Unsaturated vicinal frustrated phosphane/borane Lewis pairs as ligands in gold(i) chemistry

Article abstract of DOI:10.1039/c9cc01136f

The P/B FLP 6, formed by the 1,1-hydroboration of dimesitylphosphino(trimethylsilyl)acetylene with HB(C₆F₅)₂ forms the Au(i)X complexes 9a (X: Cl) and 10a (X: NTf₂), respectively. Both show marked Au?B interactions. The P/B FLP isomer 8, featuring the bulky SiMe₃ substituent at the carbon adjacent to boron forms gold complexes 9b and 10b, both of which show weaker Au?B interactions. Complex 10a was employed in the catalytic hydroamination of a series of alkynes with p-toluidine. Complexes 9 and 10 were characterized by X-ray diffraction.

Full text of DOI:10.1039/c9cc01136f

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DOI: 10.1039/C9CC01136F
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Unsaturated Vicinal Frustrated Phosphane/Borane Lewis Pairs as
Ligands in Gold(I) Chemistry
Atsushi Ueno, Kohei Watanabe, Constantin G. Daniliuc, Gerald Kehr and Gerhard Erker*a
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
The P/B FLP 6, formed by 1,1-hydroboration of
dimesitylphosphino(trimethylsilyl)acetylene with HB(C6F5)2
forms the Au(I)X complexes 9a (X: Cl) and 10a (X: NTf2),
respectively. Both show marked Au···B interaction. The P/B FLP
isomer 8, featuring the bulky SiMe3 substituent at carbon
adjacent to boron formes the gold complexes 9b and 10b, which
both show weaker Au···B contacts. Complex 10a was employed
in catalytic hydroamination of a series of alkynes with p-
toluidine. The complexes 9 and 10 were characterized by X-ray
diffraction.
We have recently described the formation of the pair of
geminal P/B FLPs 6 and 8.6 Compound 6 was readily prepared
by means of an unusual 1,1-hydroboration of dimesityl-
phosphino(trimethylsilyl)acetylene
4 with Piers’ borane
[HB(C6F5)2]7 at ambient conditions. There is indirect evidence
that this reaction might proceed through the respective
phosphirenium borate zwitterion8 intermediate 5 under the
conditions of kinetic control. At 100 °C compound 6
rearranges to the thermodynamically favoured isomer 8,
probably via reversible formation of the 4/HB(C6F5)2 pair,
which then undergoes the “normal” hydroboration reaction
to give 7. This might then in turn undergo rotation to the P/B
FLP 8 under the prevailing forced conditions, potentially
making use of the incipient participation of the mesomeric
phospha-iminium/borata-alkene resonance structure of the
system 7/7’ (see Scheme 2). Both the isomers 6 and 8 show
weak internal P···B interactions.
Frustrated Lewis pairs (FLPs) have seen a variety of
applications, the most important of them probably being
small molecule activation and their use in metal-free
catalysis.1 FLPs have also been used as ambiphilic ligands in
transition metal chemistry. 2,3,4 Bourissou’s complexes 1 to 3
are typical examples as is their further development to
boratrane chemistry.5
Mes
Mes
Mes2P
SiMe3
P
Me3Si
H
4
Me3Si
[B]
H
Mes2P
[B]
HB(C6F5)2
100 °C
r.t.
iPr2P
BCy2
iPr2P
BCy2
iPr2P
B
6
5
Pd Cl
Au
Au
Cl
Cl
[B] = -B(C6F5)2
H
1
2
3
Mes2P
H
SiMe3
[B]
Mes2P
SiMe3
[B]
SiMe3
[B]
Scheme 1 Previous work on transition metal complexes with amphiphilic
ligands
H
Mes2P
100 °C
7
7'
8
In compound 1, the chloride ligand is used for bridging
between Pd and B, but in both the complexes 2 there is a
Au···B contact (2: 2.90 Å, 3: 2.66 Å) that is markedly below the
sum of the Au/B van der Waals radii of ca. 3.9 Å.
