Synthesis and characterization of mononuclear and dinuclear manganese bis-acetylide complexes

Article abstract of DOI:10.1002/zaac.200801423

The symmetric d⁵ trans-bis-alkynyl complexes {Mn[(Me) ₂P(CH₂)_nP(Me)₂]₂(C= CC₆H₄R)₂} (n = 2, R = -C=CTIPS (2a); n = 3, R = -C=CTIPS (2b); n = 2, R = F (4); n

Full text of DOI:10.1002/zaac.200801423

ARTICLE
DOI: 10.1002/zaac.200801423
Synthesis and Characterization of Mononuclear and Dinuclear Manganese
Bis-acetylide Complexes
Thorsten Fritz,[a] Helmut W. Schmalle,[a] Olivier Blacque,[a] Koushik Venkatesan,[a] and
Heinz Berke*[a]
Keywords: Mixed-valent compounds; Molecular devices; Molecular wires; Nanotechnology; Single-electron devices
Abstract. The symmetric d5 trans-bis-alkynyl complexes
{Mn[(Me)2P(CH2)nP(Me)2]2(CϵCC6H4R)2} (n 2,
-CϵCTIPS (2a); n ϭ 3, R ϭ -CϵCTIPS (2b); n ϭ 2, R ϭ F (4); neutral
of dmpe. Deprotection of the TIPS group with TBAF gave
ϭ
R
ϭ
complex [IMn(dmpe)2(CϵCC6H4CϵCH)] (6) in 94 % yield. The
dinuclear
complexes
MnII/MnII
compounds
n
ϭ
3; -CϵCTIPS) were prepared by the reaction of
{[Mn((Me)2P(CH2CH2)P(Me)2)2(CϵCC6H4R)]2(µ-C4)} (R ϭ H,
Me, n-pentyl, F) were prepared by the direct reaction of
[Mn(dmpe)2Br2] with two equivalents of the corresponding acetyl-
ide LiCϵCC6H4R (R ϭ F, -CϵCTIPS). The reaction of com- {[Mn((Me)2P(CH2CH2)P(Me)2)2I]2(µ-C4)} with the corresponding
pounds 2a, 2b and 4 with [Cp2Fe][PF6] yielded the corresponding
LiCϵCC6H4R (R ϭ H, n-pentyl, F). These MnII/MnII dinuclear
compounds were further oxidized to the mixed-valent complexes
d4 complexes {Mn[(Me)2P(CH2)nP(Me)2]2(CϵCC6H4R)2}[PF6]
(n ϭ 2, R ϭ -CϵCTIPS, [2a]ϩ; n ϭ 3, R ϭ -CϵCTIPS, [2b]ϩ; and the dicationic complexes using [Cp2Fe][PF6]. All complexes
n ϭ 2, R ϭ F, [4]ϩ; n ϭ 3; -CϵCTIPS). The unsymmetrically
have been characterized by NMR, IR, and Raman spectroscopy.
substituted trans-iodo-alkynyl complex [IMn(dmpe)2(CϵCC6H4- X-ray diffraction studies were carried out on complexes 1c, 2a, 4,
CϵCTIPS)] (5) was obtained by treating MeCpMn(dmpe)I with [4]ϩ, and 6.
one equivalent of H-CϵCC6H4-CϵCTIPS in the presence
stituted manganese end groups and a C4-spacer [26Ϫ29].
In addition to the above reasons, the LmMnϪC4ϪMnLm
Introduction
The development of molecular devices requires the prep-
aration of functional materials with suitable properties
[1Ϫ3]. π-Conjugated “conducting” units containing electro-
chemically active transition-metal end groups, such as
LmM-(CϵC)n-MLm are basic constituents for electronic
materials [4Ϫ6]. Research into the synthesis and electronic
properties of metal alkynyl complexes and polymers con-
tinues to develop as a key area of organometallic chemistry
[7Ϫ17]. Owing to its high stability, ease of functionaliz-
ation, and well-defined electrochemistry, transition-metal
units have been widely used as redox-active centers that are
linked together with a wide variety of structural units such
as saturated and unsaturated carbon bridges, delocalized
fused rings, and polymeric and dendritic backbones
[18Ϫ56]. In particular, their rigid rod architectures and con-
jugated backbones have been studied in the field of linear
and non-linear optics, liquid crystallinity, and photovoltaic
cells [24, 25]. We expect that electronic properties of materi-
als with low energy work functions could be reasonably sat-
isfied by molecular units with electron-rich phosphane sub-
systems were selected as target molecules, because a build-
up of Mn-di- and oligonuclears seemed to be synthetically
feasible by acetylide substitution processes [27]. We have
shown through our recent studies that systems of the type
LmMnϪC4ϪMnLm can be achieved by coupling of Mn-C2
units, such as Mn-alkynyl and Mn-vinylidene moieties. For
instance, we have published the synthesis of redox-active
dinuclear complexes of the type {[Mn(dmpe)2(X)]2(µ-
C4)}nϩ (X ϭ I, CϵCH, CϵCϪCϵCSiMe3 and n ϭ 0Ϫ2),
which were either obtained by the reaction of two equiva-
lents of [IMn(MeCp)(dmpe)] [dmpe ϭ 1,2-bis(dimethyl-
phosphanyl)ethane] with Me3SnϪC4ϪSnMe3 and dmpe
and subsequent acetylide substitution, or by an in situ
CϪC coupling of [MnIII(dmpe)2(CϵCH)(CϵC)] units
similar to the Eglinton and McCrae oxidative coupling of
acetylenic compounds [26Ϫ29]. We had earlier suggested
from DFT calculations and experimental evidence that
the terminal end group (X) in these kind of complexes
{[Mn(dmpe)2(X)]2(µ-C4)}nϩ
(X
ϭ
I,
CϵCH,
CϵCϪCϵCSiMe3 and n ϭ 0Ϫ2), have less bearing or in-
fluence on the communication between the two metal cen-
ters [27]. However, the functionality and reactivity of the
terminal end groups does matter considering the fact of
further utilizing these molecules for the build up of longer
oligonuclear and attaching these molecules to electrode sur-
faces for single-molecule conductivity measurements [44].
