Variable Reactivity of a N-Heterocyclic Phosphenium Complex: P?C Bond Activation or “Abnormal” Deprotonation

Article abstract of DOI:10.1002/anie.201709015

The reaction of an N-heterocyclic phosphenium complex of manganese with MeLi/Et₃NHCl under formal addition of CH₄ to the Mn=P double bond can be reversed upon UV photolysis, providing a rare example for selective P?C(alkyl) bond activation. Action of LDA on the phosphenium complex does not proceed via attack at phosphorus but rather via C4-deprotonation to yield a unique P-analogue of an “abnormal” carbene. A transmetalation product of the original complex was fully characterized. The C-metalation is also applicable to bis-phosphenium complexes of other metals.

Full text of DOI:10.1002/anie.201709015

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Accepted Article
Title: New reactivity of a N-heterocyclic phosphenium complex: P-C
bond activation and abnormal deprotonation
Authors: Michael Gediga, Simon H Schlindwein, Johannes Bender,
Martin Nieger, and Dietrich Gudat
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201709015
Angew. Chem. 10.1002/ange.201709015
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10.1002/anie.201709015
Angewandte Chemie International Edition
COMMUNICATION
New reactivity of a N-heterocyclic phosphenium complex: P-C
bond activation and abnormal deprotonation
Michael Gediga[a], Simon H. Schlindwein[a], Johannes Bender[b], Martin Nieger[c], Dietrich Gudat*[a]
Dedication ((optional))
Abstract. The reaction of an N-heterocyclic phosphenium complex
of manganese with MeLi/Et3NHCl under formal addition of CH4 to the
Mn–P double bond can be reversed upon UV-photolysis, providing a
scarce example for selective P–C(alkyl) bond activation. Action of
LDA on the phosphenium complex does not proceed via attack at
phosphorus but rather via C4-deprotonation to yield a unique P-
analogue of an "abnormal" carbene. A transmetalation product of the
original complex was fully characterized. The C-metalation is also
applicable to bis-phosphenium complexes of other metals.
neutral NHP-manganese complex 1[11] and shown that this
behaviour is not changed upon metal coordination. Thus, a
nucleophilic hydride attacks at the phosphorus atom of complex
1 to give an anionic phosphane complex 2a which can be
protonated to a metal hydride 3a (Scheme 2). During attempts to
explore the reactivity of complex 1 towards bulkier nucleophiles,
we found that the P-methylated homologue of complex 3a
prepared by a similar approach underwent a unique photolytic
P–C bond activation under release of methane, while a sterically
hindered amide reacted at the C4-carbon to afford a complex
containing a previously unknown phosphorus analogue of an
anionic dicarbene III.
Deprotonation of imidazolium cations occurs preferably at the
C2-carbon atom to yield N-heterocyclic carbenes (NHCs) I.[1]
However, following the discovery that the cations can also give
rise to complexes of meso-ionic ("abnormal") carbene ligands
that bind a metal atom via the C4-carbon atom,[2] Bertrand et al.
showed that free meso-ionic NHCs II are accessible if the C2-
position is blocked by a suitable substituent.[3] Furthermore, the
C4-atom provides even in NHCs or their complexes a second
reactive site which enables H/D-isotope exchange,[4] substitution
to introduce heteroatom functionalities,[5] or deprotonation[6] to
yield derivatives of anionic dicarbenes III. To date, meso-ionic
species II, III have contributed much to widen the application of
carbenes in coordination chemistry and catalysis.[7]
R1
R1
H
R
R
R
N
N
N
ii)
i)
P
Mn(CO)4
P
Mn(CO)4
P Mn(CO)4
Li
N
N
N
R
R
R
2a,b
3a,b
1
Scheme 2. Derivatisation of 1 by subsequent attachment of a nucleophile and
an electrophile to the P=M double bond (R = 2,6-iPr2C6H2 (Dipp); R1 = H (2a,
3a), Me (2b, 3b). Reagents and conditions: i) 1 equiv. Li[BEt3H], 18 h (2a[11]) or
MeLi, 10 min (2b); ii) 1.1 equiv. Et3NHCl, 12h (2a) or 10 min (2b) in toluene.
The reaction of complex 1 with methyl lithium produced the
anionic complex 2b which was in situ protonated to the metal
hydride 3b. Both products were identified by spectroscopic data,
and the two-step sequence is completely analogous to the
transformation[11] of complex 1 into the hydride 3a. Knowing that
this species releases H2 upon irradiation, we have now studied
the photolysis of compound 3b under similar conditions.
R
N
R
N
R
N
R
N
R1
R1
R1
R1
C
C
C
R2
C
P
N
R
I
N
R
II
N
R
III
N
R
R1
R1
IV
Scheme 1. Molecular structures of "normal" (I) and meso-ionic ("abnormal")
NHCs (II) as well as N-heterocyclic anionic dicarbenes (III) and phosphenium
ions (NHPs, IV).