Scheme 2 Plausible reaction pathway of the formation of compounds 6 and 8
We have now used the pair of unsaturated P/B FLP isomers as
ligands in gold(I) chemistry. The preparation of the respective
complexes, their characterization and the use of some of
them in catalytic alkyne hydroamination chemistry will be
reported in this account.
We reacted each of the P/B FLPs 6 and 8 with ca. one molar
equivalent of Me2SAuCl. The compounds were allowed to
react during 18 h at r.t. in dichloromethane. Workup then
a. Organisch-Chemisches Institut der Universität Münster
Corrensstraße 40, 48149 Münster (Germany)
E-mail:erker@uni-muenster.de
Electronic Supplementary Information (ESI) available: experimental and analytical
details; CCDC deposition numbers are 1886734 to 1886737. See
DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
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gave the adducts 9a and 9b (see Scheme 3) as yellow solids
both in >75% yield. The FLP/gold complexes were
characterized by C,H elemental analysis, by spectroscopy and
by X-ray diffraction (see below and Table 1). We then reacted
each of these compounds with one molar equivalent of
AgNTf2. After removal of a precipitate of AgCl, the solvent was
removed in vacuo and the residue was suspended in pentane.
The respective anion exchange products 10a and 10b (see
Scheme 3) were collected by filtration and obtained in >80%
yield.
Table 1). Complex 9a shows a five-membered core formed by
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binding of the Au-Cl unit to the phosphoDruOsI: a10to.1m039o/Cf 9thCeC0P1/1B36F
FLP 6. The gold atom in complex 9a shows a marked
interaction with the boron atom B1 (see Fig. 1).
Compound 10a has the Au-NTf2 moiety bonded to the FLP
phosphane ligand in a close to linear arrangement as well. The
P1-Au bond length is the same as in 9a, but the Au1-B1
distance is markedly longer (d≈0.37 Å) (the structure of 10a
is depicted in the Supporting Information).
Me2SAuCl
8
H
6
Me3Si
H
SiMe3
[B]
Mes2P
[B]
Mes2P
9a
9b
Au
Au
Cl
Cl
AgN(SO2CF3)2
Me3Si
H
H
SiMe3
[B]
Mes2P
[B]
Mes2P
10a
10b
Fig. 1 Molecular structure of the P/B FLP gold complex 9a
Au
Au
NTf2
NTf2
Compound 9b has the Au-Cl unit close to linearly attached at
the phosphane Lewis base of the FLP. Most of the
characteristic structural data of compound 9b are similar to
those of 10a, although the Au1···B1 distance is slightly longer
(d≈0.26 Å, see Table 1). Both the complexes 9b and 10a
show envelope type conformations of their FLP/Au
frameworks with angles between the PC2B and PAuB planes
around ca. 30°. (the structure of complex 9b is depicted in
the Supporting Information).
[B] = -B(C6F5)2
Scheme 3 Preparation of gold(I) complexes with P/B ligands
Table 1 Selected structural and spectroscopic data of the complexes 9 and 10
Cmpd.
[Au]-X
9a
9b
10a
10b
Cl
Cl
NTf2
NTf2
X-ray dataa
C1-C2
1.356(18)
1.801(14)
1.550(20)
2.273(3)
2.290(4)
2.347(17)
173.7(2)
345.6(11)
22.5(10)
1.341(7)
1.827(5)
1.548(7)
2.245(1)
2.288(1)
2.973
1.339(9)
1.824(7)
1.582(10)
2.272(2)
2.160(6)
2.712(8)
169.7(2)
354.6(6)
-31.2(5)
1.328(4)
1.828(3)
1.553(4)
2.235(1)
2.114(2)
3.607
P1-C1
B1-C2
P1-Au1
Au1-X
Au1-B1
P1-Au1-X
B1CCC
176.8(1)
358.3(4)
-32.3(4)
172.2(1)
359.4(3)
-51.5(3)
C2-C1-P1-Au1
NMR datab
31P
31P(10/11B)c
11B
43.9
-15.8
34.2
11.2
19.8
-47.5
54.8
15.3
32.9
-76.7
51.0
14.0
5.2
-
59.6
16.0
19Fm,p
d
a
b
bond length in Å, angles in deg.
chemical shifts,

scale, in d2-
c
dichloromethane, 299 K, for 10a at 273 K. isotope-induced chemical shift in
ppb was calculated by using 31P(10/11B) = 31P(11B) - 31P(10B) [ref.9]. d in ppm.
