (0.273 g/ 0.75 mmol)
R= iPr, R’= iPr (0.294 g/ 1.0 mmol)
R= tBu, R’= NEt2 (0.473 g/ 1.0 mmol)
R= tBu, R’=tBu (0.273 g/ 0.75 mmol)
R= iPr, R’= iPr (0.294 g/ 1.0 mmol)
R= tBu, R’= NEt2 (0.473 g/ 1.0 mmol)
R= tBu, R’= NEt2 (3Mo)
R= tBu, R’=tBu (1W)
66
67 2
R= iPr, R’= iPr (2W)
73
R= tBu, R’= NEt2 (3W)
71
[(dippN)2M(Cl)(η2-R2P-P)]–Li+
R’2PCl
[(dippN)2M(Cl)(1,2-η-R2P-P-PR’2)]
7
M= W, R = tBu (0.100 g/ 0.098 mmol)
R’= iPr (0.015 g/ 0.098 mmol)
R= tBu, R’= iPr (4W) only NMR data
-
An alternate access to polyphosphorus ligands is a formation
and rearrangement of polyphosphorus skeletons from smaller
building blocks on transition metal centres. Reactions of R2P-
P(SiMe3)Li with [CpZrCl3] or with [CpCp*ZrCl2] or with
[Cp2HfCl2] yield complexes mainly with polyphosphorus
ligands. Thus R2P-P(SiMe3)Li can act as precursors of P2 or R2P-
P(P2) ligands with a structure of phosphanylphosphirane or as
Results and discussion.
Syntheses of diphosphanylphosphido complexes
We used [(dippN)2MCl2·dme] (M = Mo, W) as starting metal
complexes and lithium salts of triphosphanes as the precursor
of the 1,2-η-R2P-P-PR’2 ligands. Synthesis of R2P-P(Li)-PR’2 were
obtained according to literature protocols19, further modified
by us. (Scheme 1) (see experimental part).
precursors of R2P-P(P2)P-PR2 with a butterfly structure.13
A
different access to polyphosphorus ligands is a derivatization
of white phosphorus. It can be realized in reactions of white
phosphorus with transition metals complexes14,15,16 or via
alkali metals oligophosphanides, which can be accessed via
reactions of white phosphorus with main group nucleophiles.17
Taking into account that metathesis reactions of R2P-P(Li)-PR2
with chlorido substituted TM complexes were accomplished
only for bulky R = tBu 1,2,10,11, we expanded our studies on
reagents with smaller R = iPr and we present our results on
reactions of R2P–P(Li)–PR’2 (R = tBu, iPr and R’ = tBu, iPr, Et2N)
with diimido complexes [(dippN)2MCl2·dme] (M = Mo, W) in
order to test the regioselectivity of these reactions and to
establish the influence of steric and electronic properties of R
and R’ groups on the XRD structures and NMR data of resulting
complexes [(dippN)2M(Cl)(1,2-η-R2P-P-PR’2)] (Chart 1B). The
reactivity of complexes with diphosphanylphosphido ligands
was up to now not investigated. Thus, we present results of
reactions of these complexes with electrophilic [(CO)5Cr·THF]
and with a broad spectrum of nucleophilic reagents Ph2PLi,
PhLi, tBuLi, MeLi, tBuOLi and PMe3. Taking into account that
geometries of complexes [LnM(1,2-η-R2P-P-PR’2) mimic in
many aspects the ones of related phosphanylphosphinidene
complexes [LmM(η2-R2P-P)], we conducted DFT calculations
and discussed the bonding of R2P-P-PR2 moiety (R = tBu) to the
different metal centers comparably, as has been very recently
done for phosphanylphosphinidene complexes. 18
toluene
R2PP(SiMe3)Li + R'2PCl
R2PP(SiMe3)PR'2
- LiCl
nBuLi/THF
R2PP(SiMe3)PR'2
R2PP(Li)PR'2
R=tBu, iPr;
R'= tBu, iPr, NEt2
-nBuSiMe
3
Scheme 1. Synthesis of lithium salts of triphosphanes
The diphosphanylophosphido complexes with general formula
[(dippN)2M(Cl)(1,2-η-R2P-P-PR’2)] were achieved the same way
as reported by us to prepare 1W 2
. The toluene solution of
[(dippN)2MCl2·dme] was added at room temperature to a
suspension of R2P–P(Li)–PR’2 in toluene. Work-up and
crystallization from pentane solution yields red crystals of
related tungsten or molybdenum compounds 2Mo, 2W, 3Mo,
3W (Scheme 2). The products, yields and designations of
individual compounds are collected in Table 1 (method 1, run
1-6). Reactions leading to 2Mo and 2W are accompanied by
side processes yielding small amounts of isotetraphosphines
(tBu2P)3P20 and (iPr2P)3P21, as indicated by 31P-NMR
examinations of reaction solutions. In some cases (tBu2P)3P20
and (iPr2P)3P21 were indicated as contaminations in solutions
of isolated products. Furthermore reactions involving tBu2P–
P(Li)–PEt’2 (syntheses of 3Mo and 3W) are concomitant with a
formation of small amounts of a phosphetane tBu2P-P(μ2-
PNEt2)2P-PtBu2.
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PR'2
The
spectrum
of
2Mo
recorded
at
Cl
Cl
dme
R2P
P
R2P-PLi-PR'2
- LiCl
–50 °C the 31P{1H} is consistent with a side-on geometry and a
formula [(dippN)2Mo(Cl)(1,2-η-iPr2P-P-PiPr2)]. This dynamic
behavior is only visible for relatively small both R and R’ groups
within the R2P-P-PR2’ moieties. 4W does not display such
dynamic behavior and no traces of a putative 4W’ are visible at
all.