* Prof. Dr. H. Berke
E-Mail: hberke@aci.uzh.ch
[a] Institute of Inorganic Chemistry
Winterthurerstraase 190
8057, Zürich, Switzerland
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ARTICLE
The solubility of these dinuclear complexes is very much
influenced by the substituents on the phosphorus ligand
and also on the terminal end groups. Additionally, the sub-
stituents on the phosphorus atom have an effect on the re-
dox properties of these kind [Mn(dmpe)2(CϵCSiR3)X]ϩ of
molecules [27]. This insight propelled us to gain access to
new dinuclear complexes bearing end groups of the type
-CϵCϪR (R ϭ H, Me, n-pentyl, F).
Results and Discussion
Complexes of the type ML2X2 (M ϭ Mn, L ϭ dmpe,
X ϭ Br, I) are valuable starting materials for the synthesis
of bis-acetylide complexes by simple addition of lithium
acetylides [57Ϫ59]. It is well known from previous studies
that substituents on the phosphorus ligands have a signifi-
cant effect on the redox properties [27]. Hence the manga-
nese complexes 1b and 1c bearing a dmpp [dmpp ϭ 1,3-
bis(dimethylphosphanyl)propane] ligand were synthesized
starting from manganese iodide or manganese bromide.
Both complexes were isolated in excellent yields. The 1H
NMR spectrum of 1b showed broad resonances for the pro-
tons in a more downfield region at around 40.9 (PCH2),
32.4 [P(CH3)2], 11.6 (PCH2CH2) ppm than the 1c com-
plexes which had resonances at 18.9 and 4.6 ppm for the
Figure 1. Molecular structure of 1c with displacement ellipsoids
drawn at the 50 % probability level (all hydrogen atoms are omitted
for clarity). The atoms labeled with the suffix a are generated by
the symmetry operation (Ϫx, 1Ϫy, Ϫz). Selected bond lengths /A
and angles /°: Mn1ϪBr1 2.6512(5), Mn1ϪP1 2.6718(11);
Br1ϪMn1ϪBr1a 180.0, Br1ϪMn1ϪP1 87.38.
˚
methylene and methyl protons. The structure of complex 1c method. All the derivatives 2a, 2b and 4 are soluble in non-
was unequivocally established by an X-ray diffraction study polar solvents such as pentane, Et2O etc. The 1H NMR
(Figure 1).
spectra of 2a and 2b showed a broad signal at 17.6 and
Paramagnetic d5 trans-bis-alkynyl manganese com- Ϫ2.8 ppm for the aromatic protons. The protons of the
pounds [Mn((Me)2P(CH2)nP(Me)2)2(CϵCC6H4R)2] [n ϭ 2, dmpe and dmpp in 2a and 2b appeared as a broad signal
R ϭ -CϵCTIPS, (2a); n ϭ 3, R ϭ -CϵCTIPS (2b); n ϭ 2, at Ϫ15.6. These values are characteristic for these types of
R
ϭ F
(4)] can be prepared by the reaction of low spin d5 complexes. The SiiPr3 groups of 2a and 2b were
{Mn[(Me)2P(CH2)nP(Me)2]2I2} (n ϭ 2, 1a; n ϭ 3, 1b) with identified as broad resonances at 1.3 ppm.
two equivalents of LiCϵCR (R ϭ -CϵCTIPS, R ϭ F)
The structure of complexes 2a (Figure 2) and 4 (Figure
(Scheme 1, 2). Similar kinds of complexes were obtained by 3) was established by X-ray diffraction studies. Complex 2a
two other methods by the reaction of [MnCp2] (Cp ϭ C5H5, crystallizes either in an orthorhombic (2a-1) or in a triclinic
C5H4Me) with two equivalents of ECϵCSiR3 (E ϭ H, (2a-2) system. Figure 2 shows the molecular structure of
SnMe3) in the presence of dmpe or by SiR3 metathesis [27, 2a-1. The metal exhibits a pseudo-octahedral coordination
28]. However, the yields were far better using the former with both acetylide ligands in trans positions, and the four
Scheme 1.
Scheme 2.
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Z. Anorg. Allg. Chem. 2009, 1391Ϫ1401

Synthesis and Characterization of Manganese Bis-acetylide Complexes
Figure 2. Molecular structure of 2a-1 with displacement ellipsoids drawn at the 30 % probability level (all hydrogen atoms are omitted
˚
for clarity). Selected bond lengths /A and angles /°: Mn1ϪC13 1.985(5), Mn1ϪC32 1.999(6), C13ϪC14 1.182(6), C21ϪC22 1.209(6),
C32ϪC33 1.184(7), C40ϪC41 1.202(6), C22ϪSi1 1.854(6), C41ϪSi2 1.854(6); C32ϪMn1ϪC13 179.0(3).
Figure 3. Molecular structure of 4 with displacement ellipsoids drawn at the 30 % probability level (all hydrogen atoms are omitted for
˚
clarity). Selected bond lengths /A and angles /°: Mn1ϪC13 1.952(3), C13ϪC14 1.227(4), C21ϪC22 1.217(4); C13ϪMn1ϪC21 179.84(15).
phosphorous atoms defining an equatorial plane. The CϵC
˚
˚
bond in 2a-1 is 1.182(6) A for C13ϪC14 and 1.184(7) A for
C32ϪC33 similar to that found in related complexes [27].
Compounds 2a and 4 were treated with [FeCp2][PF6] to
give the oxidized complexes [2a]ϩ and [4]ϩ in high yields.