The quartet of the gold complexes 9 and 10 was characterized
by C,H respectively C,H,N elemental analysis, by spectroscopy
and by X-ray diffraction. We noted a gradual change of
essential structural and spectroscopic features on going from
9a through 10a and 9b all the way to compound 10b (see
Fig. 2 A view of the molecular structure of complex 10b
Complex 10b shows only a marginal interaction of the
phosphane moiety with the boron atom B1 of the Lewis acid
function (see Fig.2). Consequently, the overall structure of the
2 | J. Name., 2012, 00, 1-3
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core of 10b differs markedly from that of its relatives 9a,b and
10a: we find the P1-Au1 vector at the adjacent P1-C2 vector
rotated almost into a conformational gauche position to the
C1=C2 backbone. The coordination geometry at boron in
complex 10b is trigonal planar, similar as in the complexes 9b
and 10a; only complex 9a shows a markedly pyramidalized
we isolated the resulting imines 12b-f in yields around ca. 90%
as colorless oils. Hydroamination of the conjugated enyne 11g
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DOI: 10.1039/C9CC01136F
proceeded equally well under the optimized conditions and
we isolated the respective conjugated imine product in close
to 90% as well. Cyclohexylethyne (11h) and t-butylacetylene
(11i) gave slightly lower yields of ~50% under our conditions.
The internal alkyne o-aminotolane underwent intramolecular
hydroamination15 with the 10a derived catalyst system to give
the indole product 12j which we isolated in 93% yield
(Scheme 4, see the ESI for the characterization of the
hydroamination products).
geometry at boron (see Table 1).
2
Complex 10b shows a 31P NMR signal at ca.  5 with a JPH
=
26 Hz coupling constant. This is a chemical shift difference of
3
ca -27 ppm relative to its isomer 10a (see Table 1, JPH = 93
Hz). The Au-Cl complex 9a shows a characteristically high 3JPH
coupling constant of 98 Hz. Complex 10b shows a 11B NMR
resonance in the typical area of a planar-tricoordinate boron
atom in this substituent situation and a typically large 19Fm,p
chemical shift difference. This is in accord with the presence
of an almost free non-interacting borane moiety in 10b in
solution similar as it was found in the solid state by X-ray
diffraction. The 11B NMR resonances of the complexes 9b and
10a are shifted to slightly smaller values (by ca. 10 to 20%)
and their respective 19Fm,p chemical shift differences are
smaller than in 10b, both effects probably indicating some
Au···B interaction in these complexes in solution. The 11B NMR
signal of the Au-Cl complex 9a is shifted to smaller -values
by ca. 25 ppm relative to 10b (19Fm,p reduced by ca 5 ppm)
which points to some marked metal-boron interaction in this
complex in solution in accord with the X-ray diffraction result.
We also note that the complexes 9a,b and 10a show a marked
31P NMR chemical shift difference between the 10/11B
isotopologues. The FLP starting materials 6 and 8 do not show
this feature. Therefore, this might possibly serve as an
additional indication of some P-metal-B interaction in these
gold complexes9 (see Table 1).