M
M
Cl
dippN Ndipp
dippN
Ndipp
dipp =2,6-iPr2C6H3
R, R'=iPr;M= W,Mo 2W;2Mo
R=tBu; R'=NEt2; M=W,Mo 3W; 3Mo
Scheme 2. Syntheses of diphosphanylphosphido complexes 2W, 2Mo, 3W and 3Mo.
An alternate access to complexes with unsymmetrical
diphosphanylophosphido ligands are reactions of anionic
In order to check the presence of this compound at least in
reaction solution, a reaction of [(dippN)2W(Cl)(η2-iPr2P-P)]–Li+
with an excess of tBu2PCl was conducted. [(dippN)2W(Cl)(η2-
iPr2P-P)]–Li+ was generated in situ, because this complex is not
very stable in solution and isolation of this crystalline
compound succeeded only with a low yield. To our surprise,
according to 31P-NMR investigations this reaction gives a
phosphinidene complex [(dippN)2M(Cl)(η2-tBu2P-P)]–Li+
(
5W
with R2’PX, (X= Cl, Br, R= Ph)3 (Scheme 3). We used this
method for synthesis 4W in reaction of iPr2PCl with 5W
)
.
However 4W was not isolated and its structure was analyzed
only in solution by NMR spectroscopy.
mixture of 1W : 2W : 4W in molar ratio ≈ 1.0 : 0.8 : 0.6. The
PiPr2
resonances which can be attributed to 4W’ in solution, were
not visible at all. A formation of such an isomer of 4W in this
run cannot be discarded, thus the most plausible explanation
is that the equilibrium 4W’ versus 4W is completely shifted to
the side of 4W (Scheme 5) (for experimental and 31P-NMR data
of 4W see supplementary information).
tBu2P
P
tBu2P
P
iPr2PCl
Li.3dme
W
Cl
W
-LiCl
dippN
Ndipp
dippN
Ndipp
Cl
dipp = 2,6-iPr2C6H3
4W
Scheme 3. Synthesis of diphosphanylphosphido complex 4W.
Compounds 2Mo, 3Mo and 2W, 3W were isolated as red
iPr2P(2) P(3)iPr2
P(3)iPr2
iPr2P(2) P(1)
iPr2P(2)
crystalline solids from crystallization in pentane and they are
well soluble in aromatic hydrocarbons. In a crystalline form
they are relatively stable in the air. 2Mo and 2W are stable in a
sealed NMR tube in aromatic hydrocarbons, but 3Mo and 3W
decompose slowly in solution via cleavage of P–P(NEt2)2 of
coordinated R2P-P-P(NEt2)2 and a formation of complexes
[(dippN)2M(Cl)(η2-(H)P–PtBu2)] (M = Mo, W); for 31P-NMR see.2
P(1)
P(1) P(3)iPr2
M
M
M
dippN
Ndipp
dippN
Ndipp
dippN
Ndipp
Cl
Cl
Cl
Scheme 4. Dynamic behavior of iPr2P2-P1-P3iPr2 ligand
P Bu
t
P Pr
i
2
2
iPr2P
P
tBu2P
P
W
W
dippN
Ndipp
dippN
Ndipp
Cl
Cl
Elucidation of structures of diphosphanylphosphido complexes in
the solution
4W'
4W
Scheme 5. Dynamic behavior of iPr2P-P-PtBu2 ligand
The 31P NMR analysis of spectra of isolated products points
high regioselectivities of reactions denoted in table 1 as runs 3
Crystal structures
and 6 yield only and solely one type of isomers (3Mo
where the P(NEt2)2 moiety does not coordinate to metal
centers. Similarly as was established for 1Mo and 1W
31P-
, 3W)
The X-ray structure of tBu2P-PLi-P(NEt2)2 (Fig. 2) is similar to
structures of symmetrical R2P-PLi-PR2 described previously. 19
P2P1P3Li atoms form a hetero-four-membered ring with the
lithium atom located outside and solvated by two THF
molecules. The four-ring is nearly planar and the deviation
difference (RMS deviation = ±20pm) is more significant than
the one mentioned in literature 19. The P1-P2 (2.174 Å) and P2-
P3 (2.172 Å) distances are very similar and short.
,
NMR spectra indicate that compounds 3Mo and 3W display
the side-on geometry in solution at room temperature. 4W
displayed a side-on geometry with η2-tBu2P-P fragment at 25
°C as well. By contrast, 31P-NMR spectra of (2Mo and 2W) at
room temperature are broad and featureless due to a dynamic
behavior of iPr2P2-P1-P3iPr2 ligand (Scheme 4). This
assumption was supported by variable temperature (VT) 31P-
NMR experiments (Fig. 1).
Since the X-ray structures of 2Mo
- 2W and 3Mo - 3W are
similar, we discuss in the text only 2W (Fig. 3) and 3W (Fig. 4)
together with previously reported 1W. For 2Mo and 3Mo see
supplementary (Fig. S1, Fig. S2). Up to now the known
complexes with (1,2-η-R2P2-P1-P3R’2) can be divided into two
groups: i. The first group are complexes of late transition
metals [X(R3P)M(1,2-η-tBu2P-P-PtBu2)] (X = Br, Cl, M = Pt, Pd,
Ni)10,11,22 and complexes with cyclo-P5tBu4 anion
(Ph3P)2Rh(cyclo-P5tBu4)], [Ph3P(Cl)Ni(cyclo-P5tBu4)], [M(cyclo-
P5tBu4)]2 (M = Ni, Pd)23,24. This group indicates a weak bonding
of phosphido P1-atom and a stronger bonding of phosphanyl
P2 atom to metal centre. The P1-P2 distance is very short. ii.
