The insertion of terminal phosphinidene complexes into the B-H bond of amine and phosphine boranes

Article abstract of DOI:10.1002/chem.201202277

Push-pull complexation: Transient terminal phosphinidene complexes [RP-W(CO)₅] insert at 110 °C into the B-H bonds of L-BH ₃ (L = Et₃N, Ph₃P; see scheme). The reaction is probably driven by an interaction betwee

Full text of DOI:10.1002/chem.201202277

COMMUNICATION
DOI: 10.1002/chem.201202277
À
The Insertion of Terminal Phosphinidene Complexes into the B H Bond of
Amine and Phosphine Boranes
Rongqiang Tian and FranÅois Mathey*[a]
The chemistry of electrophilic terminal phosphinidene
The structure of 5 was established on the basis of a combi-
nation of NMR and HRMS data. The 31P NMR spectrum of
5 displayed a resonance at d=À84.1 ppm (CDCl3) with a
1JHP coupling of 303.7 Hz. The structure was confirmed by
[1]
À
complexes [RP M(CO)5] is dominated by their isolobal
analogy with singlet carbenes. This analogy is strikingly ob-
vious in their cycloaddition reactions with unsaturated hy-
À
drocarbons. On the contrary, their insertion reactions into
X-ray diffraction analysis (Figure 1). At 1.979(5) ꢀ, the P B
[2]
À
C H bonds, which are quite developed with carbenes, are
limited to a few examples, essentially with ferrocene,[3] azo-
benzene,[4] Wittig cyanomethylide,[5] and azulene.[6] An addi-
tional example of intramolecular reaction has also been de-
scribed with a related phosphinidene–[Fe(CO)4] complex.[7]
More encouraging results have been obtained recently on
the insertion of terminal phosphinidene complexes into the
[8]
À
Si H bond of silanes. However, it is known that the bond-
À
dissociation energy (BDE) of Si H is substantially lower
À
À
À
than that of the C H bond. The B H BDE in H3B L (L=
Lewis base) depends on the nature of L.[9] For L =NMe3,
À
the B H BDE was computed recently to be 102.5 kcal
À1
[9]
À
mol , which is very close to the BDE of the C H bond.
We reasoned that the reaction of electrophilic terminal
phosphinidene complexes toward amine boranes could be,
nevertheless, driven by an initial interaction between the
negatively charged boron atom and the electrophilic phos-
phinidene. Thus, we decided to study the reactivity of these
terminal phosphinidene complexes with amine boranes and,
by extension, with phosphine boranes.
Figure 1. X-ray crystal structure of the insertion product 5. Selected bond
À
À
À
lengths [ꢀ] and angles [8]: P1 B1 1.979(5), P1 W1 2.5365(11), P1 C6
À
1.825(4), B1 N1 1.610(5); W1-P1-B1 113.41(14), W1-P1-C6 113.06(14),
The versatile 7-phosphanorbornadiene complexes,[10] such
P1-B1-N1 116.0(3).
À
as 1, were used as precursors for [RP W(CO)5]. A slow re-
action between 1 and triethylamine borane was observed at
1108C, giving the desired insertion product 5 in good yield
[Eq. (1)].
À
bond is somewhat elongated for a single bond (P B 1.917 ꢀ
[11]
À
in H3B PPh3). The NEt3 and [W(CO)5] groups are in a
quasi-trans disposition due to steric reasons (dihedral angle
À
N-B-P-W 133.88). The rotation around the P B bond is
À
blocked, and this explains why the P H resonance appears
1
as a doublet of doublet in the H NMR spectrum. The two
H-P-B-H dihedral angles are 75.6 and 164.58. The Karplus
curve suggests that the PH proton is only coupled with the
BH proton in the trans disposition. The reaction appears to
be quite general and works in high yields with most of the
phosphinidene substituents, as shown below.
Under similar conditions, triphenylphosphine-borane is
also able to give the corresponding insertion product 11
[Eq. (2)].