The H NMR spectrum of [2a]ϩ showed a significant shift
1
in the resonances of the phenyl protons to 39.9 and Ϫ58.3
and of methyl and methylene protons to Ϫ29.1 and
Ϫ38.6 ppm, respectively. The solid-state structure of
[4]ϩ was also determined by an X-ray diffraction study
(Figure 4).
The deprotection of the TIPS group in [2a]ϩ with
[Bu4N]FϪ (5 % H2O) gave the neutral MnII compound 3a
1
in 60 % yield (Scheme 3). The H NMR spectrum revealed
resonances characteristic of the acetylide protons at δ ϭ
2.51 as a singlet. The resonances for the aromatic protons
and dmpe protons appear at 17.0 and Ϫ2.9 ppm and
Ϫ14.8 ppm, respectively. These signals are characteristic for
paramagnetic MnII complexes [29]. This complex is unique
in the sense that it has two reactive end groups that can be
Figure 4. View of the molecular structure of one of the three
crystallographically independent molecules of [4]ϩ with displace-
ment ellipsoids drawn at the 30 % probability level (all hydrogen
atoms are omitted for clarity). Selected average bond lengths /A
and angles /°: Mn1ϪCα 1.943, CαϪCβ 1.229; CαϪMn1ϪCα 178.0.
˚
Scheme 3.
Z. Anorg. Allg. Chem. 2009, 1391Ϫ1401
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T. Fritz, H. W. Schmalle, O. Blacque, K. Venkatesan, H. Berke
ARTICLE
further used to access oligonuclears in a precise fashion.
Compound 3a was oxidized to the MnIII using [FeCp2][PF6]
in 92 % yield.
Thus far, we had described the synthesis of unsymmetri-
cally substituted trans-bis-alkynyl manganese complexes
using manganese vinylidene complexes as starting materials.
Another seemingly convenient route for obtaining the re-
quired asymmetrically substituted MnII trans-bis-alkynyl
manganese complexes might be envisaged as the stepwise
substitution of dihalo complexes [Mn(dmpe)2X2](X ϭ Br,
I) through the intermediacy of appropriate monoacetylide
species trans-[Mn(dmpe)2(X)(CϵCR)] (X ϭ Br, I; R ϭ H,
SiR3) [27]. However, these trans-halo-alkynyl manganese
compounds could not be prepared by this route; all at-
tempts invariably led to ligand proportionation with mix-
tures of the corresponding [Mn(dmpe)2X2] (X ϭ Br, I) and
[Mn(dmpe)2(CϵCR)2] complexes.
Figure 5. Molecular structure of 6 with displacement ellipsoids
drawn at the 50 % probability level (all hydrogen atoms except H22
˚
are omitted for clarity). Selected bond lengths /A and angles /°:
Mn1ϪC13 1.905(5), I1ϪMn1 2.7296(8), C13ϪC14 1.218(5),
C21ϪC22 1.194(9); C3ϪMn1ϪI1 176.73(16), C14ϪC13ϪMn1
As an alternative, conversion of the complex 176.3(4).
[Mn(MeC5H4)(dmpe)I] with HϪCϵCϪC6H4ϪCϵCTIPS
and dmpe was considered, which indeed yielded the ex-
pected d5 paramagnetic trans-iodo-alkynyl compound
[Mn(dmpe)2(CϵCC6H4ϪCϵCTIPS)] (5) isolated as a pure MnϪC4ϪMn unit [27]. In this paper, we utilized simple
1
red brown solid in 73 % yield. The H NMR spectrum of 5 metathesis reaction involving addition of various lithium
in C6D6 shows resonances at ϭ 18.9 and Ϫ1.6 ppm for the acetylides to the IϪMnϪC4ϪMnϪI fragment thereby
aromatic protons and broad signal at Ϫ17.2 ppm for the developing dinuclear complexes with different end
methyl and methylene protons of the dmpe. Further reac- groups (Scheme 5). Addition of two equivalents of
tion of 5 with TBAF (5 % H2O) yielded the alkyne termin- the LiCϵCC6H4X (X
ated compound [Mn(dmpe)2(CϵCϪC6H4ϪCϵCH)] (6) in {[Mn(dmpe)2I]2(µ-C4)} gave in good yields the correspond-
94 % yield (Scheme 4). The structure of 5 was confirmed by ing
alkyne terminated dinuclear complexes
ϭ H, Me, n-pentyl, F) to
single-crystal X-ray diffraction (Figure 5). The manganese {[Mn(dmpe)2(CϵCC6H4X)]2(µ-C4)} [X ϭ H (7a); Me (7b);
1
center is in a pseudo-octahedral environment, with the n-pentyl (7c); F (7d)]. The H NMR spectrum of the com-
alkynyl and iodo ligands in a trans arrangement. The pounds 7aϪd show broad resonances between 15 to 16 ppm
C13ϪC14 and MnϪC13 distances of 1.212(4) and and Ϫ4 to Ϫ5 ppm for the aromatic protons. The signals
˚
˚
1.937(3) A and the MnϪI distance of 2.7198(4) A compare for the dmpe protons appear between Ϫ15 and Ϫ16 ppm.
well with the corresponding parameters found for related In a quantitative fashion, the paramagnetism of complexes
[Mn(dmpe)2(alkynyl)2] species and the MnϪC13ϪC14 7aϪd was confirmed by the temperature dependence of the
angle [178.9(3)°] is practically linear as in numerous other 1H NMR spectra. The chemical shifts in the temperature
LnMϪCϵCR arrangements [26Ϫ29].
Preparation of [Mn]؊C4-[Mn] rigid-rod species: We re-
range Ϫ70 to 20 °C follow Curie-Weiss behavior.