To this end, we irradiated a C6D6 solution of the complex
with a medium-pressure mercury lamp and monitored the
progress of the reaction by recording NMR spectra at certain
intervals. After 20 min, the formation of complex 1 and methane
(cf. Scheme 3) was readily detected by observing their signals in
N-heterocyclic phosphenium ions (NHPs) IV[8][9] are
considered isoelectronic analogues of NHCs I.[10] The reactivity
of NHPs is branded by their nature as P-centred electrophiles[10]
which react with nucleophiles or bases under formation of a new
phosphorus-element bond.[9] We have recently reported on a
1
1
the 31P, H and H,13C HSQC NMR spectra, respectively (see
ESI). In addition, the phosphane 4[11] was identified by its 31P
NMR signal at 111 ppm. As the reaction proceeded, the amount
of phosphenium complex 1 decayed at the expense of the dimer
5 (31P = 277 ppm) which had been proven[11] to arise from
decarbonylation of complex 1. Further signals attributable to side
products were detected but could not be assigned. After 620
minutes, the starting material had almost completely (>99%)
been converted into a mixture of complexes 5/1 (approx. 66%),
phosphane 4 (1%), and unidentified side products (see ESI).
Phosphane 4 was also observed as the exclusive product of the
thermal decomposition of complex 3b in refluxing toluene, and
we could establish that the majority of the unidentified species
[a]
M. Gediga, S. H. Schlindwein, J. Bender, Prof. Dr. D. Gudat
Institut für Anorganische Chemie
University of Stuttgart
Pfaffenwaldring 55, 70550 Stuttgart, Germany
E-mail: gudat@iac.uni-stuttgart.de
Dr. M. Nieger
Department of Chemistry
University of Helsinki,
P.O Box 55, 00014 University of Helsinki, Finland
[b]
Supporting information for this article is given via a link at the end of
the document
formed likewise upon photolysis of
a solution containing
phosphenium complex 1 and phosphane 5 but no complex 3b.
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10.1002/anie.201709015
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COMMUNICATION
R
N
R
N
R
N
ppm) as in the LiCl complex 7 (Scheme 5) of Bertrand's meso-
ionic carbene (13C 190 ppm[3]).
Me H

h
unidentified
products
P
Mn(CO)4
P
Mn(CO)4
+
P
Me +
- CH4
N
R
N
R
N
R
R
3b
1

4
h
Me3Si
N
- 1/2 CO
P Mn(CO)4
ii)
R
N
Li
N
R
R
N
R
N
(CO)3
Mn
i)
8
P Mn(CO)4
1
1/2
iii)
5
N
R
P
P
R
Mn
(CO)4
N
N
R
6
N
R
P
Cl
Mn(CO)4
N
R
N
Zn
N
9
Scheme 3. Photochemical reaction of complex 3b (R = Dipp).
Scheme 4. C4-deprotonation and subsequent substitution of 1 (R = Dipp).
Reagents and conditions: i) LDA / - HNiPr2, RT, THF; ii) Me3SiCl / - LiCl, THF,
1 h, RT; iii) ZnCl2*TMEDA / - LiCl, THF, RT, 12 h.
DFT studies[12] on a model complex 3aMe with NMe instead
of the NDipp substituents indicate that elimination of CH4 can
proceed via
energetically (G≠ = 67.0 kcal mol-1 at the B97D/def2-tzvp
level) similar to the one found[11] for the dehydrogenation of 3aMe
a transition state that is topologically and
.
R
N
R
N
R
N
Li
R'2Zn
R'2Zn
A TDDFT calculation indicates that the first excited singlet state
of 3aMe is reached via promotion of an electron from the Kohn-
Sham (KS) HOMO, which is a linear combination of an NHP -
orbital with (PC) and (PMn) bonding orbitals, into the KS-
LUMO+1, which has a strong (PN)-antibonding contribution.
Since the excited state energy is above that of the transition
state and the excitation depletes both the P–C and P–Mn
bonding regions of electron density, it can in principle account
for the methane elimination and the ligand cleavage.
Na(thf)3
Cl
Ph
N
R
N
R
N
R
Ph
[K(2,2,2-crypt)]
7
10a
10b
Scheme 5. Molecular structures of the mesoionic NHC complex 7[3] and the
bis-carbene zinc complexes 10a[6]b (R' = tBu) and 10b[6]c (R' = N(SiMe3)2).