Once again, the reaction appears to be quite general and
works in high yields with most of the phosphinidene sub-
stituents, except CH2CH2CO2Et, ester group of which is
probably partially destroyed by the borane reagent under
[a] Dr. R. Tian, Prof. Dr. F. Mathey
Nanyang Technological University
Division of Chemistry & Biological Chemistry
21 Nanyang Link, Singapore 637371
E-mail: fmathey@ntu.edu.sg
Chem. Eur. J. 2012, 00, 0 – 0
ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
&
1
&
ÞÞ
These are not the final page numbers!

of the PH group. The metalation was carried out by nBuLi
in THF at À708C. The deprotonated product was reacted
with benzaldehyde, but gave no isolable product. On the
contrary, it was possible to trap similar deprotonated species
by intramolecular alkylation in the case of 7 and 13
[Eq. (3)].
the rather harsh conditions used. The 31P NMR spectrum of
11 displayed two resonances at d=À91.1 ppm (PHPh) with
1
a JHP coupling of 315 Hz and 15.8 ppm (PPh3). There is no
measurable coupling between the two phosphorus nuclei.
The PH resonance appeared as a doublet of triplet with
3JHÀH (BH)ꢀ JHÀP (PPh3)ꢀ11.2 Hz. All of these insertion
3
products appear to be thermally quite stable.
The formation of the phosphirane rings was immediately
obvious from the inspection of the 31P NMR spectra of 16
and 17, which displayed high-field resonances at d=À265.8
and À261.3 ppm that are characteristic for three-membered
phosphiranes.[13] There is no measurable coupling between
the two phosphorus nuclei in 17. The two CH2 groups are in-
To have some idea on their electronic structures, some
DFT calculations at the B3PW91/Lanl2dz (W) level[12] on
À
À
À
model compounds [(OC)5W PH(Me) BH2 L] (L=NH3
(A), PH3 (B)) were performed. The calculated geometrical
parameters of A are in satisfactory agreements with those of
5. The most striking result is that the W-P-B unit is remarka-
À
equivalent due to a blocked rotation around the P B bond.
À
À
bly insensitive to the nature of L. For A: P W 2.546 ꢀ, P B
In toluene, at 1008C overnight in the presence of acryloni-
trile, which scavenges the boron unit, 12 was split into its
two phosphorus components [Eq. (4)].
À
À
1.956 ꢀ, B-P-W 117.78; for B: P W 2.544 ꢀ, P B 1.956 ꢀ,
B-P-W 117.18. The shapes of the HOMO and LUMO of A
and B are also remarkably similar. The HOMO and LUMO
of A are shown in Figure 2. The key point is that they are
A similar splitting was observed with [Mo(CO)6] in boil-
ing toluene [Eq. (5)].
À
It is known that phosphinoboranes R2B PR2 are unstable
as monomers and give cyclic or linear oligomers, except
when they are substituted by very bulky groups that force
phosphorus to become planar, thus allowing the formation
[14]
À
of a P B p bond. Our insertion products can be viewed
À
À
À
Figure 2. Frontier orbitals (Kohn–Sham) of [H3N BH2 PH(Me)
W(CO)5] (A).
as monomers stabilized by push–pull complexation with a
Lewis donor (NEt3 or PPh3) and
a Lewis acceptor
([W(CO)5]) without need for bulky substituents. A similar
approach has been illustrated in several papers by Scheer
and co-workers.[15] In our case, a large number of substitu-
tion schemes is possible, and the simplicity of the approach
will allow an extensive study of this class of compounds.
localized on the B-P-W unit. Obviously, L plays the role of
an ancillary ligand serving to stabilize the B-P-W unit. Be-
cause the HOMO and LUMO of A are higher in energy
than those of B by 0.11 and 0.24 eV, respectively, it seems
that A will be more reactive than B. In both cases, the reac-
tions will tend to initially take place at phosphorus or at the
À
B P bond. Our preliminary reactivity experiments were car-
ried out with 11. We first tried to exploit the deprotonation
&
2
&
www.chemeurj.org
ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 0000, 00, 0 – 0
ÝÝ
These are not the final page numbers!

