Synthesis and reactivity of [(R1R2N)2PH]Fe(CO)4 complexes. X-ray crystal structure of [(Ph2N)2PH]Fe(CO)4

Article abstract of DOI:10.1016/S0022-328X(99)00031-5

KHFe(CO)₄ reacts with tris(amino)phosphines by substitution at phosphorus leading to [bis(amino)phosphine]tetracarbonyliron complexes [(R¹R²N)₂PH]Fe(CO)₄. The X-ray structure has been determined for R¹=R²=Ph. Deprotonation of these complexes with KH affords stable potassium phosphidotetracarbonylferrates which can be alkylated or acylated at phosphorus.

Full text of DOI:10.1016/S0022-328X(99)00031-5

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 584 (1999) 390–395
Synthesis and reactivity of [(R1R2N)2PH]Fe(CO)4 complexes. X-ray
ꢀ
crystal structure of [(Ph2N)2PH]Fe(CO)4
Jean-Jacques Brunet, Remi Chauvin, Ousmane Diallo, Bruno Donnadieu, Joe¨lle Jaffart,
Denis Neibecker *
Laboratoire de Chimie de Coordination du CNRS, Unite´ No 8241,
lie´e par con6entions a` l’Uni6ersite´ Paul Sabatier et a` l’Institut National Polytechnique, 205 route de Narbonne, F-31077 Toulouse,
Cedex 4, France
Received 13 March 1998; received in revised form 29 May 1998
Abstract
KHFe(CO)4 reacts with tris(amino)phosphines by substitution at phosphorus leading to [bis(amino)phosphine]tetracarbonyliron
complexes [(R1R2N)2PH]Fe(CO)4. The X-ray structure has been determined for R1=R2=Ph. Deprotonation of these complexes
with KH affords stable potassium phosphidotetracarbonylferrates which can be alkylated or acylated at phosphorus. © 1999
Elsevier Science S.A. All rights reserved.
Keywords: Aminophosphines; Iron carbonyl; Hydridotetracarbonylferrates; Phosphidotetracarbonylferrates
Fe(CO)4 [7]. This reaction provides a very easy, labora-
tory-scale preparation of the Collman type reagents
1. Introduction
M2Fe(CO)4 (M=Na, K) for immediate use. It should
also be an easy way to prepare ironcarbonyl-stabilized
secondary bis(amino)phosphines.
As part of our interest in the chemistry of hydridote-
tracarbonylferrates M+[HFe(CO)4]− [1], we have re-
ported the reaction of K+[HFe(CO)4]− with
phosphites and phosphines [2]. These reactions proceed
by CO exchange processes [3], providing highly selective
routes to a large variety of ionic and neutral phos-
phane-substituted ironcarbonyl complexes [4–6].
We report here the synthesis of several of these
complexes and the X-ray crystal structure of
[(Ph2N)2PH]Fe(CO)4, which is the first X-ray crystal
structure of a bis(amino)phosphine coordinated to a
transition metal, along with preliminary results on both
the deprotonation of [(R2N)2PH]Fe(CO)4 derivatives
and the reactivity of the resulting phosphidotetracar-
bonylferrate complexes.
In contrast, the reaction of K+[HFe(CO)4]− with
tris(dimethylamino)phosphine does not proceed by CO
substitution. Instead, substitution of an amino group at
phosphorus is observed, affording K2Fe(CO)4 and the
neutral irontetracarbonyl complex [(Me2N)2PH]-
2. Results and discussion
2.1. Synthesis of [(R1R2N)2PH]Fe(CO)4 complexes
ꢀ PII of original article S0022-328X(98)00074-4X.
* Corresponding author. Tel.: +33 561 333195; fax: +33 561
553003; e-mail: neibeker@lcctoul.lcc-toulouse.fr.
The reaction of KHFe(CO)4
(amino)phosphines 2a–c is conducted at room tempera-
1
with tris-
0022-328X/99/$ - see front matter © 1999 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(99)00031-5

Erratum / Journal of Organometallic Chemistry 584 (1999) 390–395
391
,
ture (r.t.) in THF (Eq. (1)). For 2b, the reaction is
instantaneous, as indicated by an immediate white pre-
cipitate of K2Fe(CO)4, whereas for 2a and 2c, the
reaction occurs only on evaporation of the solvent
under reduced pressure. Classical work-up allows isola-
tion of complexes 4a–c in a 70–90% yield.