The second group are diphosphanylphosphido complexes of
Figure 1. VT-NMR for 2Mo.
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tungsten(VI) and molybdenum(VI). This group indicates a
strong bonding of phosphido P1-atom and a short bonding of
phosphanyl P2 atom. The P1-P2 distance is slightly longer than
in the first group.
Both compounds 2W and 3W contain distorted tetrahedral
tungsten centers. The alignments around P1 and P3 are
pyramidal and around P2 nearly planar, both for 2W and 3W
.
The significant feature of both structures is the side-on
geometry of the R2P2–P1 part of the ligand R2P2–P1–P3R2
alignment, which leads to short P1-P2 distances, 2.145 Å (2W
)
and 2.159 Å (3W). The distances P1-P3 are in the range for a
single P-P in diphosphanes, 2.238 Å (2W) and 2.243 Å (3W).To
discuss these values it must be taken into consideration that
Figure 2. X-ray structure of tBu2P-PLi-P(NEt2)2 showing the atom-numbering scheme
(30% probability displacement ellipsoids), H atoms have been omitted for clarity.
Important bond lengths (Å) and bond angles (deg): P1-P2 2.1742(7), P1-P3 2.1724(7),
P3-N1 1.704(2), P3-N2 1.721(2), Li-O1 1.925(3), Li-O2 1.907 (3), P2-P1-P3 91.74(3)
the reliable P-P single bond in diphosphines is 2.217 ± 0.08 Å25
,
the single P-P bonds in triphosphines are significantly shorter,
for tBu2P–PLi–PtBu2 ·2THF P-P ≈ 2.167 Å, for tBu2P–P(SiMe3)–
PtBu2 P-P≈ 2.192 Å26 and for iPr2P–PLi–PiPr2·Et2O P-P≈ 2.163
Å27. However, in DmpP(PPh2)2 (Dmp = 2,6-Mes2C6H3) the P-P
distances are 2.2427 Å (aver.) 28 and in (Ph2P)2P-(PtBu2) they
are in the range 2,2231 – 2.244629, which is in the range of a
single P-P bond.
Reactivity studies on diphosphanylphosphido complexes of Mo(VI)
and W(VI).
This study not only describes the synthesis and the structure of
diphosphanylphosphido complexes, but also, for the first time,
examines the reactivity of these complexes. For reactivity
study we selected 2Mo, 2W, 3Mo and 3W and moreover to
get the broader perspective on this issue, we decided to use
also the previously obtained 1W2. We have tested reactions of
mentioned compounds with a wide range reagents such as
electrophilic [(CO)5Cr·THF] or O-, N-, P- and C-based
nucleophiles.
Figure 3. X-ray structure of 2W showing the atom-numbering scheme (30% probability
displacement ellipsoids),
H atoms have been omitted for clarity. Important bond
lengths (Å) and bond angles (deg): P1-P2 2.145(8), P1-P3 2.238(7), P2-W1 2.520(5), P1-
W1 2.526(5), W1-Cl1 2.369(5), W1-N1 1.725 (19), W1-N2 1.706(19), P1-W1-P2
50.30(18), N1-W1-N2 114.2 (8), C1-N1-W1 158.3(16), C13-N2-W1 174.9(16), P2-P1-P3
112.80(10), P2-P1-W1 64.7(2), P3-P1-W1 109.1(3). ΣP1 = 282.0, ΣP2 = 343.3 (P2-W
bond is not included), ΣP3 = 299.0.
According to our analysis, 1W does not react with
[(CO)5Cr·THF]. It suggests that the free electron pairs on P1
and P3 atoms are not active. Natural Bonding Orbitals (NBO 6)
calculations indicate that these lone pairs do exist but consist
mostly of s orbitals, and therefore, their shapes are rather
spherical. Moreover, the steric hindrance of tBu groups at
adjacent P atoms hampers a formation of a P–Cr bond.
The reactivity of [(dippN)2M(Cl)(1,2-η-R2P2-P1-P3R’2)]
towards nucleophilic reagents depends strongly on hardness
of these reagents. All tested complexes (2Mo, 3Mo, 1W-3W)
react with phosphorus nucleophile Ph2PLi (Scheme 6) yielding
phosphinidene complexes [(dippN)2M(Cl)(η2-R2P-P)]–Li+ and
diphosphanes R2’P–PPh2. This conclusion was ascertained by
the isolation of crystals of [(dippN)2M(Cl)(η2-R2P-P)]–Li+, the
determination of their structure with XRD and by the presence
30
of strong signals of tBu2P-PPh230, iPr2P-PPh2 and (Et2N)2P-
30
PPh2 in reaction solutions (31P-NMR). In the reaction of 1W
with Ph2PLi, some amounts of Ph2P-PPh2 were also formed. It
is worth to mention that this type of reactions easily
rationalizes a formation of isotetraphosphines (tBu2P)3P20 and
(iPr2P)3P21 as side products in reactions according to Scheme 2;
in this case R2P-P(Li)-PR2 acts as Ph2PLi in Scheme 6. To our
surprise, the reactivity of nucleophiles based on the elements
Figure 4. X-ray structure of 3W showing the atom-numbering scheme (30% probability
displacement ellipsoids),
H atoms have been omitted for clarity. Important bond
lengths (Å) and bond angles (deg): P1-P2 2.159(2), P1-P3 2.243(3), P1-W1 2.495(2), P2-
W1 2.5571(19), W1-Cl1 2.3701(19), W1-N1 1.763 (7), W1-N2 1.774(7), P1-W1-P2
50.58(6), N1-W1-N2 113.4(3), C1-N1-W1 155.9(5), C13-N2-W1 172.2(6), P2-P1-
P3 110.13(11), P2-P1-W1 66.20(8), P3-P1-W1 108.65(10). ΣP1 = 284.98, ΣP2 = 345.7
(P2-W bond is not included), ΣP3 = 308.2, ΣN3 = 358.16.
