Trapping Highly Electrophilic Metalladiphosphanylcarbenes

Article abstract of DOI:10.1002/anie.200219604

A nonstandard method of carbene generation is provided by reaction of 1 with AgBF₄ to give the transient metalladiphosphanylcarbene 2. This unique dicationic singlet carbene can be trapped with bases (pyridine (Py) for example, see scheme) showing its electrophilic character, which is also confirmed by DFT calculations.

Full text of DOI:10.1002/anie.200219604

Angewandte
Chemie
silver(i) salts (AgClO or AgBF ) (Scheme 1),a nonstandard
4
4
method of carbene generation. Thus the formally anionic
À
diphosphanyliodomethanide ligand {(PPh ) CI} is converted
2
2
into the neutral ligand (PPh ) CD. Coordination of the
2
2
diphosphanylcarbene (PPh ) CD to the metal fragment
2
2
Carbene Chemistry
Scheme 1. Formation of the transient metalladiphosphanylcarbene 2.
R=tBu.
Trapping Highly Electrophilic
Metalladiphosphanylcarbenes**
through the phosphorus atoms avoids dimerization to form
5
5
[11]
the corresponding 1l ,3l -diphosphete derivative, or even
´
Javier Ruiz,* Marta E. G. Mosquera, Gabriel Garcia,
[
5b]
1
,2-migration of a phenyl group to give the phosphaalkene,
´
´
Elena Patrón, Victor Riera, Santiago Garcia-Granda,
and Francisco Van der Maelen
and enhances the electrophilicity of the carbene as the
phosphorus lone pairs can no longer be used for p donation to
the carbene carbon atom. Owing to its high electrophilicity
(see calculated electron affinities (EA) values in Table 1) 2 is
In recent years much attention has been paid to the study of
nucleophilic carbenes of Arduengo type (N-heterocyclic
[
1]
[2]
carbenes) and related diaminocarbenes (R N) CD, which
2
2
Table 1: Calculated structural parameters, singlet–triplet splittings
are stabilized by the presence of two p-donor nitrogen atoms
bonded to the carbene carbon atom. The synthesis of the first
push-pull phosphanylsilylcarbene of formula (R P)(SiMe )CD
(
DE ), and electron affinities (EA) of 2b.
ST
B3LYP6-
B3LYP6- B3LYP6- B3LYP6-
2
3
[a]
31G*,LanL2DZ 31G*,3- 31G**,3- 311++G**,3-
(
R = NiPr ) by Bertrand and co-workers was also a milestone
2
2
1G
21G*
1.682
21+G*
[
3]
in carbene chemistry. Mixed-substituent aminophosphanyl-
carbenes have recently been prepared. Of great interest are
[
4]
C-P [Š]
1.673
1.681
1.662
137.9
P-C-P [8]
DEST [kcalmol
EA [eV]
134.3
À8.96
129.2
129.3
also the analogous diphosphanylcarbenes (R P) CD,although
À1
2
2
]
À9.86 À10.00 À10.80
[
5]
they are only known as transient species, which have been
8.94 8.99
[
6]
investigated by ab initio calculations. Interestingly,their
protonated phosphoniumphosphanylcarbene derivatives
[a] Second basis for Ru, first basis for all the other atoms.
+
[7]
[
(R P)(R PH)CD] ions are known to be stable.
2
2
We report herein on the generation and trapping reactions
of the transient highly electrophilic metalladiphosphanylcar-
very unstable and instantaneously decomposes,unless a
2
+
[8]
bene [Ru(CNtBu) (PPh ) CD] (2). The electrophilic char-
trapping reagent is added. Thus,reaction of 1 with AgBF in
4
2
2
4
acter of 2 has been confirmed experimentally and by density
CH Cl as solvent in the presence of pyridine (Py) gives
complex 3,the pyridine adduct of carbene 2 (Scheme 2).
Complex 3 cocrystallizes with the silver complex salt
2
2
[
9]
[12]
functional theory (DFT) calculations.