The redox-active neutral compounds 7aϪd can be oxid-
ported the carbonϪcarbon coupling of two molecules of ized further to the corresponding mixed-valent complexes
[Mn(dmpe)2(CϵCH)][PF6] establishing
a
dinuclear [7aϪd]ϩ and the dicationic species [7aϪd]2؉ applying one
Scheme 4.
Scheme 5.
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Z. Anorg. Allg. Chem. 2009, 1391Ϫ1401

Synthesis and Characterization of Manganese Bis-acetylide Complexes
obtained mononuclear monofunctionalized acetylide
manganese complexes are envisaged to be valuable starting
materials for the construction of trinuclear or oligonuclear
compounds.
Experimental Section
General: All operations were carried out under nitrogen using
Schlenk and vacuum-line techniques or in a glove box, model MB-
150 B-G. The following solvents were dried and purified by distil-
lation under nitrogen before use, employing appropriate drying/de-
oxygenating agents: tetrahydrofurane (Na/benzophenone), toluene
(sodium), CH2Cl2 (P2O5, with filtration through active Alox). IR
spectra were obtained with a Bio-Rad FTS instrument. Raman
spectra were recorded with a Renishaw Ramanscope spectrometer
(514 nm). EPR measurements were made with MPMS-5 S and
PPMS-6000 instruments. 1H NMR spectra were recorded with
Unity 300 or Varian Gemini 200 spectrometers at 300 or 200 MHz,
respectively. 1H NMR chemical shifts are reported in ppm units
with respect to the signals of residual protons in the solvents and
referenced to TMS. C and H elemental analysis were carried on
with a LECO CHN-932 microanalyzer.
{trans-Bis[1,2-bis(dimethylphosphanyl)propane]diiodomanga-
nese(II)}, [MnI2(dmpp)2] (1b): Anhydrous MnI2 (618 mg,
2.00 mmol) was suspended in THF (20 mL) and dmpp (657 mg,
4.00 mmol) was added. The reaction mixture was stirred for 12 h
after which the resulting colorless solution was filtered through Ce-
lite and the solvents were evaporated under vacuum to give a color-
less powder. Crystallization at Ϫ30 °C in THF gave single crystals
suitable for a X-ray diffraction study. Yield 1.24 g (1.94 mmol,
Scheme 6.
or two equivalents of [Cp2Fe][PF6] (Scheme 6). Both the
96 %). C14H36I2MnP4 (637.08): calcd. C 26.39, H 5.70; found C
1
mono- and dicationic complexes are soluble in only polar 26.54, H 5.62. H NMR ([D8]THF, 200 MHz, 19 °C): δ ϭ 40.9 (s,
8 H, PCH2), 32.4 [s, 24 H, P(CH3)2], 11.6 (s, 4 H, PCH2CH2).
solvents such as THF and CH2Cl2. In striking contrast to
the diamagnetic MnIIIϪC4ϪMnIII compounds reported
earlier with silylacetylenyl end groups [26, 27], the 1H NMR
spectra of [7aϪd]2؉ displayed paramagnetic resonances
with shifted downfield aromatic protons and shifted upfield
protons of the dmpe ligand in comparison with the mixed-
valent complexes [7aϪd]ϩ and the neutral species [7aϪd].
{trans-Bis[1,2-bis(dimethylphosphanyl)propane]dibromomanga-
nese(II)}, [MnBr2(dmpp)2] (1c): dmpp (657 mg, 4.00 mmol) was ad-
ded to MnBr2 ·2THF (718 mg, 2.00 mmol) in THF (20 mL). The
reaction mixture was stirred for 12 h after which the resulting color-
less solution was filtered through Celite and the solvents were eva-
porated under vacuum to give a colorless powder. Crystallization
at Ϫ30 °C in THF gave single crystals suitable for a X-ray diffrac-
tion study. Yield. 1.03 g (1.90 mmol, 95 %). C14H36Br2MnP4
1
Conclusions
(543.08): calcd. C 30.96, H 6.68; found C 30.66, H 6.91. H NMR
([D8]THF, 200 MHz, 20 °C): δ ϭ 18.9 [s, 32 H, (CH3)2PCH2], 4.6
(s, 4 H, PCH2CH2).
A series of MnII and MnIII symmetric complexes of the
type {Mn[(Me)2(CH2)x(Me)2]2(CϵCC6H4R)2}nϩ (X ϭ 2, 3;
R ϭ -CϵCTIPS; F; n ϭ 0, 1) has been prepared. The reac-
tion of the symmetrically substituted trans-bis-alkynyl d4
manganese complexes produce with one equivalent of
{trans-Bis[1,2-bis(dimethylphosphanyl)ethane]bis[(4-(triisopropyl-
silyl)ethynyl)phenylethynyl]manganese(II)}, {[TIPS؊CϵC؊C6H4؊
CϵC]2(dmpe)2Mn} (2a): Butyllithium (1.6 ) in hexane (625 µL,
TBAF the desilylated complex {Mn[(Me)2P(CH2)2P(Me)2]2 1.00 mmol) was added to TIPSϪCϵCϪC6H4ϪCϵCϪH
(282.5 mg, 1.00 mmol) in THF (15 mL). The reaction mixture
was slowly warmed to room temperature, before being cooled
(CϵCC6H4ϪCϵCH)2}. The asymmetric trans-iodoalkynyl
complex {IMn[(Me)2(CH2)2(Me)2]2(CϵCC6H4ϪCϵCTIPS)}
which is obtained by the reaction of (CH3C5H4Mn(dmpe)I)
with HCϵCC6H4ϪCϵCTIPS and dmpe, reacts with TBAF
to yield the corresponding alkyne terminated complex
{IMn[(Me)2P(CH2CH2)P(Me)2]2(CϵCC6H4ϪCϵCH)}.
Dinuclear manganese complexes were prepared in a
to Ϫ30 °C.