The Insertion of Phosphinidene Complexes
COMMUNICATION
11B NMR: d=À29.14 ppm; HRMS: m/z calcd for C24H24BP2 [M
À
Experimental Section
W(CO)5 +H]+ 385.1446; found: 385.1450.
Synthesis of 12: Compound 1 was replaced by 2. Heating for 30 h at
1108C; yield 83%. 1H NMR: d=1.02 (dd, J=8.0 Hz, J=6.8 Hz, 3H,
General methods: All reactions were performed under nitrogen using
solvents dried by standard methods. NMR spectra were obtained using
Bruker AV400 spectrometer operating at 400 MHz for 1H, 100.56 MHz
for 13C, 161.89 MHz for 31P and 128.4 MHz for 11B. All spectra were re-
corded at 298 K in CDCl3. All coupling constants (J values) are reported
in Hertz (Hz). HRMS spectra were obtained on a Water Q–Tof Premier
MS. X-ray crystallographic analyses were performed on a Bruker X8
APEX diffractometer. Silica gel (230–400 mesh) was used for the chro-
matographic separations. Commercially available reagents were used
without further purification.
CH3), 2.35 (br, 2H, BH2), 3.53 (dm, JHP =300.0 Hz, 1H, PH), 7.48–7.52
1
(m, 6H, Ph), 7.56–7.65 ppm (m, 9H, Ph); 13C NMR: d=10.54 (dd, JCP
26.2 Hz, Me), 126.57 (dd, 1JCP =61.8 Hz, Ph C ipso), 129.35 (d, JCP
10.7 Hz, Ph CH), 132.26 (d, 4JCP =2.6 Hz, Ph CH para), 133.31 (d, JCP
9.6 Hz, Ph CH), 198.51 (d, JCP =6.7 Hz, CO cis), 201.88 ppm (d, JCP
=
=
=
=
15.8 Hz, CO trans); 31P NMR: d=15.9, À133.8 ppm (1JHP =285.6 Hz);
11B NMR: d=À29.88 ppm; HRMS: m/z calcd for C19H22BP2
[MÀW(CO)5 +H]+ 323.1290; found: 323.1300.
Synthesis of 13: Compound 1 was replaced by 3.[16] Heating for 16 h at
1108C and 8 h at 1208C; yield 79%. 1H NMR: d=1.66–1.80 (m, 2H,
Synthesis of 5: A solution of 7-phenyl-7-phosphanorbornadiene complex
(1)[10] (1.31 g, 2 mmol) and triethylamine borane (0.46 g, 4 mmol) in tol-
uene was stirred at 1108C for 22 h. After evaporation, the residue was
chromatographed on silica gel by using a hexane/dichloromethane 3:1, to
give 5 as a white solid (0.91 g, 83%). 1H NMR: d=1.07 (t, 9H, CH3),
2.45 (brs, 2H, BH2), 2.69 (m, 6H, CH2), 4.59 (dd, JHP =299.2 Hz, J=
12 Hz, 1H, PH), 7.23 (m, 1H, Ph), 7.28–7.32 (m, 2H, Ph), 7.32–7.52 ppm
(m, 2H, Ph); 13C NMR: d = 8.04 (s, CH3), 51.03 (d, J=4.9 Hz, CH2),
128.09 (d, 4JCP =2.1 Hz, Ph CH para), 128.53 (d, JCP =8.5 Hz, Ph CH),
130.00 (d, JCP =8.6 Hz, Ph CH), 137.28 (d, 1JCP =31.5 Hz, Ph C ipso),
198.23 (d, JCP =6.4 Hz, CO cis), 202.17 ppm (d, JCP =15.9 Hz, CO trans);
31P NMR: d=À84.1 ppm (1JHP =303.7 Hz); 11B NMR: d=À10.02 ppm;
HRMS: m/z calcd for C12H24BNP [MÀW(CO)5 +H]+ 224.1739; found:
224.1740.
