1,1-Phosphaboration of CC and CC bonds at gold

Article abstract of DOI:10.1039/d0cc06978g

The phosphine-borane iPr2P(o-C6H4)BFXyl2 (Fxyl = 3,5-(F3C)2C6H3) was found to react with gold(i) alkynyl and vinyl complexes via an original 1,1-phosphaboration process. Zwitterionic complexes resulting from Au to B transmetallation have been authenticated as key intermediates. X-ray diffraction analyses show that the alkynyl-borate moiety remains pendant while the vinyl-borate is side-on coordinated to gold. According to DFT calculations, the phosphaboration then proceeds in a trans stepwise manner via decoordination of the phosphine, followed by anti nucleophilic attack to the π-CC bond activated by gold. The boron center acts as a relay and tether for the organic group. This journal is

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1,1-Phosphaboration of C≡C and C=C bonds at gold
Cyril A. Theulier,a Yago García-Rodeja,b Nathalie Saffon-Merceron,c Karinne Miqueu,b Ghenwa
Bouhadira and Didier Bourissoua*
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
The phosphine-borane iPr2P(o-C6H4)BFXyl2 (Fxyl = 3,5-(F3C)2C6H3) discovered an original 1,1-phophaboration transformation.
was found to react with gold(I) alkynyl and vinyl complexes via an These results are reported hereafter. Mechanistic insights are
original 1,1-phosphaboration process. Zwitterionic complexes discussed based on the reaction intermediates authenticated
resulting from Au to B transmetallation have been authenticated as experimentally and on the reaction profiles computed by DFT.
key intermediates. X-ray diffraction analyses show that the alkynyl-
borate moiety remains pendant while the vinyl-borate is side-on
coordinated to gold. According to DFT calculations, the
phosphaboration then proceeds in a trans stepwise manner via
decoordination of the phosphine, followed by anti nucleophilic
attack to the -CC bond activated by gold. The boron center acts as
a relay and tether for the organic group.
Due to their accessibility and rich reactivity, CC multiple bonds
are among the most widely used building blocks in synthesis.
This stimulates the search for new ways to activate and
transform C≡C and C=C bonds. Spectacular progress has been
Chart 1 Schematic representation of the activation of CC -bonds by gold complexes and
Frustrated Lewis Pairs; reaction of phosphine-boranes with alkynyl/vinyl gold(I)
complexes as studied in this work.
achieved in the area over the past few decades. In particular,
gold complexes have proved to possess unique carbophilic
properties making them extremely powerful catalysts for a
range of C–C and C–X bond-forming transformations based on
For this study, we employed the phosphine-borane iPr2P(o-
-activation (Chart 1a).1 On the other hand, Frustrated Lewis
C6H4)BFXyl2 (Fxyl = 3,5-(F3C)2C6H3)
1 that we recently found to