TIPSϪCϵCϪC6H4ϪCϵCϪLi
After 30 min the
was
cooled
added
solution
dropwise
of
to
[MnI2(dmpe)2] (304 mg, 0.50 mmol) in THF (10 mL) at Ϫ30 °C.
The reaction mixture was stirred at room temperature for 1 h and
was evaporated under vacuum to yield a red brown solid. The solid
was extracted with pentane (5 ϫ 10 mL), filtered through Celite
and the solvent was evaporated under vacuo to give a solid. Yield
449 mg (0.489 mmol, 98 %). Crystallization at Ϫ30 °C in pentane
straightforward
fashion
by
the
reaction
of
{[Mn(dmpe)2I]2(µ-C4)} with LiCϵCC6H4R. All these com-
plexes exhibit characteristic paramagnetic behaviour. The gave single crystals suitable for an X-ray diffraction study.
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T. Fritz, H. W. Schmalle, O. Blacque, K. Venkatesan, H. Berke
ARTICLE
C50H82MnP4Si2 (918.19): calcd. C 65.40, H 9.00; found C 65.23, H tion mixture was stirred at that temperature for 1 h during which
8.74. 1H NMR ([D8]THF, 200 MHz, 20 °C): δ ϭ 17.2 (s, 4 H, the color changed from deep green to dark red. The solvent was
ArHm), 1.2 {s, 6 H, Si[CH(CH3)2]3}, 1.08 {s, 36 H, Si[CH(CH3)2]3}, evaporated under vacuum to give a solid. The solid was washed
Ϫ3.0 (s, 4 H, ArHo), Ϫ14.7 [s, 32 H, CH2P(CH3)2]. Raman: with diethyl ether (10 mL) and extracted with toluene (3 ϫ 5 mL)
ν(TIPSϪCϵC) ϭ 2147 (m), ν(CϵCϪMn) ϭ 2022 (m), ν(Cϭ
and filtered through Celite. The solvent was evaporated to give a
C)Ar ϭ 1591 (vs), ν(CϭC)Ar ϭ 1171 (s), ν(PϪC) ϭ 946 (m), red brown solid. Yield 75 mg (0.124 mmol, 62 %). C32H42MnP4
1
ν(HCϭCH)Ar ϭ 836 (m), ν(MnϪC) ϭ 650 (m), ν(MnϪP) ϭ 345 (605.51): calcd. C 63.47, H 6.99; found C 63.15, H 7.31. H NMR
(s) cmϪ1. IR (KBr): ν(CϪH) ϭ 2942 (s), 2902 (s), 2864 (s),
([D8]THF, 200 MHz, 22 °C): δ ϭ 17.0 (s, 4 H, ArHm), 2.31 (s, 2 H,
1998 (vs), CϵCH), Ϫ2.9 (s, 4 H, ArHo), Ϫ14.8 [s, 32 H, CH2P(CH3)2].
ν(CϭC)Ar ϭ 1589 (s), ν(PϪC) ϭ 995 (w), 936 (s), δ(HCϭCH)Ar ϭ Raman: ν(HϪCϵC) ϭ 2100 (m), ν(CϵCϪMn) ϭ 2010 (m),
ν(TIPSϪCϵC)
ϭ 2146 (m), ν(CϵCϪMn) ϭ
835 (s) cmϪ1
.
ν(CϭC)Ar ϭ 1593 (vs), ν(CϭC)Ar ϭ 1166 (s), ν(PϪC) ϭ 948 (m),
ν(HCϭCH)Ar ϭ 816 (m), ν(MnϪC) ϭ 649 (m), ν(MnϪP) ϭ 342
(s) cmϪ1. IR (KBr): ν(HϪCϵC) ϭ 3308 (m), ν(CϪH) ϭ 2962 (m),
2902 (m), ν(HϪCϵC) ϭ 2100 (w), ν(CϵCϪMn) ϭ 1992 (vs),
{trans-Bis[1,2-bis(dimethylphosphanyl)propane]bis[(4-triisopropyl-
silylethynyl)phenylethynyl]manganese(II)}, {[TIPS؊CϵC؊C6H4؊
CϵC]2(dmpp)2Mn} (2b): Butyllithium (1.6 ) in hexane (625 µL, ν(CϭC)Ar ϭ 1589 (s), ν(PϪC) ϭ 941 (m), δ(HCϭCH)Ar ϭ 841
1.00 mmol) was added to 1-ethynyl-4-(triisopropylsilyl)ethynylben-
zene (283 mg, 1.00 mmol) in THF (15 mL) at Ϫ30 °C. The reaction
mixture was slowly warmed to room temperature, before being
cooled again to Ϫ30 °C. After 30 min the cooled
(m) cmϪ1
.
{trans-Bis[1,2-bis(dimethylphosphanyl)ethane]-bis[(4-ethynyl)phenyl-
ethynyl]manganese(III)} Hexafluorophosphate, {[HCϵC؊C6H4؊
CϵC]2(dmpe)2Mn}[PF6], [3a]؉: CH2Cl2 (10 mL) was added to 3a
(182 mg, 0.30 mmol) and [Cp2Fe][PF6] (100 mg, 0.30 mmol) and
the reaction mixture was stirred for 30 min. The color changed
from deep red to dark green during this time. The reaction mixture
was evaporated under vacuo and washed with pentane (8 ϫ 5 mL)
and ether (3 ϫ 5 mL). The solid was extracted with THF (15 mL),
filtered through Celite and the solvents were evaporated under vac-
uum to give a green solid. Yield 207 mg (0.276 mmol, 92 %).