4 | J. Name., 2012, 00, 1-3
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of the second row of periodic table is significantly different. reversible reaction at P1 is supported by formation of Ph2P–
The O-based nucleophile – tBuOLi and N-based – (Me3Si)2NLi PPh2 visible in the 31P-NMR (Scheme 8). The harder PhLi reacts
do not react with 1W. The carbon nucleophile tBuLi does not at P3 and W and the hardest MeLi reacts almost solely at W-
react as well but MeLi and PhLi do react with 1W. The 31P-NMR atom.
examinations of reaction solutions unambiguously clear up the The reactivity of diphosphanylphosphido complexes towards
processes in solutions. The yield of reactions performed with tertiary phosphines depends significantly on the art of R’
MeLi and PhLi are significantly different. The first reaction groups and on the steric properties of phosphine. PMe3 does
proceeds in only 10% yield, whereas the second reaction not react with 1W at room temperature but it reacts at this
proceeds in 60% yield. MeLi reacts with 1W slowly and nucleo- temperature in the presence of AgBF4 yielding a mixture of
philic substitution occurs at metal centre.
products containing several tungsten complexes, among
others the [(dippN)2W(PMe3)(η2-tBu2P-P)]. The identity of this
complex was ascertained by comparison of its already
published 31P-NMR spectra.8 Furthermore, PMe3 is prone to
the reaction with 3W at 25 °C yielding (Et2N)2PCl and
[(dippN)2W(PMe3)(η2-tBu2P-P)] (Scheme 9). The more bulky
tertiary phosphines such us Me2PPh does not react with 1W
or 3W even in the presence of AgBF4.
Scheme 6. The reaction of 1W - 3W and 2Mo - 3Mo with Ph2PLi.
Scheme 7. The reaction 1W with MeLi
Scheme 9. The reaction of 3W with PMe3
The comparison of P1–P3R’2 distances for 3Mo vs 1Mo
(2.240 Å vs 2.238 Å) and 3W vs 1W (2.245 Å vs 2.236 Å)
indicates that Et2N substituents cause very slightly elongations
of P1–P3 bonds. According to NBO calculations these are single
bonds polarized in direction of P1. Natural Population Analysis
indicates charges: P3 +0.408 and P1 -0.176 for 1W and P3
+0.902 and P1 -0.233 for 3W, which means that P1-P3 bond is
significantly stronger polarized in 3W. This leads to enhanced
reactivity of this bond and facilitates the elimination of
(Et2N)2PCl.
Scheme 8. Reactivity 1W towards Ph2PLi
Moreover, a new compound is formed, which displays similar
31P-NMR signals as 1W and was attributed to [(dippN)2W(Me)-
(1,2-η-tBu2P-P-PtBu2)] (Scheme 7), (see experimental part and
supplementary for NMR details).
DFT calculations
In order to explain features of X-ray structures of
diphosphanylphosphido complexes of transition metals and to
rationalize reactivity of this class of compounds, we have
conducted DFT calculations (see supplementary for details).
Moreover, we compare the influence of transition metal on
the geometry in complexes with 1,2-η-R2P-P-PR’2 ligands vs
complexes with η2-R2P-P ligand18. For our studies we selected
platinum complex [(1,2-η-tBu2P2=P1–P3tBu2)Pt(Cl)P4(pTol)3]
PhLi reacts with 1W in two ways: i. as MeLi yielding
[(dippN)2W(Ph)(1,2-η-1,2-η-tBu2P-P-PtBu2)].
ii.
yielding
tBu2PPh 31 and 5W. To get deeper insight into the reactivity of
this class of complexes, we conducted Condensed Fukui
Function and Local Softness calculations for 1W (the
localization of these functions was based on Hirshfeld
Population Analysis). In the whole publication, the numbers of
atoms are compatible with X-ray data. To select atoms which
are prone to nucleophilic substitutions, the Condensed Fukui
Minus Functions were considered.32a-g The values are 0.072 for
P1, 0.066 for P3, 0.039 for P2, and 0.019 for W. The local
softness values are for P1 0.889, for P3 0.815, for P2 0.383,
and for W 0.235. It means that P1 and P3 atoms are most
prone to the substitution with soft nucleophile (R2PLi). These
calculations support the reactivity studies. The soft Ph2PLi
reacts in two positions, at P1 which leads to equilibrium and at
P3 which leads to formation of [(dippN)2M(Cl)(η2-tBu2P-P)]– as
a leaving group in an irreversible process. The existence of a
(
1Pt) and tungsten complexes 1W
The NBO and NLMO analyses revealed substantial differences
in structure of Pt versus W complexes. In case of 1Pt
, 2W and 3W.