Transient carbene 2 is formed from the cationic complex
+
[10]
[
Ru(CNtBu) {(PPh ) CI}] (1) by iodide abstraction with
[Ag(Py) ]BF giving suitable crystals for X-ray analysis
4
2
2
2
4
13]
[
(
Figure 1).
In the new pyridinium diphosphanylylide
ligand the C1ÀN1 bond is slightly shortened with respect to
´
[
*] Dr. J. Ruiz, Dr. M. E. G. Mosquera, G. Garcia, E. Patrón,
single bond,and the pyridinium plane is coplanar with the P1-
P2-C1 plane allowing a p interaction of the ylide carbon atom
C1 with the p system in the ring. The P1ÀC1 and P2ÀC1 bonds
Prof. Dr. V. Riera
´
Departamento de Quimica Orgµnica e Inorgµnica
´
Facultad de Quimica
Universidad de Oviedo
are appreciable shorter than single bonds indicating that the
negative charge at the ylide carbon atom is also shared with
both coordinated phosphorus atoms,thus stabilizing the ylide
structure. Another adduct of carbene 2 is formed by treat-
33071 Oviedo (Spain)
Fax: (+34)98-5103-446
E-mail: jruiz@sauron.quimica.uniovi.es
´
Dr. S. Garcia-Granda, Dr. F. Van der Maelen
Departamento de Quimica Fisica y Analitica
ment of 1 with AgBF in the presence of tetrahydrothiophene
4
´
´
´
(
(
tht). The reaction occurs readily to give complex 4
´
Facultad de Quimica
[
14]
1
Scheme 2).
The H NMR spectrum of 4 shows three
Universidad de Oviedo
3
3071 Oviedo (Spain)
**] This work was supported by the Spanish DGES (Project 1FD97-
750) and by the Principado de Asturias (Project PR-01-GE-7).
resonance signals for the CH groups of tht (see Experimental
2
Section),as the two protons of each
a-CH2 unit are
[
0
inequivalent owing to its different orientation respect to the
Angew. Chem. Int. Ed. 2003, 42, 4767 –4771
DOI: 10.1002/anie.200219604
ꢀ 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4767

Communications
Figure 2. A view of the structure of the cation 4 (thermal ellipsoids set
at 20% probability). Methyl groups in the CNtBu ligands are omitted
for clarity. Selected bond lengths [Š] and angles [8]: P1-C1 1.774(6), P2-
C1 1.771(6), S1-C1 1.707(6), S1-C2 1.820(7), S1-C5 1.812(7); P1-Ru1-
P2 70.51(5), S1-C1-P2 124.5(3), S1-C1-P1 134.9(4), C1-S1-C2 114.2(3),
C1-S1-C5 109.8(3).
Scheme 2. Trapping reactions of carbene 2. [Ru]=[Ru(CNtBu)4],
tht=tetrahydrothiophene.
2+
[
Ru(CNtBu) {(PPh ) C=O}] (5) is obtained,after precip-
4 2 2
itation of AgI (Scheme 2). This result implies the transfer of
À
an oxygen atom from the ClO4 group to the transient
carbene 2,which probably proceeds through nucleophilic
attack of the oxoanion to the carbene carbon atom. The IR
spectrum of 5 reveals the presence of the ketone group
À1
13
1
(
~n CO = 1721 cm (m)),as well as the C{ H} NMR spectrum
1
which shows a triplet at d = 216.6 ppm ( J(P,C) = 16 Hz) for
the P CO carbon atom. The solid structure of 5 has also
[
15]
2
been confirmed by X-ray analysis (not shown).