CH2P), 2.34 (br, 2H, BH2), 3.23–3.47 (m, 2H, CH2Cl), 3.59 (dm, JHP
=
299.2 Hz, 1H, PH), 7.49–7.54 (m, 6H, Ph), 7.58–7.67 ppm (m, 9H, Ph);
1
13C NMR: d=29.41 (d, JCP =20.1 Hz, CH2P), 43.26 (s, CH2Cl), 126.17 (d,
1JCP =61.9 Hz, Ph C ipso), 129.55 (d, JCP =10.7 Hz, Ph CH), 132.54 (d,
4JCP =2.3 Hz, Ph CH para), 133.30 (d, JCP =9.6 Hz, Ph CH), 197.99 (d,
J
CP =6.3 Hz, CO cis), 200.78 ppm (d, JCP =16.8 Hz, CO trans); 31P NMR:
d=15.8, À121.7 ppm (1JHP =302.7 Hz); 11B NMR: d=À30.71 ppm;
HRMS: m/z calcd for C20H23BP2Cl [MÀW(CO)5 +H]+ 371.1057; found
371.1056.
Synthesis of 14: Compound 1 was replaced by 9.[17] Heating for 30 h at
1108C. Eluent used: hexane/dichloromethane 1:1; yield 71%. 1H NMR:
d=1.43–1.49 (m, 2H, CH2CN), 2.4 (br, 2H, BH2), 2.17–2.37 (m, 2H,
CH2P), 3.67 (dm, JHP =297.6 Hz, 1H, PH), 7.52–7.56 (m, 6H, Ph), 7.61–
CCDC-881724 (5) contains the supplementary crystallographic data for
this paper. These data can be obtained free of charge from The Cam-
bridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_re-
quest/cif.
1
7.68 ppm (m, 9H, Ph); 13C NMR: d=16.20 (s, CH2CN), 21.58 (d, JCP
=
21.6 Hz, CH2P), 118.67 (d, JCP =12.2 Hz, CN), 126.01 (d, 1JCP =63.8 Hz,
Ph C ipso), 129.61 (d, JCP =10.6 Hz, Ph CH), 132.60 (d, 4JCP =2.4 Hz, Ph
CH para), 133.23 (d, JCP =9.5 Hz, Ph CH), 197.72 (d, JCP =6.2 Hz, CO
J
CP =17.4 Hz, CO trans); 31P NMR: d=15.7,
Synthesis of 6: Compound 1 was replaced by 2. Heating for 32 h at
1108C; yield 53%. 1H NMR: d=1.23 (t, 9H, CH3), 1.52 (dd, 3H, PMe),
cis), 200.29 ppm (d,
À112.3 ppm (1JHP =298.2 Hz); 11B NMR: d=À30.90 ppm; HRMS: m/z
calcd for C21H23BNP2 [MÀW(CO)5 +H]+ 362.1399; found: 362.1404.
2.03–2.41 (br, 2H, BH2), 2.95 (m, 6H, CH2), 3.59 ppm (dm, JHP
=
288.4 Hz, 1H, PH); 13C NMR: d=8.30 (s, CH3), 9.85 (d, 1JCP =24.9 Hz,
Synthesis of 15: Compound 1 was replaced by 10.[18] Heating for 28 h at
1158C. Eluent used: hexane/dichloromethane 2:1; yield 30%. 1H NMR:
d=1.19 (t, 3H, JHH =7.2 Hz, CH3), 1.48–1.67 (m, 2H, CH2C=O), 2.45 (br,
2H, BH2), 2.13–2.38 (m, 2H, CH2P), 3.54 (dm, JHP =298.4 Hz, 1H, PH),
4.03 (q, 2H, JHH =6.8 Hz, CH2O), 7.49–7.53 (m, 6H, Ph), 7.57–7.66 ppm
(m, 9H, Ph); 13C NMR: d=14.19 (s, CH3), 20.48 (d, 1JCP =22.6 Hz,
PMe), 51.58 (d, J=5.5 Hz, CH2), 198.60 (d,
JCP =6.5 Hz, CO cis),
201.56 ppm (d,
J
CP =15.2 Hz, CO trans); 31P NMR: d=À132.5 ppm
(1JHP =307.5 Hz); 11B NMR: d=À9.65 ppm; HRMS: m/z calcd for
C7H22BNP: [MÀW(CO)5 +H]+ 162.1583; found: 162.1583.