,
triphosphorus ligand exhibits P1=P2 double bond and P1-P3
single bond (Figure 5a-c). Moreover, lone pairs are located on
P1 and P3 atoms, whereas on P2 atom no lone pair is present
(Figure 5d-e). The lone pair on P1 atom interacts with σ*(P2C)
antibonding orbitals, which is manifested by the increased
cumulative occupancy of NBOs ascribed to these orbitals
(0.293) (negative hyperconjugation). The calculation of NPA
charges for 1Pt shows a large positive charge on P2(+0.694)
and a relatively smaller positive charge on the second,
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terminal P3 atom (+0.380) and negative charge on the central Our DFT calculation revealed that 1W
Journal Name
,
2W and 3W display
P1 atom (-0.210), while Pt is almost neutral (0.079). The similar structural features. Because of this reason, these
interactions between Pt metal center and triphosphorus ligand compounds will be discussed together. In contrast to 1Pt, only
are similar to those observed in Pt ethylene complexes. The single P-P bonds are present within the ligand R2P2–P1–P3R’2
Pt(0) metal center in 1Pt possess d10 electronic configuration. (R = tBu, iPr; R’= tBu, iPr, NEt2) (Figure 7a-b). Due to NPA
The π(P1P2) bonding orbital interacts with the empty s orbital analysis of representative 1W complex, terminal P1 and P3
of platinum (Figure 6a). On the other hand, a strong back- atoms bear positive charges (+0.518 and +0.417 respectively),
donation is observed from filled d orbital of platinum to while P1 has negative charge (-0.197). A large positive charge
π*(P1P2) antibonding orbital (Figure 6b). This statement is (+1,14) is present on tungsten atom. Furthermore, lone pairs
supported by reduced occupancy of NBO associated to π(P1P2) are located on P1 and P3 atom (Figure 7c-d), however electron
(1.67) and the high occupancy of NBO attributed to π*(P1P2) pair on P2 atom interacts with tungsten atom forming σ-bond
(0.90). Furthermore, Pt participates in NMLOs attributed to (Figure 7f). Additionally, the triphosphorus ligand is connected
π(P1P2) and π*(P1P2) where significant contribution of the to metal center via the second single σ-bond P1-W (Figure 7e).
metal is visible (10.0% and 36.2% respectively) (Figure 6ab). Reduced occupancy of NBO attributed to lone pair on P1 (1W
:
Taking this observation into account, the structure of 1.87) together with increased cumulative occupancies of NBOs
triphosphorus ligand in 1Pt can be described as of σ*(P2C) (1W: 0.23) reveals interaction between these
phosphanyldiphosphenium cation R2P(+)=P–PR, σ2-σ3 bonding orbitals resulting in shortening P1-P2 bonds (negative
motif C according to Weigand.33
hyperconjugation).
Figure 7. Graphical representation of the NBOs of 1W associated to: a) σ(P1P2), b)
Figure 5. Graphical representation of the NBOs of 1Pt associated to: a) σ(P1P2), b)
σ(P2P3), c) P1 lone pair, d) P3 lone pair, e) σ(P1W), f) σ(P2W).
σ(P2P3), c) π(P1P2), d) P1 lone pair, e) P3 lone pair.
Moreover small contribution of W atom in NMLO of P1 lone
pair (1W: 1.86%) indicates weak interactions of this orbital
with metal center. The results of our calculations points that
triphosphorus ligand in tungsten complexes has a structure of
diphosphanylphosphide R2P–P(-)–PR’2, σ2-σ3 bonding motif D
according to Weigand.33
In case of tungsten complexes with R2P–P–PR’2 ligands
containing mixed substituents (R = tBu and R’= iPr, NEt2, Ph)
we observed that in all obtained complexes tBu2P phosphanyl
group coordinates to the metal center. This phenomena can be
Figure 6. Graphical representation of the NLMOs of 1Pt associated to: a) π(P1P2), b)
π*(P1P2).
6 | J. Name., 2012, 00, 1-3
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explain by comparison of nucleophilic properties of tBu2P, Synthetic procedures
iPr2P, (Et2N)2P and Ph2P. In a course of our studies on
(1) Synthesis of tBu2P-P(Li)-P(NEt2)2
·
2.4THF35,36 (5,352g,
diphosphines with different substituents we observed that
tBu2P moiety is the strongest nucleophile due to inductive
effect of tBu groups30. Despite of a presence of amino
1a. The solution of tBu2P-P(SiMe3)Li
0.0125 mol) in toluene (40 mL) was slowly dropped to the
cooled (-30 C) solution of (Et2N)2PCl (2.758 g, 0.0131 mol). The
reaction mixture was stirred at -30 C for 3 h and finally at
°
electron-donating group, (Et2N)2P moiety is
a weaker
°
nucleophile in comparison to tBu2P because of the strong
delocalization of charge. The Ph2P moiety is the weakest
nucleophile in the series due to electron-accepting properties
of phenyl group. As we can expect metal center prefers,
formation of σ-bond with phosphanyl group possessing the
strongest nucleophilic properties (tBu2P).
ambient temperature for 12 h. The solvent was then
evaporated under vacuum (2x10-3 Torr). The residue was
dissolved in n-pentane and filtered. The solvent removed
under reduced pressure to afford pure tBu2P-P(SiMe3)-P(NEt2)2
as yellow oil. Yield: 5.439g (96%)
δP (400 MHz, C6D6, H3PO4, 25°C) 111.5 (dt, P3), 45.6 (dd, P2),
–141.9 (dd, 1JP1-P2 = 430 Hz, 1JP1-P3 = 138 Hz, 2JP2-P3 =72 Hz, P1)
1b. The solution of 2.5 M n-BuLi (5.27 cm3, 0.0132 mol) in
hexane was slowly dropped to the cooled THF solution of
tBu2P-P(SiMe3)-P(NEt2)2 (5.439 g, 0.01198 mol). The reaction
The comparison of structures of 1Pt and 1W with
corresponding phosphanylphosphinidene complexes18 shows a
few similarities between these two class of compounds
(Scheme 8). 1Pt can be seen as substituted
phosphanylphosphinidene complex of Pt where one electron
pair on terminal P atom has been replaced by tBu2P moiety.