Structural evidence for the presence of a C4-deprotonation
product was obtained after quenching complex 6 with Me3SiCl to
yield the C-silylated complex 8 and with [Zn(tmeda)Cl2] (tmeda =
tetramethyl ethylenediamine) to give transmetalated complex 9,
respectively. Both products were fully characterized.[18] Their
molecular structures (Figures 1, 2) show typical features of
phosphenium complexes[9] like a planar environment at the
phosphorus atom and short P–Mn bonds (8: 2.0706(7) Å, 9:
2.083(7) Å), which are only marginally longer than in 1 (P–Mn
2.0625(11) Å[11]). The Zn–C distance of 1.969(13) Å in 9
compares to those in 10a (2.058(3) Å[6]b) and 10b (2.008(1) Å[6]c).
The experimental and computational findings led us to
conclude that the products observed during photolysis of
complex 3b are formed via two main pathways: a photochemical
reaction yields phosphenium complex 1 and CH4, and a
competing thermally or photolytically initiated ligand fission gives
phosphane 4 which may then undergo follow-up reactions with
other constituents of the reaction mixture. In line with this
hypothesis, we observed that the yield of the photolysis products
5/1 increased to 75% when the photolysis was carried out at 0°C.
The photolysis of complex 3b is noteworthy as an example
of the specific fission of a P–C(alkyl) bond, which is considered
kinetically more inert and thus less reactive than the adjacent
polar P–N bonds. Well studied photolytic P–C bond breaking
processes involve splitting of acyl[14] or benzyl[15] groups from
phosphane oxides or phosphonic acids, of which the photolysis
of acyl phosphine oxides has industrial importance. Analogous
reactions of phosphorus(III) compounds involve mostly fission of
phenyls from transition metal bound triorgano-phosphanes,[16]
while photolytic P-alkyl cleavage is very scarce.[17]
Si1
C5
N2
P1
Mn1
C12
Treatment of complex 1 with a bulkier and less nucleophilic
base than MeLi, lithium diisopropylamide (LDA), did not proceed
via attack at phosphorus like the reactions of uncoordinated
phosphenium halides with amides,[12] but via "abnormal"
deprotonation to give a C-lithiated phosphenium complex 6
(Scheme 4). Even if high moisture sensitivity and limited long-
term stability prevented as yet the isolation of this species in
crystalline form, its identity was proven by NMR studies.
Decisive spectral features include the further deshielding of the
31P NMR signal (31P 272 ppm) compared to complex 1, the
observation of 1H NMR signals attributable to two distinguishable
Dipp-substituents but only one proton at the NHP-backbone and,
most importantly, the appearance of the 13C NMR signal of a
quaternary carbon atom with a similar chemical shift (186.2
N1
Figure 1. Molecular structure of 8 in the crystal. Hydrogen atoms are omitted
for clarity, and peripheral substituents are drawn using a wire model. Thermal
ellipsoids are drawn at the 50% probability level. Selected distances [Å] and
angles [°]P1-Mn1 2.0706(7), P1-N1 1.6795(17), P1-N2 1.6860(17), N1-C12
1.387(3), N2-C5 1.418(2), C5-C12 1.347(3), C5-Si1 1.885(2), N1-P1-N2
89.04(8), N1-P1-Mn1 137.76(7), N2-P1-Mn1 137.15(6).
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10.1002/anie.201709015
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COMMUNICATION
N2
N1A
C2A
N3
Cr1
Si2
P2
P1
P1
Mn1
Si1
C2
N1
N4
N1
Zn1
Cl1
Figure 2. Molecular structure of 9 in the crystal. Hydrogen atoms and one of
the two positions for the disordered part of the molecule (see ESI) are omitted
for clarity. Dipp-substituents and the TMEDA ligand are drawn using a wire
model. Thermal ellipsoids are drawn at the 50% probability level. Selected
distances [Å]: P1-Mn1 2.083(7), P1-N1 1.671(16), P1-N1A 1.676(15), C2-Zn1
1.969(13), sum of bond angles at P1 359.9(10)°.
Figure 3. Molecular structure of 13 in the crystal. Hydrogen atoms are omitted
for clarity, and peripheral substituents are drawn using a wire model. Thermal
ellipsoids are drawn at the 50% probability level. Selected distances [Å] and
angles [°]: P1-Cr1 2.1179(4), P1-N2 1.7050(11), P1-N1 1.6998(12), P2-Cr1
2.1130(4), P2-N3 1.6993(12), P2-N4 1.7031(11), P1-Cr1-P2 133.325(18), sum
of bond angles at P1 359.85(14)° and at P2359.83(14)°.
The 13C NMR spectrum of complex 9 displays the signal of
the zincated carbon atom at a chemical shift of 150.3 ppm which
once more matches the values of bis-carbene complexes 10a
(13C 153.7 ppm[6]b), 10b (13C 152.6 ppm[6]c). The observation
of H NOESY cross peaks between the signals of the remaining
ring hydrogen atom and the methylene protons of TMEDA
confirms that the dimetallic assembly persists in solution.