Synthesis of 7: Compound 1 was replaced by 3;[16] yield 54%. 1H NMR:
d=1.24 (t, 9H, CH3), 2.19 (m, 1H, CH2P), 2.40 (m, 1H, CH2P), 2.95 (m,
1
CH2P), 32.84 (s, CH2C=O), 60.44 (s, CH2O), 126.39 (d, JCP =61.4 Hz, Ph
C ipso), 129.39 (d, JCP =10.7 Hz, Ph CH), 132.31 (d, JCP =2.5 Hz, Ph CH
4
6H, NCH2), 3.67–3.86 (2 m, 2H, CH2Cl), 3.68 ppm (dm, JHP =287.2 Hz,
1
1H, PH; BH2 nonvisible); 13C NMR: d=8.32 (s, Me), 29.26 (d, JCP
=
para), 133.29 (d, JCP =9.6 Hz, Ph CH), 172.44 (d, JCP =14.0 Hz, CO),
198.15 (d, JCP =6.4 Hz, CO cis), 201.01 ppm (d, JCP =16.2 Hz, CO trans);
31P NMR: d=16.1, À113.4 ppm (1JHP =297.9 Hz); 11B NMR: d=
À30.76 ppm; HRMS: m/z calcd for C23H28O2BP2 [MÀW(CO)5 +H]+
409.1658; found: 409.1668.
18.8 Hz, CH2P), 44.08 (s, CH2Cl), 51.79 (d, JCP =5.5 Hz, CH2N), 198.08
(d,
JCP =6.7 Hz, CO cis), 200.39 ppm (d, JCP =16.0 Hz, CO trans);
31P NMR: d=À120.7 ppm (1JHP =282.2 Hz); 11B NMR: d=À10.53 ppm;
HRMS: m/z calcd for C8H23BNPCl [MÀW(CO)5 +H]+ 210.1350; found:
210.1354.
Synthesis of 17: nBuLi (0.3 mL, 0.48 mmol) was added to a solution of 13
(240 mg, 0.37 mmol) in THF at À708C. After stirring at À708C for
15 min, several drops of aqueous HCl were added to the solution to
quench the reaction. The reaction mixture was filtered over silica gel and
washed with CH2Cl2. After evaporation, the residue was chromatograph-
ed on silica gel by using a hexane/dichloromethane 3:1, to give 17 as a
white solid (176 mg, 77%). 1H NMR: d=0.85 (m, 2H, H phosphirane),
1.00 (m, 2H, H phosphirane), 2.03 (br, 2H, BH2), 7.48–7.52 (m, 6H, Ph),
7.57–7.63 ppm (m, 9H, Ph); 13C NMR: d=10.98 (d, 1JCP =15.3 Hz,
CH2P), 11.05 (d, 1JCP =15.2 Hz, CH2P), 126.17 (d, 1JCP =62.3 Hz, Ph C
ipso), 129.30 (d, JCP =10.7 Hz, Ph CH), 132.25 (d, 4JCP =2.5 Hz, Ph CH
para), 133.46 (d, JCP =9.6 Hz, Ph CH), 197.79 (d, JCP =7.1 Hz, CO cis),
199.48 ppm (d, JCP =21.8 Hz, CO trans); 31P NMR: d=15.2, À261.3 ppm;
Synthesis of 8: Compound 1 was replaced by 4;[17] yield 72%. 1H NMR:
d=1.23 (t, 9H, CH3), 2.77 (m, 6H, NCH2), 3.80 (s, Me-N), 4.81 (dd,
J
HP =304 Hz, 1H, PH), 6.07 (brs, 1H, pyr), 6.27 (brs, 1H, pyr), 6.71 ppm
(brs, 1H, pyr; BH2 nonvisible); 13C NMR: d=8.12 (s, Me), 35.77 (d,
CP =2.4 Hz, MeN), 50.95 (d, JCP =5.0 Hz, CH2N), 108.28 (d, JCP =6.9 Hz,
J
CH pyr), 115.51 (d, JCP =6.3 Hz, CH pyr)), 123.38 (d, 1JCP =38.8 Hz, CP
pyr), 126.35 (d, JCP =2.1 Hz, CH pyr), 198.21 (d, JCP =6.1 Hz, CO cis),
201.56 ppm (d, JCP =115.76.0 Hz, CO trans); 31P NMR: d=À115.3 (1JHP
nonvisible); 11B NMR: d=À10.73 ppm; HRMS: m/z calcd for
C11H25BN2P [MÀW(CO)5 +H]+ 227.1848; found: 227.1846.