Both in 1Pt and in platinum phosphanylphosphinidene
complex P=P double bond is present and it interacts with Pt(0)
metal center in the similar way: π(P1P2)→s(Pt) donaꢀon and
d(Pt) → π*(P1P2) back-donation. In phosphanylphosphinidene
complex of tungsten phosphorus ligand is bonded to metal
center via P2-W single bond and P1=W double bond, whereas
in case of diphosphanylphoshido complex 1W triphosphorus
ligand is bonded only via two σ-bonds P1-W and P2-W. In both
tungsten complexes P1-P2 bond has single bond character.
mixture was stirred at -30°C for 3 h and finally at ambient
temperature for 12 h. The resulting solution was evaporated
under vacuum (1 mTorr, 3 h). The residue was dissolved in a
mixture of THF and pentane. The solution was stored at 30 °C
yielding a precipitate of solvated tBu2P-P(Li)-P(NEt2)2. Yield:
3.611g (63.7%)
δH (400 MHz; C6D6; Me4Si; 25°C) 3.13 (8 H, m, CH2), 1.23 (4 H,
3
d, CH3 t-buthyl), 0.97 (12 H, t, CH3 ethyl, JHH = 7.1 Hz)
δP (400 MHz, C6D6, H3PO4, 25°C) 158.4 (dt, P3), 51.3 (dd, P2),
–127.0 (dd, 1JP1-P2 = 284 Hz, 1JP1-P3 = 329 Hz, 2JP2-P3 =308 Hz, P1)
(2) Reactions of iPr2P-P(Li)-PiPr2 with [(dippN)2MoCl2] in
toluene. Synthesis of [(dippN)2(Cl)Mo(1,2-η-iPr2P-P-PiPr2)]
(2Mo)
A solution of [(dippN)2MoCl2·dme] (0.562 g, 1.0 mmol) in
toluene (2 mL) was added dropwise at room temperature to a
suspension of iPr2P-P(Li)-PiPr2·0,3THF (0.294 g, 1.0 mmol) in
toluene (2 mL). The reaction mixture was stirred for 1 day, the
suspension dissolved completely and turned red. The solvent
was then evaporated under vacuum (2x10-3 Torr) for 2 h. The
residue was dissolved in n-pentane (4 mL) and filtered. The
volume was concentrated to 1 mL . After cooling for 2 days at
4°C, dark red crystals of 2Mo were formed (0.381 g, 51%
yield). Elemental analysis (Found: C, 57.63; H, 8.29; N, 3.71%,
Calc. for C36H62MoN2P3Cl: C, 57.87; H, 8.36; N, 3.75% )
Scheme 8. The comparison of structures of 1Pt and 1W with corresponding
phosphanylphosphinidene complexes A and B.
δH (400 MHz; toluene-d8; Me4Si; -50°C) 7.0–6.7 (6 H, m,
3
overlapped, C6H3), 3.85 (4 H, sept, CH dipp, JHH = 6.8 Hz), 2.08
Experimental parts
(4 H, br s, CHP), 1.07 (12 H, d, CH3 dipp, 3JHH = 6.8 Hz), 1.04 (12
H, d, CH3 dipp, 3JHH = 6.8 Hz), 1.2 - 0.9 (24 H, br s, CH3)
Materials and methods
All experiments and other manipulations were carried out in
an argon atmosphere. Pentane, petrol ether, toluene and DME
were dried with benzophenone and Na/K and distilled under
argon. All operations were carried out using Schlenk-type
glassware at a vacuum line or in a glovebox. All solid materials
δP (400 MHz, toluene-d6, H3PO4, -50°C) 29.7 (dd, P3), 7.8 (dd,
2
1
1
P2), –135.2 (dd, JP1-P2 = 398 Hz, JP1-P3 = 202 Hz, JP2-P3 =12 Hz,
P1)
δC (100.6 MHz, toluene-d8, Me4Si, 25 °C) 153.5 (s, CN), 144.8 (s,
Ci), 126.6 (s, Cp), 122.3 (s, Cm), 28.5 (d, J = 2.5 Hz, CH ), 24.4 (d, J
= 1.3 Hz, CH3), 23.3 (bs, CH3), signals iPr groups at P atoms are
invisible on account a dynamic behavior of iPr2P2-P1-P3iPr2
ligand.
were dried under vacuum. 31P, 13C, and H NMR spectra were
1
recorded on Bruker AV400 spectrometer (external standard
1
TMS for H, 13C; 85% H3PO4 for 31P) at ambient temperature.
Literature methods were used to prepare [(dippN)2MCl2 dme]
(dipp = 2,6-iPr2C6H3, M= Mo, W)5,34 and 1W 1Mo2
, .