The formation of carbene 2 by treatment of 1 with AgBF4
in the presence of H O yields the cationic complex [Ru(CNt-
2
2
+
Bu) {(O=PPh )(PPh )CH }] (6; Scheme 2),which contains a
4
2
2
2
mono-oxidized methylenebis[(diphenyl)phosphane] (dppm)
ligand arising from activation of both OÀH bonds in the water
molecule by the carbene. The structure of 6 has been
3
1
1
confirmed by P and H NMR spectroscopy (see Experimen-
tal Section) and by X-ray analysis. On the basis of the known
trapping reactions of transient diphosphanylcarbenes with
[
5a]
alcohols,
the formation of 6 could proceed through
insertion of carbene 2 into a OÀH bond of water,followed
by a 1,2-shift of the OH group to a phosphorus atom and
further proton migration to the central carbon atom.
Figure 1. A view of the structure of the cation 3 (thermal ellipsoids set
at 20% probability). Methyl groups in the CNtBu ligands are omitted
for clarity. Selected bond lengths [Š] and angles [8]: Ru1-P1 2.355(2),
Ru1-P2 2.359(2), P1-C1 1.761(9), P2-C1 1.756(10), N1-C1 1.428(10);
P1-Ru1-P2 70.48(9), N1-C1-P2 128.9(7), N1-C1-P1 129.8(7), P2-C1-P1
To investigate the iodide abstraction leading to carbene 2
we treated 1 with some soluble silver(i) and gold(i) complexes.
With the silver derivative Ag(ClO )(PPh ),the interaction
1
01.3(4).
4
3
with iodide is so strong that formation of [{AgI(PPh )} ] is
3
4
immediately observed with parallel formation of [Ru(CNt-
2
+
lone pair of sulfur. The solid-state structure of 4 was solved by
X-ray analysis (Figure 2),and clearly shows a tht solvent
molecule stabilizing carbene 2 with a rather strong CÀS
Bu) {(PPh ) CH }] as decomposition product of the car-
4 2 2 2
bene. Fortunately,treatment of 1 with [AuCl(tht)] allowed the
isolation of the complex [Ru(CNtBu) (PPh ) C(AuCl)I] (7;
Scheme 3). The structure of this cation (Figure 3) shows the
AuCl unit bonded to the methanide carbon atom,but also a
close Au···I contact of 3.35 Š which is shorter than the sum of
+
4
2 2
interaction (C1-S1 1.707(6) Š).
When carbene 2 is generated by treatment of 1 with an
excess of AgClO ,the diphosphanylketone complex
4
4
768
ꢀ 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Angew. Chem. Int. Ed. 2003, 42, 4767 –4771

Angewandte
Chemie
In conclusion we have present an approach to generate a
unique dicationic singlet carbene (2),whose electrophilic
character has been confirmed experimentally and by DFT
calculations. This new type of carbene,as well as its isolated
pyridine and tetrahydrothiophene adducts,show promise as
reaction intermediates for the preparation of new function-
alized diphosphane ligands,as exemplified with the synthesis
of the diphosphanylketone derivative 5.
Scheme 3. Formation of the heterometallic ruthenium(ii)/gold(i) com-
plex 7. R=tBu.
Experimental Section
All reactions and manipulations were performed under a atmosphere
of dry nitrogen by using standard Schlenk and glovebox techniques.
Solvents were distilled over appropriate drying agents under dry
nitrogen prior to use. Chemical shifts of the NMR spectra are
1
13
31
referenced to internal SiMe
4 3 4
( H and C) or external H PO ( P).
3
-(BF ) ·0.5{[Ag(Py) ]BF }: Pyridine (81 mL,1 mmol) was added
4
2
2
4
to a solution of [Ru(CNtBu) {(PPh ) CI}]I (1-I; 0.11 g,0.1 mmol) in
4
2 2
CH Cl (20 mL). This solution was transferred by canula to a Schlenk
2
2
containing AgBF (0.08 g,0.4 mmol) previously cooled to À758C and
4
covered to protect from the light. The mixture was stirred for 10 min
and then allowed to warm to room temperature and stirred for a
further hour. Filtration of the mixture gave a clear yellow solution.