C32H42F6MnP5 (750.47): calcd. C 51.21, H 5.64; found C 51.34, H
5.91. 1H NMR ([D8]THF, 200 MHz, 20 °C): δ ϭ 39.7 (s, 4 H,
ArHm), Ϫ26.4 (s, 2 H, CϵCH), Ϫ29.4 (s, 8 H, PCH2), Ϫ38.7 [s,
24 H, P(CH3)2], Ϫ58.2 (s, 4 H, ArHo). Raman: ν(HϪCϵC) ϭ 2152
(w), ν(CϵCϪMn) ϭ 2037 (vs), ν(CϭC)Ar ϭ 1593 (vs), ν(Cϭ
C)Ar ϭ 1174 (s), ν(HCϭCH)Ar ϭ 840 (w), ν(MnϪP) ϭ 337 (w)
cmϪ1. IR (KBr): ν(HϪCϵC) ϭ 3306 (m), ν(CϪH) ϭ 2950 (s),
2883 (s), ν(HϪCϵC) ϭ 2160 (m), ν(CϵCϪMn) ϭ 2035 (m), ν(Cϭ
TIPSϪCϵCϪC6H4ϪCϵCϪLi
was
added
dropwise
to
[MnI2(dmpp)2] (319 mg, 0.50 mmol) in THF (10 mL) at Ϫ30 °C.
The reaction mixture was stirred at room temperature for 1 h and
was evaporated under vacuo to yield a red brown solid. The solid
was extracted with pentane (5 ϫ 10 mL), filtered through Celite
and the solvent was evaporated under vacuum to give a dark red
solid. Yield 304 mg (0.321 mmol, 64 %). C52H86MnP4Si2 (946.24):
calcd. C 66.00, H 9.16; found C 65.71, H 8.91. 1H NMR (C6D6,
200 MHz, 22 °C):
δ ϭ 17.6 (s, 4 H, ArHm), 1.3 {s, 6 H,
Si[CH(CH3)2]3}, 1.10 {s, 36 H, Si[CH(CH3)2]3}, Ϫ2.8 (s, 4 H,
ArHo), Ϫ15.6 [s, 32 H, CH2P(CH3)2]. IR (KBr): ν(CϪH) ϭ 2940
(s), 2903 (s), 2863 (s), ν(TIPSϪCϵC) ϭ 2142 (m), ν(CϵCϪMn) ϭ
1992 (s), ν(CϭC)Ar ϭ 1586 (vs), δ(CH2) ϭ 1410 (m), ν(PϪC) ϭ
994 (w), 933 (s), δ(HCϭCH)Ar ϭ 831 (vs) cmϪ1
.
{trans-Bis[1,2-bis(dimethylphosphanyl)ethane]-bis[(4-triisopropyl-
silylethynyl)phenylethynyl]manganese(III)} Hexafluorophosphate,
C)Ar ϭ 1619 (m), ν(PϪC) ϭ 998 (w), 947 (m), δ(HCϭCH)Ar
ϭ
{[TIPS؊CϵC؊C6H4؊CϵC]2(dmpe)2Mn}[PF6], [2a]؉: Compound
2a (275 mg, 0.30 mmol) and [Cp2Fe][PF6] (100 mg, 0.30 mmol)
were added to CH2Cl2 (10 mL) and the reaction mixture was stirred
at room temperature for 30 min. Afterwards, the solvent was re-
moved under vacuo, was washed with pentane (8 ϫ 5 mL) and sub-
sequently with diethyl ether (3 ϫ 5 mL). The remaining solid was
dissolved in THF (15 mL), filtered through Celite and the solvents
844 (vs) cmϪ1
.
{trans-Bis[1,2-bis(dimethylphosphanyl)ethane]-bis(fluorophenyl-
ethynyl)manganese(II)}, {[FC6H4CϵC]2(dmpe)2Mn} (4a): Butyllith-
ium (1.6 ) in hexane (1.5 mL, 2.40 mmol) was added to para-
fluorophenylacetylene (288 mg, 2.40 mmol) in THF (15 mL) at
were evaporated under vacuum to give a dark green solid. Yield Ϫ30 °C. The reaction mixture was slowly warmed to room
309 mg (0.291 mmol, 97 %). C50H82F6MnP5Si2 (1063.15): calcd. C temperature, before being cooled to Ϫ30 °C. The cooled
56.49, H 7.77; found C 56.70, H 7.49. 1H NMR ([D8]THF, LiϪCϵCC6H4F was added dropwise to [MnI2(dmpe)2] (609 mg,
200 MHz, 22 °C): δ ϭ 39.9 (s, 4 H, ArHm), 1.14 {s, 42 H, 1.00 mmol) in THF (15 mL) at Ϫ30 °C. The reaction mixture was
Si[CH(CH3)2]3}, Ϫ29.1 (s, 8 H, PCH2), Ϫ38.6 [s, 24 H, P(CH3)2], stirred at room temperature for 2 h and the solvent was evaporated
Ϫ58.3 (s, 4 H, ArHo). ((ՅAuthor: please check spectroscopic under vacuo to yield a red brown solid. The solid was extracted
data.)) 19F NMR ([D8]THF, 188.16 MHz, 20 °C): δ ϭ Ϫ75.8 (d, with diethyl ether and (3 ϫ 5 mL) and filtered through Celite.
1JFP ϭ 714 Hz, 6 F, PF6). 31P NMR (CD2Cl2, 80.95 MHz, 22 °C):
Evaporation of ether fraction under vacuo resulted in an oil, which
was washed with 10 mL of pentane and filtered through Celite.
The solid over the Celite was extracted with toluene (3 ϫ 5 mL).