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3
(3) Reactions of iPr2P–P(Li)-PiPr2 with [(dippN)2WCl2] in (3H, sept, CH dipp, JHH = 6.8 Hz), 3.19 (4H, m, CH2 Et), 3.00
toluene. Synthesis of [(dippN)2(Cl)W(1,2-η-iPr2P-P-PiPr2)] (4H, m, CH2 Et), 1.58 (18 H, d, tBu2P, 3JPH =16.4 Hz), 1.27 (24 H,
(2W)
m, CH3 dipp), 0.92 (12 H, t, CH3 Et, 3JHH = 7.0 Hz)
Analogously to
2
, the new triphosphorus complex 2W was δP (400 MHz, toluene-d6, H3PO4, 25°C) 117.3 (d, P3), 40.8 (dd,
prepared from [(dippN)2WCl2·
dme] (0.695 g, 1.0 mmol) and P2), –135.0 (dd, 1JP1-P2 = 403 Hz, 1JP1-P3 = 249 Hz, 2JP2-P3 =2.5 Hz,
iPr2P–P(Li)–PiPr2·0,3THF (0.294 g, 1.0 mmol). The overnight 1JP1-W = 83 Hz, 1JP2-W = 19.5 Hz, P1)
storage at 4°C yielded dark red crystals of 2W (0.609 g, 73% δC (100.6 MHz, toluene-d8, Me4Si, 25 °C) 152.8 (s, CN), 145.5 (s,
yield). Elemental analysis (Found: C, 51.68; H, 7.52; N, 3.38%;
Calc. for C36H62WN2P3Cl: C, 51.78; H, 7.48; N, 3.35% )
Ci), 125.8 (s, Cp), 121.9 (s, Cm), 44.1 (dd, J= 17.5 Hz, 9.4 Hz,
CH2Et), 38.4 (m, CtBu), 31.8 (ddd, J = 2.6 Hz, 5.0 Hz, CH3tBu), 27.8
δH (400 MHz; toluene-d8; Me4Si; -50°C) 7.0–6.6 (6 H, m, (dd, J = 1.3 Hz, 2.0 Hz, CHiPr), 22.6 (s, CH3iPr), 14.7 (dd, J=0.6 Hz,
overlapped, C6H3), 2.48 (3 H, sept, CH, 3JHH = 6.8 Hz ) 1.07 (9 H, 3.7 Hz, CH3Et
d, CH3, 3JHH = 6.8 Hz), 1.04 (9 H, d, CH3, 3JHH = 6.8 Hz)
)
δP (400 MHz, toluene-d6, H3PO4, -50°C) 29.9 (dd, P3), 11.8 (dd, (6) Reaction of 1W with Ph2PLi. Synthesis of
1
1
2
P2), –158.2 (dd, JP1-P2 = 360Hz, JP1-P3 = 197Hz, JP2-P3 =13 Hz, [(dippN)2W(Cl)(η2-tBu2P-P)]–Li+
1JP1-W = 63 Hz, P1)
A solution of Ph2PLi (0.0384 g, 0.2 mmol) in DME was added
δC (100.6 MHz, toluene-d8, Me4Si, 25 °C) 152.5 (s, CN), 144.8 (s, dropwise to a solution of 1W (0.178 g, 0.2 mmol) in DME at
Ci), 126.0 (s, Cp), 121.9 (s, Cm), 28.2 (s, CH ) 24.3 (s, CH3), 23.3 room temperature. During the reaction, the color of the
(bs, CH3)
solution changed from red to purple. The volume was reduced
to one-half under reduced pressure, and the resulting solution
(4) Reactions of tBu2P-P(Li)-P(NEt2)2 with [(dippN)2MoCl2] in was analyzed by 31P{1H}, 31P, and 1H-NMR. The rest of the
toluene.
P(NEt2)2)] (3Mo)
Analogously to
Synthesis
of
[(dippN)2(Cl)Mo(1,2-η-tBu2P-P- solvent was then evaporated under reduced pressure and the
residue extracted with 5 mL of toluene. The extract was
2, but using [dippN)2MoCl2·dme] (0.562 g, 1.0 filtrated off and concentrated to 1 mL. After cooling for 1 day
mmol) and tBu2P–P(Li)–P(NEt2)2·1,6THF (0.473 g, 1.0 mmol). at -30°C, dark red crystals of 5W 1 were formed.
The overnight storage at 4°C yielded dark red crystals of 3Mo
(0.549 g, 66% yield). Elemental analysis (Found: C, 57.40; H, (7) Reaction of 3W with Ph2PLi. Synthesis of
8.60; N, 6.67% Calc. for C40H72MoN4P3Cl: C, 57.65; H, 8.71; N, [(dippN)2W(Cl)(η2-tBu2P-P)]–Li+
6.72%)
Analogously to 6, but using Ph2PLi (0.0384 g, 0.2 mmol) and
δH (400 MHz; toluene-d8; Me4Si; 25°C) 7.15–6.9 (6 H, m, 3W (0.184 g, 0.2 mmol). The overnight storage at -30°C yielded
overlapped, C6H3), 4.12 (4 H, sept, , CH dipp, 3JHH = 6.8 Hz), 3.20 dark red crystals of 5W1
(4H, m, CH2), 3.02 (4H, m, CH2), 1.60 (18 H, d, tBu2P, 3JPH =16.2
.