Half of the solvent was removed in vacuo and diethyl ether (15 mL)
was carefully added. Storage at À188C for 4 days afforded yellow
crystals,yield: 0.094 g (67%). Elemental analysis (%) calcd for
C H N Ag0.5B2.5F N P Ru: C 53.05,H 5.34,N 6.75; found: C 52.53,
5
5
66
7
10
6 2
À1
H 5.10,N 6.77; IR (CH Cl ): ~n = 2215 (w),2180 cm
P{ H} NMR (121.5 MHz,CD Cl ): d = 10.5 ppm; H NMR
(s) (CNtBu);
2
2
3
1
1
1
2
2
(
0
300 MHz,CD Cl ): d = 8.1–7.3 (35H),1.53 (s,18H,CN
tBu),
2
2
1
3
.95 ppm (s,18H,CN tBu); C NMR (75.5 MHz,CD Cl ): d =
2
2
Figure 3. A view of the structure of the cation 7 (thermal ellipsoids set
at 20% probability) showing a three-cation aggregate. Phenyl groups
are omitted for clarity. Selected bond lengths [Š] and angles [8]: Au1-C1
133.5–126.3 (Ph and Py),59.7 (s,CN C(CH ) ),59.0 (s,CN C(CH ) ),
3
3
3
3
1
61.8 (t, J(P,C) = 49,P 2CPy,30.7 (s,CNC( CH ) ) 29.9 ppm (s,
3
3
CNC(CH ) ). Resonance for CNC(CH ) not observed.
3
3
3 3
2
.100(19), Au1-Cl1 2.326(5), C1-I1 2.171(18), C1-P1 1.837(12); P1-Ru1-
P1 71.48(18), C1-Au1-Cl1 178.7(5), P1-C1-P1 97.4(9), P1-C1-Au1
04.4(7), P1-C1-I1 122.4(6), Au1-C1-I1 103.7(8).
4-(BF ) : A solution of 1-I (0.1 g,0.093 mmol) and THT (1 mL) in
THF (30 mL) was added through a canula to a Schlenk containing
4 2
1
AgBF (0.062 g,0.318 mmol). The mixture was stirred for 20 min and
4
then filtered and the filtrate concentrated to 15 mL to afford white
crystals of the compound,yield: 0.056 g (56%). Elemental analysis
(
5
(
%) calcd for C H N B F P RuS: C 54.61,H 5.99,N 5.20; Found: C,
49 64 4 2 8 2
van der Waals radii of both atoms (3.64 Š). Some activation is
À1
4.32; H,5.96; N,5.09; IR (CH Cl ): ~n = 2214 (m),2172 cm
(vs)
2
2
also observed in the CÀI bond in 7 (2.177(18) Š) compared to
3
1
1
CNtBu);
P{ H} NMR (121.5 MHz,CD Cl ): d = 0.38 ppm;
2
2
[
16]
1
coordinated diphosphanyliodomethanide (2.115(4) Š). All
these structural data indicate that 7 can be considered an
isolated intermediate for the formation of transient carbene 2
by halide abstraction from 1 with metal fragments. Addition-
ally the solid structure of 7 is of interest in forming
supramolecular triangular aggregates,with central I···I con-
tacts and peripheral CÀH···Cl hydrogen bonds (Figure 3).
H NMR (300 MHz,CD Cl ): d = 7.7–7.6 (20H,Ph),3.46 (m,2H,
2 2
tht),1.85 (m,2H,tht),1.82 (m,4H,tht) 1.55 (s,18H,CN
.15 ppm (s,18H,CN tBu).