1
δ
ϭ
Ϫ143.9 (sept, JPF
ϭ
716 Hz, 1 P, PF6). Raman:
ν(TIPSϪCϵC) ϭ 2147 (w), ν(CϵCϪMn) ϭ 2030 (vs), ν(Cϭ
C)Ar ϭ 1589 (vs), ν(CϭC)Ar ϭ 1171 (s), ν(HCϭCH)Ar ϭ 837 (w), Evaporation of the toluene fraction under vacuum resulted in a
ν(MnϪC) ϭ 652 (w), ν(MnϪP) ϭ 340 (w) cmϪ1. IR (KBr): solid. Crystallization at Ϫ30 °C in diethyl ether gave single crystals
ν(CϪH) ϭ 2942 (s), 2864 (s), ν(TIPSϪCϵC) ϭ 2152 (m),
suitable for a X-ray diffraction study. Yield 542 mg (0.913 mmol,
ν(CϵCϪMn) ϭ 2033 (m), ν(CϭC)Ar ϭ 1626 (m), ν(PϪC) ϭ 996 91 %). C28H40F2MnP4 (593.45): calcd. C 56.67, H 6.79; found C
(w), 944 (s), δ(HCϭCH)Ar ϭ 838 (s) cmϪ1
.
56.82, H 6.87. 1H NMR (C6D6, 200 MHz, 22 °C): δ ϭ 16.4 (s, 4 H,
ArHm), Ϫ5.7 (s, 4 H, ArHo), Ϫ14.8 [s, 32 H, CH2P(CH3)2]. 19F
NMR (C6D6, 188.16 MHz, 22 °C): δ ϭ Ϫ104.2 (s, 2 F, ArF). IR
{trans-Bis[1,2-bis(dimethylphosphanyl)ethane]-bis[(4-ethynyl)phenyl-
ethynyl]manganese(II)}, {[HCϵC؊C6H4؊CϵC]2 (dmpe)2Mn} (3a): (ATR): ν(CϪH) ϭ 2965 (w), 2900 (m), ν(CϵC) ϭ 2004 (s), ν(Cϭ
TBAF (1 ) in THF (5 % H2O, 0.2 mL, 0.2 mmol) was added to
C)Ar ϭ 1493 (s), ν(CϪF) ϭ 1216 (s), 1198 (s), ν(PϪC) ϭ 923 (s),
[2a]ϩ (213 mg, 0.2 mmol) in THF (15 mL) at room temp. The reac-
δ(HCϭCH)Ar ϭ 827 (s) cmϪ1
.
1396
www.zaac.wiley-vch.de
 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2009, 1391Ϫ1401

Synthesis and Characterization of Manganese Bis-acetylide Complexes
{trans-Bis[1,2-bis(dimethylphosphanyl)ethane]-bis(fluorophenyl- Mn]2(µ-CϵC؊CϵC)} (7a): Lithium phenylacetylide (0.40 mmol),
ethynyl)manganese(III)} Hexafluorophosphate, {[FC6H4CϵC]2-
synthesized from phenylacetylene (39 mg, 0.40 mmol) and 1.6 
Butyllithium in hexane (250 µL, 0.40 mmol) at Ϫ30 °C, in THF
(dmpe)2Mn}[PF6], [4a]؉: Compound 4 (297 mg, 0.50 mmol) was
oxidized with [Cp2Fe][PF6] (165 mg, 0.50 mmol) in CH2Cl2 (15 mL) was added to {[Mn(dmpe)2I]2(µ-C4)} (101 mg, 0.10 mmol)
(10 mL). The reaction mixture was stirred at room temperature for
1 h, after which the solvent was evaporated under vacuo to give a
solid. The solid was washed with ethyl ether (5 ϫ 10 mL) followed
by extraction with THF (10 mL). The extract was filtered through
Celite and the solvents were evaporated under vacuum to give a
dark violet solid. Yield 365 mg (0.494 mmol, 99 %). Crystallization
at Ϫ30 °C in CH2Cl2 gave single crystals suitable for a X-ray dif-
in THF and the reaction mixture was stirred at room temperature
for 6 h. The solvent was evaporated under vacuum to give a brown
solid. The solid was washed with pentane (3 ϫ 10 mL) extracted
with diethyl ether (3 ϫ 5 mL) and filtered through Celite. The deep
red solution was evaporated under vacuum to give a red solid. Yield
82 mg (0.085 mmol, 85 %). C44H74Mn2P8 (960.72): calcd. C 55.01,
H 7.76; found C 55.10, H 7.78. 1H NMR (C6D6, 200 MHz, 20 °C):
fraction study. C28H40F8MnP5 (738.41): calcd. C 45.54, H 5.46; δ ϭ 16.8 (s, 4 H, ArHm), Ϫ0.3 (s, 2 H, ArHp), Ϫ4.1 (s, 4 H, ArHo),
1
found C 45.19, H 5.31. H NMR (CD2Cl2, 300 MHz, 22 °C): δ ϭ Ϫ15.0 [s, 64 H, P(CH3)2, PCH2].
35.3 (s, 4 H, ArHm), Ϫ29.3 (s, 8 H, PCH2), Ϫ38.7 (s, 24 H, PCH3),
Ϫ58.2 (s, 4 H, ArHo). 19F NMR (CD2Cl2, 282.33 MHz, 22 °C): δ ϭ
{Bis-[trans-bis(1,2-bis(dimethylphosphanyl)ethane)phenyl-
Ϫ75.8 (d, 1JFP ϭ 712 Hz, 6 F, PF6), Ϫ105.2 (s, 2 F, ArF). 31P NMR
(CD2Cl2, 121.47 MHz, 22 °C): δ ϭ Ϫ144.2 (sept, JPF ϭ 707 Hz,
ethynylmanganese(II/III)]-(µ-1,3-butadiyne)} Hexafluorophosphate,
{[(PhCϵC)(dmpe)2Mn]2(µ-CϵC؊CϵC)} [PF6], [7a]؉: [Cp2Fe][PF6]
(17 mg, 0.051 mmol) in CH2Cl2 (10 mL) was added to 7a (50 mg,
0.052 mmol) at room temperature whilst stirring. After a few mi-
nutes, the color of the reaction mixture changed to green. The reac-
tion mixture was evaporated under vacuum and the solid was
washed with diethyl ether (5 ϫ 10 mL). The solid was extracted
with THF and filtered through Celite. The solvent was evaporated
under vacuum to give a deep green solid. Yield 53 mg (0.048 mmol,
94 %). C44H74F6Mn2P9 (1105.69): calcd. C 47.80, H 6.75; found C
1
1 P, PF6). IR (ATR): ν(CϪH) ϭ 2961 (w), 2898 (m), ν(CϵC) ϭ
2034 (s), ν(CϭC)Ar ϭ 1527 (s), ν(CϪF) ϭ 1214 (s), 1201 (s),
ν(PϪC) ϭ 930 (s), δ(HCϭCH)Ar ϭ 828 (s) cmϪ1
.