[(Me2N)3P]Fe(CO)4 (2.245 A) and for (Ph3P)Fe(CO)4
,
(2.244 A) [10]. The geometry at phosphorus is approxi-
mately tetrahedral, the average bond angle N1–P1–N2,
Fe–P1–N1 and Fe–P2–N2 being 115°. The sum of the
angles about nitrogen is equal to 360°. The most in-
triguing structural feature is that, although the geome-
try at each nitrogen atom is perfectly trigonal planar,
the two P–N bond lengths are unexpectedly very differ-
Complex 4c is reported for the first time. 4a and 4b
have previously been prepared by reacting either
THF, RT
2KHFe(CO)4+P(NR1R2)3−ꢀꢀRꢀꢀRꢀNꢀHꢁ ¡K2Fe(CO)4+[(R1R2N)2PH]Fe(CO)4
(1)
1
2
3
4
1
2
a R1=R2=Me, 90%
b R1=R2=iPr, 90%
c R1=Et, R2=Ph, 70%
(iPr2N)2PH with Fe(CO)4(THF) (4b) [8] or
[PPh4][HFe(CO)4] with the corresponding bis(dialkyl-
amino)chlorophosphine (4a, 4b) [9].
ent (P1–N2=1.670(3); P1–N1=1.739(4) A) and in the
,
range found for phosphorus–nitrogen compounds con-
2
,
taining sp -type nitrogen atoms (1.66–1.68 A [10,11])
The synthesis of complexes 4 from tris(amino)-
phosphines (Eq. (1)) thus appears as an interesting
alternative to the above-mentioned procedures via a
P–N bond activation process instead of a P–Cl one.
Nevertheless, when tris(amino)phosphines are not read-
ily accessible, the reaction shown in Eq. (2) [9] involv-
ing such a P–Cl bond activation is the best synthetic
procedure and has been used to obtain 4c and the
previously unreported [(Ph2N)2PH]Fe(CO)4, 4d.
and sp3-type nitrogen atoms (1.73–1.74
respectively.
A [11]),
,
2.3. Reaction of [(R1R2N)2PH]Fe(CO)4 complexes 4
with KH
Several mechanistic proposals involving terminal
phosphinidene complexes as intermediates [12] encour-
KHFe(CO)4+(R1R2N)2PClTꢀHꢀFꢀ,ꢀRꢀTꢁ[(R1R2N)2PH]Fe(CO)4
(2)
1
−KCl
4
c R1=Et, R2=Ph, 72%
d R1=R2=Ph, 32%
2.2. X-ray crystal structure of 4d
aged us to study the deprotonation of complexes 4
under non-reversible conditions.
Reaction of 4a,c,d with excess KH in Et2O or THF
at r.t. results in the quantitative formation (31P-NMR)
of the air-sensitive phosphido complexes 5a,c,d (Eq.
(3)).
The structure of 4d has been determined by X-ray
diffraction analysis (Table 1). A view of the molecular
structure with atom labelling scheme is shown in Fig. 1.
The Fe atom adopts an approximately trigonal-bipyra-
midal geometry with a nearly perfect trigonal plane of
three CO ligands for which each C–Fe–C bond angle is
Et O, RT
2
[(R1R2N)2PH]Fe(CO)4+KHꢀꢀꢀꢀꢀꢁ[{(R1R2N)2P}Fe(CO)4]−K+
(3)
4
5
a R1=R2=Me
b R1=Et, R2=Ph
d R1=R2=Ph
120°. The phosphorus atom and the fourth CO ligand
occupy axial sites (P1–Fe–C2=176.6°). The Fe–P1
As verified for 5c, complexes 5a,c,d can alternatively
,
bond length (2.234(1) A) is close to that found for
be obtained by allowing K2Fe(CO)4 to react with the

392
Erratum / Journal of Organometallic Chemistry 584 (1999) 390–395
Fig. 1. Molecular structure of complex 4d showing the atom numbering scheme.
corresponding (R1R2N)2PCl in DMAC, according to
the route reported from Na2Fe(CO)4 and Ar2PCl [13].