-(ClO ) : AgClO (0.025 g,0.12 mmol) was added to a solution
tBu),
1
5
4
2
4
of 1-I (0.05 g,0.048 mmol) in CH 2Cl2 (10 mL). The mixture was
stirred for 10 min in the absence of light. After filtration,the solvent
was removed from the filtrate in vacuo and the residue recrystallized
from CH Cl /diethyl ether affording yellow crystals,yield: 0.036 g
(73%). Elemental analysis (%) calcd for C45
5
2
2
Table 1 shows some selected results of the calculations
H
56
N
4
Cl
2
O
9
P
2
Ru: C
Cl ):
2
+
2.43,H 5.47,N 5.43; Found: C,52.35; H,5.31; N,5.29; IR (CH
performed on the carbene [Ru(CNH) (PH ) CD] (2b),a
2
2
4
2 2
À1
À1
31
1
~
(s) (CNtBu),1721 cm
(m) (CO); P{ H}
model structure obtained from 2 by replacing tBu and Ph
1
[
9]
Cl
2
2
): d = 76.2 ppm; H NMR (300 MHz,
substituents by hydrogen atoms. The optimized structure
shows a perfect C2v symmetry in the highest levels of
calculation,both for singlet and triplet states,although for
the triplet state PÀC distances are clearly longer (1.788 Š)
tBu),0.95 ppm (s,
8H,CN tBu); C NMR (75.5 MHz,CD Cl ): d = 134–126 (Ph),216.6
2
2
13
1
(
2
2
1
t, J(P,C) = 16 Hz) P CO,61.4 (s,CN C(CH ) ),60.6 (s,CN C(CH ) ),
2 3 3 3 3
30.5 (s,CNC( CH ) ) 29.3 ppm (s,CNC( CH ) ). Resonance for
CNC(CH
3
3
3 3
and P-C-P angles are much smaller (113.18) than for the
singlet ground state (the values of which are shown in
Table 1). These results are much in line with those found for
other symmetrically substituted cyclic diphosphanylcar-
3 3
) not observed.
6
-(BPh ) : A solution containing 1-I (0.09 g,0.08 mmol) and
4
2
water (4 mL,0.22 mmol) in CH 2Cl2 (20 mL) was added through a
canula to AgBF (0.08 g,0.4 mmol) placed in a Schlenk previously
cooled to À758C and covered from the light. The mixture was stirred
for 10 min and then allowed to warm to room temperature and stirred
for a further hour. Filtration of the solution and evaporation of the
solvent from the filtrate afforded a white solid of 6-(BF ) Yield:
4
[
6b]
benes,
and clearly differ from symmetrically substituted
[
6a]
acyclic diphosphanylcarbenes, which prefer an asymmetric
PÀC multiple-bond phosphorus vinyl ylide structure.
4
2
Angew. Chem. Int. Ed. 2003, 42, 4767 –4771
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ꢀ 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
4769

Communications
0
.086 g (70%). To obtain suitable crystals for an X-ray diffraction
structures for both singlet and triplet states. Further calculations
were made by using DFT methods with the B3LYP hybrid
study,a metathesis of the anion was performed by treating a CH Cl /
MeOH solution of the compound with an excess of NaBPh4.
Elemental analysis (%) calcd for C H N B OP Ru: C 75.86,H
2
2
[
17b]
functional
and increasing the size of the basis set from the
[
17c]
9
3
98
4
2
2
quasi-relativistic pseudo-potential LanL2DZ basis set
and the standard 6-31G* basis set
H,N,and P),used in a first round,to the 3-21 + G*
for Ru
for all the other atoms (C,
[
17d]
6
.70,N 3.80; Found: C 75.79; H 6.45,N 4.02; IR (CH Cl ): ~n = 2223
2
2
À1
31
1
[17e]
(w),2181 (s),2164 cm
(sh) (CNtBu); P{ H} NMR (121.5 MHz,
basis set
for the latter
2
2
[17f,g]
CD Cl ): d = 67.7 (d, J(P,P) = 29 Hz),41.4 ppm (d, J(P,P) = 29 Hz);
for the former and the 6-311 + + G** basis set
2
2
1
H NMR (300 MHz,CD Cl ): d = 8.0–7.4 (60H,Ph),4.01 (dd,
used in the final round. All calculated structures represent real
minima as harmonic frequencies calculated at the same levels of
theory showed no imaginary frequencies. Scaled zero-point
energies (ZPE) were added to the final electronic energies to
2
2
2
2
J(P,H) = 11, J(P,H) = 9 Hz,2H,CH 2),1.73 (s,9H,CN tBu),1.53 (s,
H,CN tBu),1.10 ppm (s,18H,CN tBu).