p-Tol
N
X
X
12a-f
11a-f
a
b
c
d
e
f
+
X: H Br Et Ph NMe2 OMe
cat. [10a]
(2 mol%)
CH2Cl2
(%): 95 92 92 93 94
87
NH2
40°C, 4h
p-Tol
p-Tol
N
NaBH4
HN
+
R
R
R
12g,(h,i)
13h,i
11g-i
g
h
i
R:
1-cyclo- cyclo-
hexenyl hexyl
tert-
butyl
12 (%):
13 (%):
87
-
-
55
-
59
NH2
H
N
Ph
Ph
11j
12j (93%)
Intra- and intermolecular hydroamination reactions have
attracted quite some attention. Most these reactions are
metal-catalysed, with early examples concentrating on f-
element and the group 4 metal derived catalysts.10,11 More
recent examples have used a great variety of metal catalysts
throughout the periodic table.12 Even B(C6F5)3 induced
hydroamination reactions were reported.13 Since cationic Au+
catalysts have come into focus for this reaction in the recent
years14 we have employed some of the here described
FLPAuX examples for the hydroamination of a small series of
alkynes with the primary amine p-toluidine (see Scheme 3).
We carried out the reaction of phenylacetylene 11a with p-
toluidine at 40 °C in dichloromethane catalyzed by the
FLPAuNTf2 complex 10a (2 mol%) which we generated in situ
by treatment of the FLPAuCl complex 9a with AgNTf2. Workup
after 4 h reaction time furnished the ketimine product 12a in
ca. 90% yield. A control experiment that was carried with
removal of AgCl prior to the actual catalytic reaction gave a
similar result. We compared the relative rates of this
hydroamination reactions between the in situ generated FLP
FLPAuNTf2 species 10a and 10b and found the reaction
involving the 10a system markedly faster (see the ESI for
details). Therefore, we employed the 10a derived catalyst for
the additional experiments. Catalytic hydroamination of the
aryl alkynes 11b-f with p-toluidine went smoothly at 40 °C and
Scheme 4 Catalytic alkyne hydroamination reaction
The rigid FLPs 6 and 8 turned out to be very suitable ligands
for the preparation of gold(I) complexes. The X-ray crystal
structure analyses and NMR spectroscopy indicated a P,B
chelate structure of the Au(I)-Cl complex 9a. The Au···B
interaction in the here described complexes shows a marked
steric response: placement of the bulky -SiMe3 group at the
-position to boron markedly diminished the strength of the
gold-boron contact. In this sense, the FLPAuNTf2 complex 10a
seems to represent the best compromise between electronic
metal-main group element interaction and repulsive features.
This complex showing the SiMe3 group at the -carbon atom
of the bridge adjacent to phosphorus and in a remote position
to boron is characterized by only a slightly enlarged Au···B
distance relative to 9a, but already shows some indication of
residual Lewis acid properties at boron. Consequently, the
system 10a provided the basics for the most active alkyne
hydroamination catalyst in the series. It is likely that the
active FLPAu(I)+ cation is generated by Tf2N-anion dissociation
under the actual reaction conditions. We assume that the
marked interaction of the metal centre with the strong boron
Lewis acid may serve to enhance the electrophilic properties
of the incipient gold(I) cation, so that it shows enhanced
alkyne hydroamination reactivities. It seems to be promising
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7
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e.g. gold(I) catalysis and to consider using FLP ligands in
catalysis more frequently.
A.U. thanks the JSPS for a postdoctoral stipend.
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Conflicts of interest
There are no conflicts to declare
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4 | J. Name., 2012, 00, 1-3
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ChemComm
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Journal Name
COMMUNICATION
View Article Online
DOI: 10.1039/C9CC01136F
TOC: The unsaturated vicinal P/B FLP obtained from the unusual 1,1-
hydroboration of dimesitylphosphino(trimethylsilyl)acetylene with Piers’
borane serves as an ambiphilic ligand in gold(I) chemistry.
Me3Si
H
Me3Si
H
Me3Si
H
Me2SAuCl
AgNTf2
Mes2P
[B]
Mes2P
[B]
Mes2P
[B]
Au
Au
Cl
NTf2
[B]: B(C6F5)2
Catalytic alkyne
hydroamination
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