In the case of 4b (R1=R2=iPr), the reaction with
KH regenerates [HFe(CO)4]− and (iPr2N)2PH, indicat-
ing that H− acts as a competitive ligand for the
[Fe(CO)4] moiety.
The phosphidotetracarbonylferrates 5 can be repre-
sented by the resonance forms shown in Scheme 1 and
are characterized by a low-field 31P-NMR signal in the
range 220–230 ppm.
This deshielding suggests the participation of the
amido-stabilized phosphinidene resonance form in the
description of the complex. This proposal is supported
by analogy with literature data on base-stabilized ironsi-
lylene complexes, e.g. [Fe(CO)4{SiMe2–(NMe2H)}] [14],
and by the behaviour of complex 5a. Indeed, although
complexes 5c and 5d are stable in THF, complex 5a
slowly decomposes at r.t. Thus, stirring a solution of 4a
in the presence of excess KH in THF leads to the clean
formation of 5a (31P{1H}-NMR).
(4)

Erratum / Journal of Organometallic Chemistry 584 (1999) 390–395
393
Scheme 1.
After 2 days at r.t. the 31P{1H}-NMR spectrum of the
solution indicates the almost complete disappearance of
used to prepare (i-Pr2N)3P, (EtPhN)3P, (i-Pr2N)2PCl,
(EtPhN)2PCl, (Ph2N)2PCl [17], solutions of
the singlet signal of 5a (l=231.2 ppm) to leave an AB
KHFe(CO)4 in THF [2] and K2Fe(CO)4 [7]. NMR
spectra were recorded on Bruker AC-200 or Bruker
AMX-400 spectrometers. 31P{1H}-NMR-spectra were
1
type spectrum (lP1=169.4, lP2=202.9 ppm, JP1–P2
=
1
550 Hz). Restoring the H coupling results for the P1
signal in two symmetrical septuplets (3JP–H=15 Hz)
indicating that the P1 atom bears only one NMe2
substituent. In contrast, the signal of the P2 atom is
now a doublet of a complex pattern reminiscent of the
31P-NMR spectrum of 5a, thus suggesting that the P2
atom bears two NMe2 substituents. These NMR data
do not correspond to those expected for the methyl
analogue 6 of the previously reported diphosphene
complex 7 (Fig. 2) [12a], but rather to the proposed
structure 8a. Such a complex may result from the
reaction of 5a with an ironcarbonyl phosphinidene
intermediate (Eq. 4). Unfortunately, all attempts to
isolate complex 8a and to obtain X-ray quality crystals
have failed so far.
1
referenced to external H3PO4. H-NMR spectra were
referenced to the residual proton resonance of the
deuterated solvents (SDS) (CDCl3, lH=7.27; C6D6,
lH=7.15; THF-d8, lH=3.60 ppm). 13C{1H}-NMR
spectra were referenced to the carbon resonance of the
solvents (CDCl3, lC=77.0; C6D6, lC=128.5; THF-d8,
lC=25.8 ppm). Satisfactory C, H, N analysis (90.6%)
were obtained for complexes 4a–d, 9c and 10c (Labora-
tory In-house Service, Perkin–Elmer 2400 apparatus).
3.2. Preparation of complexes 4
Complexes 4a and 4b were prepared from
KHFe(CO)4 and the corresponding tris(dialkyl-
amino)phosphine, as previously described for (Me2N)3P
[7]. 4b could also be prepared from KHFe(CO)4 and
(i-Pr2N)2PCl. 4a and 4b displayed similar NMR spectra
as those previously reported [7,9].
4c: (EtPhN)2PCl (4.9 mmol) was added to a solution
of KHFe(CO)4 (5.0 mmol) in THF (15 ml) at r.t. After
10 min stirring, the solvent was evaporated and pentane
(20 ml) was added. The liquid phase was cannulated
By contrast, the phosphido character (Scheme 1) of
complexes 5 is revealed by their reaction with CH3I or
CH3COCl to afford the expected alkyl- or acyl-
bis(amino)phosphinetetracarbonyliron complexes 9c
and 10c in good yield, as demonstrated for 5c (Eq. 5).
These reactions are additional examples of the depro-
tonation-alkylation sequence of coordinated secondary
phosphines known for a long time [15] and of the
synthesis of coordinated acylphosphines [16].