-[Au(Cl)(I)]: [Au(Cl)(tht)] (0.031 g,0.096 mmol) was added to a
9
7
solution of 1-I (0.050 g,0.048 mmol) in THF (12 mL) and the resulting
mixture stirred for 10 min. The solution was then concentrated to
obtain singlet–triplet splittings (DE ) and electron affinities
ST
[
17h]
(EA). Scale factor used for ZPE: 0.9804.
10] Compound 1-I was prepared from [Ru(CNtBu) {(PPh ) CH ]-
6
0
mL and let to stand over night to afford yellow crystals,yield:
[
4
2
2
2
À1
.065 g (90%). IR (CH Cl ): ~n = 2215 (s),2177 cm
(vs) (CNtBu);
2
2
(ClO ) in a similar way to that described for the synthesis of
4 2
3
1
1
1
P{ H} NMR (121.5 MHz,CD Cl ): d = 13.4 ppm; H NMR
´
[Mn(CO) {(PPh ) CI}]: J. Ruiz,V. Riera,M. Vivanco,S. Garci a-
4 2 2
2
2
(
300 MHz,CD 2Cl ): d = 7.7–7.4 (20H,Ph),1.63 (s,18H,CN
tBu),
´
2
Granda,M. R. Di az, Organometallics 1998, 17,4562.
1
.44 (s,9H,CN tBu),0.99 ppm (s,9H,CN tBu).
[
[
11] H. Keller,G. Maas,M. Regitz, Tetrahedron Lett. 1986, 27,1903.
12] Carbene–pyridine adducts have been spectroscopically charac-
terized and used as evidence for the formation of carbenes: J. L.
Received: June 24,2002
Revised: June 23,2003 [Z19604]
Wang,J. P. Toscano,M. S. Platz,V. Nikolaev,V. Popik,
J. Am.
Chem. Soc. 1995, 117,5477; J. P. Toscano,M. S. Platz,V.
Nikolaev,V. Popic, J. Am. Chem. Soc. 1994, 116,8146.
Keywords: carbene ligands · density functional calculations ·
P ligands · ruthenium
.
[
13] Crystal data for [3-(BF ) ] ·[(AgPy )·(BF )]·(CH Cl ) ·(H O)
4
2
2
2
4
2
2
3
2
2
(
C113H142AgB Cl F N O P Ru ): M = 2781.03,monoclinic,
5 6 20 12 2 4 2 r
space group P2 /n, a = 16.8409(1), b = 14.9234(2), c =
1
3
5
1
5
3.8328(5) Š, B = 93.830(1)8, V= 13499.2(2) Š , Z = 4, 1
.368 gcm , F(000) = 5688,Cu Ka radiation (l = 1.5418 Š), m =
.134 mm ; crystal dimensions 0.42 ” 0.17 ” 0.27 mm. Data col-
=
calcd
[
1] For recent reviews see: a) A. J. Arduengo, Acc. Chem. Res. 1999,
2,913; b) D. Bourissou,O. Guerret,F. P. Gabbaï,G. Bertrand,
À3
3
À1
Chem. Rev. 2000, 100,39 – 91; c) W. A. Herrmann, Angew.
Chem. 2002, 114,1326; Angew. Chem. Int. Ed. 2002, 41,1290.
lection was performed at 120(2) K on a Nonius KappaCCD
single crystal diffractometer. Crystal structure was solved by
direct methods (SHELXS-97) and refined using full-matrix least
[
2] a) R. W. Alder,P. R. Allen,M. Murray,A. G. Orpen,
Chem. 1996, 108,1211; Angew. Chem. Int. Ed. Engl. 1996, 35,
121; b) A. J. Arduengo,J. R. Goerlich,W. J. Marshall, J. Am.
Angew.