The bridging unit in the bimetallic complexes (6, 9, 12, 14)
can be regarded as a zwitterionic carbene-phosphenium ligand
15 which represents a neutral phosphorus analogue of an
anionic bis-carbene. In view of the diagonal phosphorus-carbon
analogy,[21] which states that formal replacement of a CH unit
embedded in a -electron system by a P atom induces minor
perturbations in the electronic structure, one would expect an
even closer relation between 15 and a meso-ionic carbene. DFT
studies confirm indeed that the model ligand 15Me (with R = Me)
exhibits, like the carbenes, a singlet ground state with a singlet-
1
The "abnormal" deprotonation of a phosphenium complex is
no singular result but applicable to mono- or bis-phosphenium
complexes of other metals. Thus, the chromium complex 11
reacted with an excess n-BuLi to afford the dilithiated product 12. triplet gap of 41.2 kcal mol-1 at the B3LYP/def2-tzvp level of
Once more, this species was only identified spectroscopically,
but was readily converted into a trimethylsilyl derivative 13 which
was fully characterized (Figure 3)[18] and reveals a close
structural similarity to complex 6.[19] Reaction of complex 11 with
LDA occurred likewise at the C4-position of the phosphenium
ligand to afford as main product the mono-lithiated complex 14
which was spectroscopically identified but could not yet be
isolated.[20]
theory, and that the frontier orbitals and Wiberg bond indexes of
15Me and an isoelectronic meso-ionic carbene bear quite close
similarity (see ESI). Comparing NBO[22] atomic charges for the
ligand 15Me, complex 1Me, and the N-heterocyclic phosphenium
ion MeNHP+ suggests that the charge distribution stays similar,
and the phosphorus atom is in all compounds the most
electrophilic site. This finding is well reflected in the observed P-
attack of hydride and methyl nucleophiles on complex 1. We
therefore assume that the redirection of the bulkier LDA towards
the C4-atom arises mainly from the steric shielding of the
electrophilic site by the bulky N-aryl substituents and the metal
carbonyl fragment whereas electronic effects are less important.
Me3Si
Li
NR
NR
NR
P
P
P
RN
RN
RN
RN
i) RN
RN
ii)
In summary, the photolytic reversal of the stepwise addition
of methane to the metal-phosphorus double bond and the
"abnormal" C-deprotonation in the heterocycle backbone
represent two reaction pathways that are unprecedented for
phosphenium complexes. In particular the second reaction offers
interesting prospects for new synthetic applications which are
currently being explored in our laboratory.
Cr(CO)3
Cr(CO)3
Cr(CO)3
P
P
P
11
12
NR 13
NR
NR
Me3Si
Li
iii)
Li
NR
R
P
RN
RN
N
Cr(CO)3
14
P
15
Acknowledgements
P
N
R
NR
M. G. thanks the Landesgraduiertenförderung of Baden-
Württemberg for a scholarship. The authors acknowledge
support by the state of Baden-Württemberg through bwHPC and
the German Research Foundation (DFG) through grant no INST
40/467-1 FUGG and grant no GU415/15-1. We further thank B.
Förtsch for elemental analyses, and J. Trinkner and Dr. W. Frey
Scheme 6. Lithiation and subsequent silylation of complex 11 (R = Dipp).
Reagents and conditions: i) 2 n-BuLi / - 2 BuH, THF, 10 min RT; ii) 2 Me3SiCl /
- 2 LiCl, THF, 18 h RT; iii) LDA / - HNiPr2, THF, RT.
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from the Institute of Organic Chemistry for mass spectra and the
collection of the X-ray data sets, respectively.
obtained free of charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data.
[19] A CSD database query revealed that 15 exhibits the shortest P–Cr
distance reported to date.
Keywords: phosphenium ions • carbenes • isoelectronic
analogues • phosphorus heterocycles • C-H activation
[20] An excess of LDA afforded a mixture of 12 and 14, indicating that the
second deprotonation is likewise feasible but at a greatly reduced rate.
Furthermore, 14 was also formed – although less selectively – upon
treatment of 11 with one equivalent of n-BuLi or MeLi, respectively.
[21] K. B. Dillon, F. Mathey, J. F. Nixon, in Phosphorus: the Carbon Copy. J.
Wiley & Sons: Chichester 1998.
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Entry for the Table of Contents (Please choose one layout)
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COMMUNICATION
Two-sided reactivity of a phosphenium
complex towards small and bulky
nucleophiles enables either the
synthesis of a phosphane metal
hydride which may undergo photolysis
under PC bond activation and
cleavage of CH4, or an "abnormal"
deprotonation to produce an
Michael Gediga, Simon H. Schlindwein,
Johannes Bender, Martin Nieger,
Dietrich Gudat*
Page No. – Page No.
New reactivity of a N-heterocyclic
phosphenium complex: P-C bond
activation and abnormal
deprotonation
unprecedented P-functionalized
meso-ionic carbene.
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