(5)
into another Schlenk flask and evaporated to give
[(EtPhN)2PH]Fe(CO)4 4c (oil, 72%). 31P{1H}-NMR
(162.0 MHz) (THF-d8) l (ppm)=136.3; 1H-NMR
(400.1 MHz) (THF-d8) l (ppm)=0.94 (t, 6H, CH3CH2,
3JH–H=7.0 Hz); 3.58 and 3.78 (ABC3Y system, 4H,
3. Experimental
3.1. General procedure and reagent syntheses
3
2
CH3CH2, JH–P=8.9 Hz, JH–H=14.0 Hz); 7.1–7.35
All manipulations were performed under argon using
standard Schlenk tube and vacuum line techniques.
THF (SDS) and diethylether (SDS) were dried and
deaerated by distillation from sodium–benzophenone
ketyl under argon. n-Pentane (SDS) was dried and
deaerated by distillation from P2O5 under argon. Sam-
ples of (Me2N)3P and KH as a dispersion in mineral oil
were purchased from Fluka and Aldrich, respectively.
Literature methods or methods adapted therefrom were
1
(10H, aromatic H); 8.0 (d, 1H, HP, JH–P=454.3 Hz;
Fig. 2. Unsymmetrical diphosphene bis(irontetracarbonyl) complexes.

394
Erratum / Journal of Organometallic Chemistry 584 (1999) 390–395
Table 1
ml) was then added and the reaction mixture was stirred
until gas evolution ceased. The supernatant phase was
then cannulated into another Schlenk flask and the
solvent removed under vacuum to afford 5c (73%).
Complexes 5a and 5d were similarly prepared but only
5d could be isolated (70% yield) (see text).
Crystal and collection data for complex 4d
Crystal parameters
Empirical formula
M (g)
Shape (color)
Size (mm)
C
536.31
Plate (orange)
0.5×0.5×0.07
Triclinic
28H21FeN2O4P
5a: 31P{1H}-NMR (162.0 MHz) (THF-d8) l (ppm)=
Crystal system
Space group
1
231.2; H-NMR (400.1 MHz) (THF-d8) l (ppm)=2.47
(
P1
3
(d, CH3, JH–P=9.0 Hz); 13C{1H}-NMR (50.3 MHz)
,
a (A)
9.051(1)
11.111(2)
13.827(2)
100.66(1)
109.50(2)
104.53(2)
1212.6(4)
2
(THF-d8) l (ppm)=43.1 (d, CH3, 2JC–P=15 Hz); 222.1
(d, CO, 2JC–P=3 Hz).
,
b (A)
,
c (A)
5c: 31P{1H}-NMR (162.0 MHz) (THF-d8) l (ppm)=
h (°)
i (°)
k (°)
1
231.2; H-NMR (400.1 MHz) (THF-d8) l (ppm)=1.09
3
(t, 6H, CH3CH2, JH–H=6.8 Hz); 3.58 and 3.78 (ABC3
3
,
V (A )
system, 4H, CH3CH2, 2JH–H=15.0 Hz); 6.85–7.15 (10H,
aromatic H); 13C{1H}-NMR (100.6 MHz) (THF-d8) l
Z
F(000)
4040
1.40
6.9
Dcalc. (g cm−3
)
2
(ppm)=14.6 (CH3CH2); 45.0 (d, CH3CH2, JC–P=8
v (Mo–Ka) (cm−1
Data Collection
Diffractometer
Monochromator
Radiation
)
Hz); 117.3 (d, JC–P=2 Hz), 120.0 (d, JC–P=17 Hz),
128.7, 151.7 (d, 2JC–P=19 Hz) (aromatic C); 220.3 (CO).
5d: 31P{1H}-NMR (81.0 MHz) (C6D6) l (ppm)=
208.3; 13C{1H}-NMR (50.3 MHz) (C6D6) l (ppm)=
118.5, 122.4, 126.7 (d, JC–P=7.5 Hz), 129.5, 130.6, 151.8
IPDS Stoe
Graphite
Mo–Kh (u=0.71073)
ƒ
Scan mode
ƒ range (°)
ƒ incr. (°)
2q range (°)
No. of rflns collected
No. of unique rflns
No. rflns used (I\3|(I))
Refinement
R
Rw
0BƒB250
2
2.9BqB48.4
8963
3449
2337
2
(d, JC–P=3 Hz) (aromatic C); 218.6 (d, CO, JC–P=3
Hz).