2
squares on F (SHELXL-97). Non-hydrogen atoms were aniso-
1
tropically refined,except for some atoms on three disordered
anions and the solvent molecules. Hydrogen atoms were geo-
metrically placed and left riding on their parent atoms. Some
restrains on the disordered anions and one solvent molecule
Chem. Soc. 1995, 117,11027; c) M. K. Denk,A. Thadani,K.
Hatano,A. J. Lough, Angew. Chem., 1997, 109,2719; Angew.
Chem. Int. Ed. Engl. 1997, 36,2607; d) D. Enders,K. Breuer,G.
Raabe,J. Runsink,J. H. Teles,J. Melder,K. Ebel,S. Brode,
Angew. Chem. 1995, 107,1119; Angew. Chem. Int. Ed. Engl.
2
2
were applied. wR (F > 2s(F )) = 0.1889,conventional R [on F
2
2
2
values for 24246 reflections] (F > 2s(F )) = 0.0695 for 1452
1
995, 34,1021 – 1023.
3] A. Igau,A. Baceiredo,G. Trinquier,G. Bertrand, Angew. Chem.
989, 101,617; Angew. Chem. Int. Ed. Engl. 1989, 28,621. For a
parameters. Crystal data for 4-(BF4) (C H B F N P RuS):
[
2
49 64
2
8
4 2
M = 1077.73,monoclinic,space group P2 /c, a = 14.5238(5), b =
1
r
1
2
0.9879(8), c = 17.9357(6) Š, b = 99.508(2)8, V= 5392.1(3) Š3,
review on phosphanylcarbenes see: D. Bourissou,G. Bertrand,
Adv. Organomet. Chem. 1999, 44,175.
À3
Z = 4, 1calcd = 1.328 gcm , F(000) = 2232,Cu Ka radiation (l =
1
À1
.5418 Š), m = 3.816 mm
;
crystal dimensions 0.25 ” 0.10 ”
[
4] N. Merceron,K. Miqueu,A. Baceiredo,G. Bertrand,
J. Am.
0.10 mm. Data collection was performed at 120(2) K on a
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105,1245; Angew. Chem. Int. Ed. Engl. 1993, 32,1167.
2
2
left riding on their parent atoms. wR2 (F > 2s(F )) = 0.2001,
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(
[
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I
3
À3
8] Similar Mn carbenes are apparently implicated in the formation
V= 10689.2(3) Š , Z = 6, 1calcd = 1.489 gcm , F(000) = 4596,
À1
of diphosphanylketenimines,which open routes to an unprece-
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Crystal structure was solved by direct methods and refined using
´
7,3835; b) J. Ruiz,F. Marqui nez,V. Riera,M. Vivanco,S.
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1
2
´
´
full-matrix least squares on F . All non-hydrogen atoms were
´
anisotropically refined,except for the chlorine atom in the
counteranion which is disordered in three positions. In the
counteranion the gold atom shows positional disorder. Hydro-
gen atoms were geometrically placed and left riding on their
parent atoms. Some restrains on a phenyl group and the solvent
Angew. Chem. Int. Ed. 2000, 39,1821; c) J. Ruiz,F. Marqui nez,V.
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,
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9] The calculations were performed with the Gaussian98 program
2
[
[
17a]
package.
The experimental geometry of 3 was used as a
2
2
starting point for 2b and a preliminary calculation using the HF/
LanL2DZ level of theory converged to the first optimized
molecule were applied. wR2 (F > 2s(F )) = 0.2498,conven-
2
2
tional R [on F values for 6792 reflections] (F > 2s(F )) = 0.0864
4
770
ꢀ 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2003, 42, 4767 –4771

Angewandte
Chemie
for 322 parameters. CCDC-187344 (3),CCDC-211797 ( 4),
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mentary crystallographic data for this paper. These data can be
obtained free of charge via www.ccdc.cam.ac.uk/conts/retrie-
ving.html (or from the Cambridge Crystallographic Data Centre,
12 Union Road,Cambridge CB21EZ,UK; fax: ( + 44)1223-336-
033; or deposit@ccdc.cam.ac.uk).
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2
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3
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´
[
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