Synthesis of 11: Triethylamine borane was replaced by triphenylphos-
phine borane; yield 86%. 1H NMR: d=2.64 (br, 2H, BH2), 4.51 (dt,
11B NMR:
d
À27.02 ppm; HRMS: m/z calcd for C20H22BP2
J
HP =310.0 Hz, JHH =11.2 Hz, 1H, PH), 7.03 (s, 3H, Ph), 7.11–7.16 (m,
[MÀW(CO)5 +H]+ 335.1290; found: 335.1291.
2H, Ph), 7.29–7.33 (m, 6H, Ph), 7.37–7.46 ppm (m, 9H, Ph); 13C NMR:
d=126.05 (d, 1JCP =62.4 Hz, Ph3P C ipso), 127.83 (d, 4JCP =1.2 Hz, PhP
CH para), 128.21 (d, JCP =9.0 Hz, PhP CH), 129.22 (d, JCP =10.7 Hz,
Synthesis of 16: Same procedure as for 17 with triphenylphosphine
borane replaced by triethylamine borane; yield 77%. 1H NMR: d=1.18
Ph3P CH), 131.10 (d, JCP =9.0 Hz, PhP CH), 132.19 (d, 4JCP =2.2 Hz,
Ph3P CH para), 133.33 (d, JCP =9.6 Hz, Ph3P CH), 136.74 (d, JCP
(m, 4H, H phosphirane), 1.23 (t, 9H, Me), 3.00 ppm (q, 6H, CH2N);
1
1
13C NMR: d=8.38 (s, Me), 10.67 (d, JCP =15.9 Hz, CH2P), 51.71 (d, JCP
=
=
35.7 Hz, PhP C ipso), 198.48 (d, JCP =6.3 Hz, CO cis), 202.38 ppm (d,
J
7.2 Hz, CH2N), 198.17 (d, JCP =6.3 Hz, CO cis), 198.91 ppm (d, JCP
=
CP =16.0 Hz, CO trans); 31P NMR: d=15.8, À91.1 ppm (1JHP =315.0 Hz);
20.2 Hz, CO trans); 31P NMR: d=À265.8 ppm; 11B NMR: d=À6.28 ppm;
Chem. Eur. J. 2012, 00, 0 – 0
ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
&
3
&
ÞÞ
These are not the final page numbers!

F. Mathey and R. Tian
HRMS: m/z calcd for C8H22BNP [MÀW(CO)5 +H]+ 174.1583; found:
[11] J. C. Huffman, W. A. Skupinski, K. G. Caulton, Cryst. Struct.
Commun. 1982, 11, 1435.
174.1583.
[12] Gaussian 03, Revision B.05, M. J. Frisch, G. W. Trucks, H. B. Schle-
gel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomer-
y, Jr., T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyen-
gar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N.
Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K.
Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda,
O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian,
J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E.
Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W.
Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J.
Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C.
Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari,
J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cio-
slowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaro-
mi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng,
A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W.
Chen, M. W. Wong, C. Gonzalez, J. A. Pople, Gaussian, Inc., Wall-
ingford CT, 2004.
Acknowledgements
The authors thank Dr. Rakesh Ganguly for the X-ray crystal structure
analysis of 5 and the Nanyang Technological University in Singapore for
the financial support of this work.