3.4. Alternati6e generation of complex 5c
A solution of (PhEtN)2PCl (0.25 mmol) in DMAC (1.2
ml) was dropped by means of a syringe into a magneti-
cally stirred solution of K2Fe(CO)4 (0.25 mmol) in
DMAC (4 ml) at r.t. After 15 min, the 31P{1H}-NMR
spectrum of the crude solution indicated the quantitative
formation of 5c.
0.053
0.059
Chebyshev
3.17; −0.408; 2.59
1.10
330
Weighting scheme
Coeff. Ar
Goodness-of-fit
L.s parameters
13C{1H}-NMR (50.3 MHz) (THF-d8) l (ppm)=15.0 (d,
CH3CH2, JC–P=4 Hz); 47.5 (d, CH3CH2, JC–P=8
Hz); 127.1, 128.8, 130.6, 146. (d, 2JC–P=3 Hz) (aromatic
C); 214.6 (d, CO, 2JC–P=20 Hz).
3.5. Synthesis of complexes 9c and 10c
3
2
Methyl iodide (or acetyl chloride) (0.4 mmol) was
added to a solution of 5c (0.4 mmol) in diethyl ether (5
ml) at r.t. After a few minutes, the liquid phase was
cannulated into another Schlenk flask and the solvent
evaporated under vacuum to afford 9c or 10c as solids in
an 85 and 75% yield, respectively.
4d: (Ph2N)2PCl (2.5 mmol) was added to a solution of
KHFe(CO)4 (4 mmol) in THF (15 ml) at r.t. After 5 h
stirring, the solvent was evaporated and pentane (20 ml)
was added. The liquid phase was cannulated into another
Schlenk flask in which [(Ph2N)2PH]Fe(CO)4 4d slowly
crystallised as orange plates (32%). 31P{1H}-NMR (81.0
MHz) (CDCl3) l (ppm)=120.4; 1H-NMR (200.1 MHz)
(CDCl3) l (ppm)=7.00–7.30 (20H, aromatic H); 8.77
(d, 1H, HP, 1JH–P=444.0 Hz; 13C{1H}-NMR (50.3
MHz) (CDCl3) l (ppm)=125.8, 127.3 (d, JC–P=3 Hz),
129.2, 145.9 (aromatic C); 212.6 (d, CO, 2JC–P=20 Hz).
9c: 31P{1H}-NMR (162.0 MHz) (C6D6) l (ppm)=
1
135.7; H-NMR (400.1 MHz) (C6D6) l (ppm)=0.85 (t,
6H, CH3CH2, 3JH–H=7.0 Hz); 1.34 (d, 3H, CH3P,
2JH–P=7.3 Hz); 3.36 and 3.62 (ABC3Y system, 4H,
3
2
CH3CH2, JH–P=7.0 Hz, JH–H=14.0 Hz); 6.70–7.15
(5H, aromatic H); 13C{1H}-NMR (100.6 MHz) (C6D6) l
(ppm)=14.6 (CH3CH2); 25.9 (d, CH3P, 1JC–P=49 Hz);
2
47.9 (CH3CH2); 127.4, 129.6, 131.3, 143.8 (d, JC–P=4
3.3. Synthesis of complexes 5a,c,d
Hz) (aromatic C); 215.3 (d, CO, 2JC–P=20 Hz).
10c: 31P{1H}-NMR (162.0 MHz) (C6D6) l (ppm)=
1
In a typical experiment, an excess of KH in mineral oil
was washed with THF (3×2 ml) and the solvent was
evaporated under vacuum until a mobile powder was
obtained. A solution of 4c (2 mmol) in diethyl ether (10
149.5; H-NMR (200.1 MHz) (C6D6) l (ppm)=0.72 (t,
3
6H, CH3CH2, JH–H=7.0 Hz); 1.89 (d, 3H, CH3COP,
3JH–P=4.0 Hz); 3.44 and 3.53, ABC3Y system, 4H,
3
2
CH3CH2, JH–P ca. 7 Hz, JH–H=14.0 Hz); 7.00–7.30

Erratum / Journal of Organometallic Chemistry 584 (1999) 390–395
395
(5H, aromatic H); 13C{1H}-NMR (100.6 MHz) (C6D6)
l (ppm)=14.3 (d, CH3CH2, 3JC–P=3 Hz); 28.3 (d,
CH3COP, JC–P=48 Hz); 48.7 (d, CH3CH2, JC–P=6
Hz); 127.3, 129.8, 130.2, 143.6 (aromatic C); 211.9 (d,
CH3COP, 1JC–P=25 Hz); 214.0 (d, CO, 2JC–P=17 Hz).