be an highly-active metal-free catalyst for the dehydrogenation
of amine-boranes,7 as well as a versatile ambiphilic ligand to
Pairs have been shown to readily react with a variety of CC
multiply-bonded molecules.2 Most typical are the trans 1,2-
additions of phosphine-boranes and phosphino-boranes to
alkynes, alkenes… (Chart 1b).3,4 Our interest in ambiphilic
ligands5 and gold chemistry6 prompted us to explore the
reactivity of phosphine-boranes towards gold(I) complexes
featuring alkynyl/vinyl groups (Chart 1c). Doing so, we
stabilize low-valent Rh complexes.8 The reaction of
1
with the
CPh (L = (2,4-tBu2-C6H3-O)3P
or 2,6-Me2C6H3NC) led to the zwitterionic vinyl complexes and
(Scheme 1). The phosphite complex was obtained within 1
day at room temperature, whereas the formation of the related
isonitrile complex required 4.5 h of heating at 90°C. Both
gold(I) alkynyl complexes (L)AuC
≡
2
3
2
3
species were isolated by cristallization and fully characterized
(isolated yields are moderate, 22 and 28%, respectively, due to
high solubility).9 The two complexes display similar NMR data.
The most diagnostic features are the sharp high-field 11B NMR
signal typical for a borate moiety ( ~ –5 ppm), the significant
a.CNRS / Université Paul Sabatier, Laboratoire Hétérochimie Fondamentale et
Appliquée (LHFA, UMR 5069). 118 Route de Narbonne, 31062 Toulouse Cedex 09
(France). Email : dbouriss@chimie.ups-tlse.fr
b. CNRS / Université de Pau et des Pays de l’Adour, E2S UPPA, Institut des Sciences
Analytiques et de Physico-Chimie pour l’Environnement et les Matériaux (IPREM,
UMR 5254), Hélioparc, 2 Avenue du Président Angot, 64053 Pau Cedex 09, France
(France).
JPB coupling (~
22 Hz) and the very deshielded 13C NMR signal
for the carbon atom bonded to gold ( ~ 205-210 ppm).10 X-Ray
diffraction studies were also performed on both complexes.9
Most noticeable are: (i) the transformation of the alkynyl
moiety at gold into a vinyl group, with a tetrasubstituted short
c. Institut de Chimie de Toulouse (FR 2599). 118 Route de Narbonne, 31062 Toulouse
Cedex 09 (France).
†
Electronic Supplementary Information (ESI) available: Experimental procedures
and characterization of complexes (PDF). Crystallographic data for (CIF),
CCDC 2036098,2035740–2035744. See DOI: 10.1039/x0xx00000x
2-
7
2-7
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4 converts inVtieow A3r.ticIlenOtnhlinies
and planar C=C bond (1.340(4) and 1.357(4) Å for
respectively) and (ii) the quaternarisation of the phosphorus transformation, the C
and boron atoms, their geminal addition to the C
leading to a 5-membered ring.
2
and
3
,
Upon heating to 90°C, complex
C triple bond inseDrtOsI:in10t.o10t3h9e/DP0–CACu06b9o7n8Gd
with complete regio and stereo-selectivity. Such a process,
which can also be seen as the 1,2-trans addition of P and Au
across the C C triple bond (see below for further mechanistic
≡
≡C triple bond of 4
Complexes
2
and
3
result from phosphaboration of the C
≡C
≡
triple bond at gold. The reaction is regio and stereo-selective. discussions) is unusual. So far, it has only been observed with
Only the 1,1-addition products with the phosphorus atom alkynyl-functionalized phosphines (intramolecular)15 or a very
sitting in trans position to the Au(L) fragment are observed.11 As activated
alkyne,
mentioned in the introduction, the addition of phosphorus and (intermolecular).10b,c The characterization of
boron to alkynes has some precedent, in particular 1,2-trans 1,1-phosphaboration of the C
additions.3,4 Analogous 1,1-additions are comparatively scarce. complexes
and is a 2-step process assisted by Au/B
dimethylacetylene
carboxylate
shows that the
4
≡C bond at gold leading to
2
3
The only example we are aware of was reported recently by cooperation. Transmetalation of the alkynyl group from Au to B
Doherty and Wescott upon reacting the phosphino-borane is followed by an intramolecular rearrangement. Some analogy
Ph2PBpin with phenylacetylene under Rh catalysis (Chart 1b).4a can be drawn with the metal-induced metallate rearrangement
of boron “ate” complexes, as discovered and developed
recently by Morken et al.16
C39
C38
B
C13
N
P
Au
Scheme 2 Phosphine gold(I) complex 4 with a pendant alkynyl-borate moiety, en route
to the 1,1-phosphaboration complex 3. Molecular structure of 4, as determined by X-Ray
diffraction analysis. Ellipsoids are shown at 50% probability; hydrogen atoms are
omitted; iPr, Fxyl and Xyl are simplified for clarity. Selected bond distances (Å) and angles
(°): B1–C38 1.605(5), C38–C39 1.201(5), P–Au 2.294(1), Au–C13 1.990(4), B–C38–C39
170.8(4), C38–C39–C40 177.0(4), P–Au–C13 167.3(1).
Scheme 1 Formation of the zwitterionic vinyl gold(I) complexes 2 and 3 by addition of
the phosphine-borane 1 to alkynyl gold(I) precursors. Molecular structure of 3 as
determined by X-Ray diffraction analysis. Ellipsoids are shown at 50% probability;
hydrogen atoms are omitted; iPr, Fxyl and Xyl are simplified for clarity. Selected bond
distances (Å) and angles (°): P1–C2 1.814(3), B1–C2 1.648(5), C2–C1 1.357(4), C1–Au
2.043(3), B1–C2–P1 107.6(2), P–C2–C1 122.9(2), C1–C2–B1 129.0(3), C2–C1–Au 122.2(2),
Au–C1–C3 113.6(2), C3-C1-C2 124.1(3).
To assess the generality of this unusual phosphaboration
transformation, the reaction of the phosphine-borane
gold(I) vinyl precursors was then investigated. The zwitterionic
complexes and obtained as shown in Scheme 3 were
1 with
5
6
characterized by multi-nuclear NMR spectroscopy and X-ray
diffraction analyses.9 The vinyl group has been transferred from
gold to boron, which is now tetracoordinate (sharp 11B NMR
signals are observed at  ~ –9 ppm). The bonding situation of
the vinyl group deserves further comments. The corresponding
1H and 13C NMR signals are noticeably down-field shifted. For
example, the =CH2 resonance signal appears at  ~ 88 ppm in
Interestingly, the phosphine-borane
isonitrile gold(I) precursor to give complex
isolated in 42% yield after 1 day at room temperature (Scheme
2). This zwitterionic species results from the coordination of the
1
first reacts with the
which could be
4
phosphine moiety of
alkynyl group from gold to boron (transmetalation). The gold
centre is 2-coordinate and about linear in
, with a P–Au–CCNXyl
bond angle of 167.3(1)°. No sign of noticeable interaction
between the alkynyl group and gold is detected: the B–C
1 to gold, with concomitant transfer of the
4
complexes
> 120 ppm.17,18 Furthermore, short Au–CH2 and Au–CH
distances are observed in the solid state (2.276(4) and 2.275(4)
Å in
), while the C=C bond is elongated at 1.383(6) Å19 and the
P–Au–L skeleton is strongly bent (126.6(2)° in
).20 These data
as a whole indicate that the vinyl group transferred to boron is
-bonded to gold. Since 3-coordinate gold(I) -complexes are
rare, in particular with phosphorus-based ligands,21 the bonding
situation in
was analyzed computationally.9 Geometry
5 and 6, whereas free vinyl borates display signals at