Hz), 1.27 (6H, d, CH3 dipp, JHH= 6.8 Hz), 1.25 (6H, d, CH3 dipp, (8) Reaction of 1W with PhLi
JHH= 6.8 Hz), 1.23 (12H, d, CH3 dipp, JHH= 6.8 Hz), 0.92 (12 H, t, A solution of PhLi (0.0185 g, 0.24 mmol) in DME was added
3
CH3 JHH = 7.1 Hz)
dropwise to a solution of 1W (0.178 g, 0.2mmol) at room
δP (400 MHz, toluene-d6, H3PO4, 25°C) 112.7 (dd, P3), 41.0 (dd, temperature. During the reaction, the color of the solution
P2), –109.7 (dd, 1JP1-P2 = 441 Hz, 1JP1-P3 = 252 Hz, 2JP2-P3 =4.0 Hz, changed from red to purple. The volume was reduced under
P1)
reduced pressure, and the resulting solution was analyzed by
δC (100.6 MHz, toluene-d8, Me4Si, 25 °C) 153.8 (s, CN), 145.7 (s, 31P{1H}, 31P, and 1H-NMR. After cooling at -30 °C, dark red
Ci), 126.5 (s, Cp), 122.2 (s, Cm), 44.1 (dd, J = 9.3 Hz, 17.4 Hz, crystals of 5W 1 were formed. 31P{1H}-NMR examination of the
CH2Et), 34,2 (s, CtBu), 31.7 (ddd, J = 2.8 Hz, 4.9 Hz, CH3tBu), 28.1 reaction solution: 1W (35%)2, [(dippN)2W(Ph)(1,2-η-tBu2P-P-
(dd, J = 1.5 Hz, 2.0 Hz, CHdipp), 24.6 (s, CH3dipp), 23.6 (s, CH3dipp), PtBu2)] (65%)
14.6 (d, J = 3.2 Hz, CH3Et
)
1W: δP (400 MHz, C6D6, H3PO4, 25°C) 45.1 (bd, P3), 30.6 (dd,
P2), –143.9 (dd, 1JP1-P2 = 417.3 Hz, 1JP1-P3 = 272.9 Hz, 2JP2-P3 = 13
(5) Reactions of tBu2P-P(Li)-P(NEt2)2 with [(dippN)2WCl2] in Hz, P1)
toluene. Synthesis of [(dippN)2(Cl)W(1,2-η-tBu2P-P-P(NEt2)2)] [(dippN)2W(Ph)(1,2-η-tBu2P-P-PtBu2)]: δP (400 MHz, C6D6,
1
H3PO4, 25°C) 45.1 (bd, P3), 24.8 (dd, P2), –156.7 (dd, JP1-P2
(3W)
=
Analogously to 2, but using [(dippN)2WCl2·
dme] (0.695 g, 1.0 429 Hz, 1JP1-P3 = 297 Hz, 2JP2-P3 = 12.5 Hz, P1)
mmol) and tBu2P–P(Li)–P(NEt2)2·1,6THF (0.473 g, 1.0 mmol). 1H NMR and 1H-31P HMBC NMR see supplementary materials.
The overnight storage at 4°C yielded dark red crystals of 3W
(0.653 g, 71% yield). 3W crystallize together with the substrate (9) Reaction of 1W with MeLi.
(dippN)2WCl2
·
DME. The NMR spectra and elemental analysis A solution of MeLi (0.0053 g, 0.24 mmol) in DME was added
crystal composition: 80% 3W 20% dropwise to a solution of 1W (0.178 g, 0.2 mmol) at room
·DME Elemental analysis: (Found: C, 51.50; H, temperature. During the reaction, the color of the solution
reported
a
;
(dippN)2WCl2
7.71; N, 5.89%; Calc. for C37.2H65.6WN3.6P2.4Cl1.2O0.2: C, 51.50; H, changed from red to purple. The volume was reduced under
7.57; N, 5.82% )
reduced pressure, and the resulting solution was analyzed by
δH (400 MHz; toluene-d8; Me4Si; 25°C) 7.2–6.8 (6 H, m, 31P{1H}, 31P, and 1H-NMR. 31P{1H}-NMR examination of the
overlapped, C6H3), 4.23 (1H, sept, CH dipp, 3JHH = 6.8 Hz), 4.09
8 | J. Name., 2012, 00, 1-3
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reaction solution: 1W (90%)2, [(dippN)2W(Me)(1,2-η-tBu2P-P- A.W, R.G. and Ł.P. thank the National Science Centre, Poland
PtBu2)] (10%)
(Grant 2016/21/B/ST5/03088) for financial support.
1W: δP (400 MHz, C6D6, H3PO4, 25°C) 45.3 (dd, P3), 31.1 (dd,
P2), –143.7 (dd, 1JP1-P2 = 417 Hz, 1JP1-P3 = 273 Hz, 2JP2-P3 = 13 Hz,
1JP1-W = 101.3 Hz, 1JP2-W = 28.3 Hz, 2JP3-W = 8.6 Hz,P1)
Notes and references
[(dippN)2W(Me)(1,2-η-tBu2P-P-PtBu2)]: δP (400 MHz, C6D6,
1
1
2
3
R. Grubba, K. Baranowska, J. Chojnacki, J. Pikies, Eur. J. Inorg.
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H3PO4, 25°C) 39.4 (dd, P3), 16.1 (dd, P2), –177.7 (dd, JP1-P2
417 Hz, 1JP1-P3 = 277 Hz, 2JP2-P3 = 13.5 Hz, P1)
=
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A solution of Me3P (0.0076g 0.1mmol) in DME was added
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temperature. NMR analysis of the reaction mixture gave the
following data: 3W and
4
5
[(dippN)2W(Me3P)(1,2-η2-tBu2P=P)]3: δP (400 MHz, C6D6,
1
2
H3PO4, 25°C) 53.4 (dd, JP-P = 530 Hz, JP-P = 22 Hz,1JP-W = 246
1990, 9, 2262.
W. R. H. Wright, A. S. Batsamov, J. A. K. Howard, R. P. Tooze,
2
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2
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6
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8
9
1
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1
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PMe3); −29.3 (dd, JP-P = 530 Hz, JP-P = 44 Hz, JP-W = 48 Hz,
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(Et2N)2PCl: δP (400 MHz, C6D6, H3PO4, 25°C) 153 (s)
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The
first
transition
metal
complexes
containing
diphosphanylophosphido ligands with mixed dialkylphosphanyl
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On the other hand, steric influence of R2P groups on
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10 | J. Name., 2012, 00, 1-3
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