Acknowledgements
2
2
This work was supported by the Centre National de
la Recherche Scientifique. Thanks are due to Dr J.-C.
Daran for helpful discussions.
3.6. X-ray diffraction study of 4d
X-ray quality crystals were obtained by slow evapora-
tion of a pentane solution. The data were collected on
a Stoe Imaging Plate Diffraction System (IPDS). The
crystal-to-detector distance was 80 mm. A total of 125
exposures (4 min per exposure) were obtained with
0BƒB250° and with the crystals rotated through 2° in
ƒ. Coverage of the unique set was over 95% complete to
at least 24.2°. Crystal decay was monitored by measuring
200 reflexions per image. The final unit cell parameters
were obtained by the least-squares refinement of 2000
reflections. Only statistical fluctuations were observed in
the intensity monitors over the course of the data
collection. Owing to the rather low vx value, 0.35, no
absorption correction was considered.
References
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The structure was solved by direct methods (SIR92)
[18] and refined by least-squares procedures on Fo. H
atoms were located on difference Fourier maps, but those
attached to C atoms were introduced in calculation in
,
idealized positions ((d(CH)=0.96 A) and their atomic
coordinates were recalculated after each cycle. They were
given isotropic thermal parameters 20% higher than
those of the carbon to which they are attached. The H
atom attached to the phosphorus was refined isotropi-
cally. Least-squares refinements were carried out by
minimizing the function ꢀw(ꢁFoꢁ–ꢁFcꢁ)2, where Fo and Fc
are the observed and calculated structure factors. The
weighting scheme used in the last refinement cycles was
w=w%{1-[DF/6|(Fo)]2}2 where w%=1/ꢀ1ArTr(x) with
n
three coefficients Ar for the Chebyshev polynomial
ArTr(x) where x was Fc/Fc(max) [19]. Models reached
convergence with R=ꢀ(ꢂFoꢁ–ꢁFcꢂ)/ꢀ(ꢁFoꢁ) and Rw=
[ꢀw(ꢁFoꢁ–ꢁFcꢁ)2/Sw(Fo)2]1/2, having values listed in Table
1. Criteria for a satisfactory complete analysis were the
ratios of rms shift to standard deviation less than 0.1 and
no significant features in final difference maps.
The calculations were carried out with the CRYSTALS
package programs [20] running on a PC. The drawing of
the molecule was realized with the help of CAMERON [21].
[17] (a) H. Falius, M. Babin, Z. Anorg. Allg. Chem. 420 (1976) 65.
(b) M.J.S. Gynane, A. Hudson, M.R. Lappert, P.P. Power, H.
Goldwhite, J. Chem. Soc. Dalton Trans. (1980) 2428. (c) H.N.
Rydon, B.L. Tonge, J. Chem. Soc. (1957) 4682.
[18] A. Altomare, G. Cascarano, G. Giacovazzo, et al., SIR92–a
program for automatic solution of crystal structures by direcct
methods, J. Appl. Cryst. 27 (1994) 435.
4. Supplementary material
[19] E. Prince, Mathematical Techniques in Crystallography, Berlin,
Springer-Verlag, 1982.
[20] D.J. Watkin, C.K. Prout, J.R. Carruthers, P.W. Betteridge,
CRYSTALS Issue 10, Chemical Crystallography Laboratory, Uni-
versity of Oxford, Oxford, 1996.
[21] D.J. Watkin, C.K. Prout, L.J. Pearce, CAMERON, Chemical
Crystallography Laboratory, University of Oxford, Oxford,
1996.
Complete tables of interatomic distances, bond an-
gles, fractional atomic coordinates with the equivalent
thermal parameters for all atoms but H, anisotropic
thermal parameters for non hydrogen atoms and
atomic coordinates for H atoms have been deposited at
the Cambridge Crystallographic Data Centre.
.