≡C
fragment is only marginally bent (170.8(3)°) and the carbon
atoms remain distant from gold (2.954(3) and 3.319(3) Å). This
bonding situation contrasts with the strong
6
6
-coordination
observed in alkynyl-borate gold(I) complexes prepared recently
by treating alkynyl precursors with B(C6F5)3.12 Note that the
formation of zwitterionic complexes by ionisation of M–X bonds
with ambiphilic ligands is known, but not very common.5 We
reported some examples in gold chemistry, using strong Lewis
acid moieties (P,Al and P,Ga ligands) to abstract chloride from
gold.13 As far as organic groups are concerned, the transfer of
Me groups from Ni and Rh to boron were previously
described.14


6
optimization at the B3PW91/6-31G(d,p),SDD+f(Au) level of
theory resulted in a structure very much resembling that
determined crystallographically. According to NBO analyses,
the vinyl-gold interaction is dominated by C=C
→Au donation
(91.6 kcal/mol), but Au→ back-donation is substantial
*
C=C
2 | J. Name., 2012, 00, 1-3
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(20.7 kcal/mol). Overall, the C=C bond is weakened, as apparent from a stepwise process involving decoordinationVoiefwPArftircolemOnAlinue
DOI: 10.1039/D0CC06978G
from the corresponding Wiberg bond index (1.598). Note that (this is the rate-determining step). The ensuing linear
-
another structure 6⊥ was localized on the potential energy complexes are 16.2-17.2 kcal/mol higher in energy than the
surface.9 It is very close in energy (+0.9 kcal/mol) but very starting zwitterionic complexes. They undergo anti nucleophilic
different in geometry and bonding. Here, the P–Au–L fragment attack of the phosphine, with the boron moiety acting as a
much less deviates from linearity (166.1°) and the vinyl group is tether. This step is almost barrierless (0.4-2.3 kcal/mol) but very
nearly perpendicular with long Au∙∙∙C distances (> 2.76 Å). The exergonic (by 25-37 kcal/mol). Of note, the activation barrier
vinyl group only weakly interacts with gold in this case, as computed for the rearrangement of
confirmed by NBO (weak C=C→Au donation of 8.6 kcal/mol and well with that measured experimentally. For sake of
insignificant Au→ back-donation of 0.1 kcal/mol). The comprehensiveness, we looked for possible alternative
6 into 7 (25.5 kcal/mol) fits