Keywords: bond energy
·
boron
·
phosphiranes
·
phosphorus · synthetic methods
[1] Reviews: F. Mathey, Dalton Trans. 2007, 1861; K. Lammertsma,
M. J. M. Vlaar, Eur. J. Org. Chem. 2002, 1127; F. Mathey, N. H. Tran
Huy, A. Marinetti, Helv. Chim. Acta 2001, 84, 2938.
[2] M. P. Doyle, R. Duffy, M. Ratnikov, L. Zhou, Chem. Rev. 2010, 110,
704.
[13] F. Mathey, Chem. Rev. 1990, 90, 997.
[14] P. P. Power, Chem. Rev. 1999, 99, 3463.
[3] J. Svara, F. Mathey, Organometallics 1986, 5, 1159.
[4] N. Hoa Tran Huy, L. Ricard, F. Mathey, New J. Chem. 1998, 22, 75.
[5] N. Hoffmann, C. Wismach, P. G. Jones, R. Streubel, N. H. Tran Huy,
F. Mathey, Chem. Commun. 2002, 454.
[6] R. E. Bulo, A. W. Ehlers, F. J. J. de Kanter, M. Schakel, M. Lutz,
A. L. Spek, K. Lammertsma, B. Wang, Chem. Eur. J. 2004, 10, 2732.
[7] D. Champion, A. H. Cowley, Polyhedron 1985, 4, 1791.
[8] K. Vaheesar, T. M. Bolton, A. L. L. East, B. T. Sterenberg, Organo-
metallics 2010, 29, 484; R. A. Rajagopalan, B. T. Sterenberg, Orga-
nometallics 2011, 30, 2933.
[15] U. Vogel, P. Hoemensch, K.-C. Schwan, A. Y. Timoshkin, M. Scheer,
Chem. Eur. J. 2003, 9, 515; A. Adolf, M. Zabel, M. Scheer, Eur. J.
Inorg. Chem. 2007, 2136; U. Vogel, A. Y. Timoshkin, M. Scheer,
Angew. Chem. 2001, 113, 4541; Angew. Chem. Int. Ed. 2001, 40,
4409; U. Vogel, A. Y. Timoshkin, K.-C. Schwan, M. Bodensteiner,
M. Scheer, J. Organomet. Chem. 2006, 691, 4556; A. Adolf, U.
Vogel, M. Zabel, A. Y. Timoshkin, M. Scheer, Eur. J. Inorg. Chem.
2008, 3482.
[16] B. Deschamps, F. Mathey, Tetrahedron Lett. 1985, 26, 4595.
[17] N. H. Tran Huy, Y. Lu, F. Mathey, Organometallics 2011, 30, 1734.
[18] A. Espinosa-Ferao, B. Deschamps, F. Mathey, Bull. Soc. Chim. Fr.
1993, 130, 695.
[9] J. Hioe, A. Karton, J. M. L. Martin, H. Zipse, Chem. Eur. J. 2010, 16,
6861.
[10] A. Marinetti, F. Mathey, J. Fischer, A. Mitschler, J. Chem. Soc.
Chem. Commun. 1982, 667.
Received: June 27, 2012
Published online: && &&, 0000
&
4
&
www.chemeurj.org
ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 0000, 00, 0 – 0
ÝÝ
These are not the final page numbers!

The Insertion of Phosphinidene Complexes
COMMUNICATION
Synthetic Methods
R. Tian, F. Mathey* .......... &&&& — &&&&
The Insertion of Terminal Phosphini-
À
dene Complexes into the B H Bond
of Amine and Phosphine Boranes
Push–pull complexation: Transient ter-
scheme). The reaction is probably
driven by an interaction between the
nucleophilic boron and the electro-
philic phosphorus.
À
minal phosphinidene complexes [RP
À
W(CO)5] insert at 1108C into the B H
À
bonds of L BH3 (L = Et3N, Ph3P; see
Chem. Eur. J. 2012, 00, 0 – 0
ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
&
5
&
ÞÞ
These are not the final page numbers!