*
C=C
Wiberg bond index for the C=C bond is 1.893.
pathways on the potential energy surface. Migratory insertion
has little precedent in gold chemistry and usually hardly
competes with trans addition. Recently, we have shown it is
sometimes viable and actually quite easy.22 Concerted syn
insertion of the C≡C / C=C bonds into the P–Au bonds of 4* and
6
was indeed found to be conceivable (via a 4-membered
transition state) and potentially competing (the difference in
activation barrier is only 1 kcal/mol).9
F
F
N
C1
C3
C2
B
P
Au
B
P
C3
C2
C1
N
Au
Scheme 3 Phosphine gold(I) complexes 5 and 6 with a pendant vinyl-borate moiety, en
route to the 1,1-phosphaboration complex 7. Molecular structures of complexes 6 (left)
and 7 (right), as determined by X-Ray diffraction analysis. Ellipsoids are shown at 50%
probability; hydrogen atoms are omitted; iPr, Fxyl and Xyl are simplified for clarity.
Selected bond distances (Å) and angles (°). 6: C2–C3 1.383(6), Au–C1 2.014(5), Au–C2
2.275(4), Au–C3 2.276(4), P–Au–C1 126.6(2). 7: P–C3 1.810(3), B1–C3 1.688(5), C3–C2
1.544(4), C2–Au 2.049(3), Au–C1 1.979(4), C2–Au–C1 175.2(1).
With the aim to induce phosphaboration of the C=C bond,
Fig. 1. Two-step mechanism accounting for the trans-phosphaboration of the C=C double
bond at gold from 6 to 7. Insert: transition state for concerted syn insertion of the C=C
bond into the P–Au bond of 6. Corrected Gibbs free energies computed at
complexes
observed for the phosphite complex, but the isonitrile species
was found to slowly and cleanly evolve into a new complex at
5 and 6 were then heated. Only degradation was
SMD(benzene)-B3PW91/6-311G(2df,2pd),
SDD+2fg(Au)//B3PW91/6-
7
31G(d,p),SDD+f(Au) level and Gibbs free (in parentheses) at B3PW91/6-
90°C. The spectroscopic data clearly establish the insertion of
the vinyl group between P and Au. In particular, the B–CH=CH2
vinylic 13C NMR signals are replaced by high-field resonances at
31G(d,p),SDD+f(Au) level. Energy values, G, in kcal/mol.
In conclusion, an original 1,1-phosphaboration process was

28.8 and 15.8 ppm. The structure of 7 was unambiguously
discovered upon reacting the ambiphilic ligand
alkynyl and vinyl complexes. This transformation represents a
rare example of phosphine-borane phosphonium-borate
rearrangement, for which a few precedents involving distinct
mechanisms have been reported.3b,23 Mechanistic studies
revealed that boron acts in concert to gold, abstracting and
tethering the organic group. Zwitterionic complexes are first
formed by Au to B transmetallation. Decoordination of the
1 with gold(I)
confirmed by X-ray diffraction analysis (Scheme 3).9 In addition,
kinetic studies were performed using mesitylene as solvent and
4,4’-difluorobiphenyl as internal standard.9 The rearrangement
→
of
6
into
7
was found to follow first-order kinetics, and a Gibbs
G≠ of 28.2 ± 3.3 kcal/mol was
free energy of activation
estimated from an Eyring plot in the 70-110°C temperature
range.

To gain further insight into these phosphaboration
processes and better understand the interplay between Au and
B, the reaction profiles for the formation of complexes 3* (with
phosphine, followed by anti nucleophilic attack to the -CC
bonds activated at gold then affords the phosphaboration
products. Bifunctional ligands are currently gathering more and
more interest in gold chemistry. In particular, they have been
shown to trigger unprecedented reactivity paths.23 The results
reported here suggest that ambiphilic ligands may open new
avenues in this context and are certainly worthwhile to be
studied further.
C≡CH instead of C≡CPh) and
7 were studied by DFT at
SMD(benzene)-B3PW91/6-311G(2df,2pd),SDD+2fg(Au)//
B3PW91/6-31G(d,p),SDD+f(Au) level of theory.9 As shown in
Figure 1 and Figures S186-188,9 trans-phosphaboration of the
alkynyl and vinyl gold complexes 4* and
6 was found to result
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
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12 M. M. Hansmann, F. Rominger, M. P. Boone, D. W. Stephan,
and A. S. K. Hashmi, Organometallics,D2O01I:410, .31033,9V4i/e4Dw60A1Cr-tCi4c0l4e67O90n7.l8inGe
13 For P^Al, see (a) M. Sircoglou, N. Saffon, K. Miqueu, G.
Bouhadir, and D. Bourissou, Organometallics, 2013, 32, 6780-
6784; (b) M. Sircoglou, G. Bouhadir, N. Saffon, K. Miqueu, and
D. Bourissou, Organometallics, 2008, 27, 1675-1678; (c) M.
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Sircoglou, M. Mercy, N. Saffon, Y. Coppel, G. Bouhadir, L.
Financial support from the Centre National de la Recherche
Scientifique, the Université de Toulouse and the Agence
Nationale de la Recherche (ANR-15-CE07-0003) is gratefully
acknowledged. C.A.T. thanks MESRI (Ministère de
l’Enseignement Supérieur, de la Recherche et de l’Innovation)
for his PhD fellowship (Contrat Doctoral Spécifique Normalien).
The NMR service of ICT (Pierre Lavedan, Marc Vedrenne) is
acknowledged for assistance with the NOESY 1H–1H
experiments. The “Direction du Numérique” of the Université
de Pau et des Pays de l’Adour, CINES under allocation
A007080045 made by Grand Equipement National de Calcul
Intensif (GENCI) and MCIA (Mesocentre de calcul Intensif
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11 This stereochemical arrangement has also been supported in
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2
4 | J. Name., 2012, 00, 1-3
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