{trans-Bis[1,2-bis(dimethylphosphanyl)ethane]-[4-(triisopropylsilyl-
ethynyl)]phenylethynyl-iodomanganese(II)}, {[TIPS؊CϵC؊C6H4؊
CϵC](dmpe)2MnI} (5): TIPSϪCϵCϪC6H4ϪCϵCϪH (283 mg,
1.00 mmol) was added to [MeCpMn(dmpe)I] (411 mg, 1.00 mmol)
dissolved in THF (20 mL). The reaction mixture was stirred for
30 min at room temperature and dmpe (150 mg, 1.00 mmol) was
further added. The reaction mixture was stirred at room tempera-
ture for additional 6 h resulting in an intense red colored solution.
The reaction mixture was evaporated under vacuum and the re-
sulting residue was extracted with pentane (5 ϫ 10 mL) until the
solution was colorless. The pentane extract was filtered through
Celite and the solvents evaporated under vacuum to give a red
brown solid. Yield 557 mg (0.729 mmol, 73 %). C31H57IMnP4Si
1
47.49, H 6.54. H NMR ([D8]THF, 200 MHz, 20 °C): δ ϭ 28.7 (s,
4 H, ArHm), Ϫ22.1 (s, 16 H, PCH2), Ϫ26.5 [s, 50 H, P(CH3)2,
ArHp], Ϫ31.9 (s, 4 H, ArHo).
{Bis-[trans-bis(1,2-bis(dimethylphosphanyl)ethane)phenyl-
ethynylmanganese(III/III)]-(µ-1,3butadiyne)} Bis(hexafluorophos-
phate), {[(PhCϵC)(dmpe)2 Mn]2(µ-CϵC؊CϵC)}[PF6]2, [7a]2؉: To
7a (50 mg, 0.052 mmol) in CH2Cl2 (10 mL), [Cp2Fe][PF6] (34.4 mg,
0.104 mmol) was added and the reaction mixture was stirred 30 min
at room temp. The solvent was evaporated under vacuum and
washed with diethyl ether (5 ϫ 10 mL), filtered and further washed
with a small amount of THF (5 mL). The violet product was ex-
tracted with a 1/1 mixture of THF/CH2Cl2 (10 mL), filtered
through Celite and the solvents were evaporated under vacuum to
1
(763.61): calcd. C 48.76, H 7.52; found C 48.41, H 7.80. H NMR
(C6D6, 200 MHz, 22 °C): δ ϭ 18.9 (s, 2 H, ArHm), 1.31 {s, 3 H,
Si[CH(CH3)2]3}, 1.14 {s, 18 H, Si[CH(CH3)2]3}, Ϫ1.6 (s, 2 H,
ArHo), Ϫ17.2 [s, 32 H, CH2P(CH3)2]. IR (ATR): ν(CϪH) ϭ 2940
(m), 2889 (m), 2867 (m), ν(TIPSϪCϵC)
ν(CϵCϪMn) ϭ 2001 (s), ν(CϭC)Ar ϭ 1592 (s), ν(PϪC) ϭ 992
(w), 940 (s), δ(HCϭCH)Ar ϭ 845 (s) cmϪ1
ϭ
2137 (m),
yield
a
violet solid. Yield 58 mg (0.046 mmol, 89 %).
C44H74F12Mn2P10 (1250.65): calcd. C 42.26, H 5.96; found C 42.17,
H 6.04. 1H NMR (CD3CN, 200 MHz, 20 °C): δ ϭ 36.6 (s, 4 H,
ArHm), Ϫ29.2 (s, 16 H, PCH2), Ϫ38.5 [s, 48 H, P(CH3)2], Ϫ52.7 (s,
2 H, ArHp), Ϫ56.9 (s, 4 H, ArHo).
.
{trans-Bis[1,2-bis(dimethylphosphanyl)ethane]-(4-ethynyl)phenyl-
ethynyl-iodo-manganese(II)}, {[H؊CϵC؊C6H4؊CϵC](dmpe)2-
MnI} (6): Tetrabutylammonium fluoride (0.4 mL of 1 , Bu4NF;
TBAF) in THF (5 % H2O) was added to 5 (305 mg, 0.40 mmol) in
THF (10 mL). The reaction mixture was stirred at room tempera-
ture for 2 h and the solvents were evaporated under vacuum to
yield a solid residue. The solid residue was first washed with pen-
tane and extracted with ethyl ether (2 ϫ 5 mL). The ether extract
was filtered through Celite and the solvents were evaporated under
vacuum to give a solid. Yield 238 mg (0.392 mmol, 98 %). Crystalli-
zation at Ϫ30 °C in THF gave single crystals suitable for an X-ray
diffraction study. C22H37IMnP4 (607.27): calcd. C 43.51, H 6.14;
{Bis-[trans-bis(1,2-bis(dimethylphosphanyl)ethane)(methyl)phenyl-
ethynylmanganese(II/II)]-(µ-1,3-butadiyne)},
{[(CH3C6H4CϵC)-
(dmpe)2Mn]2(µ-CϵC؊CϵC)} (7b): Lithium-para-(methyl)phenyl-
acetylide (0.40 mmol) in THF (15 mL), [which was synthesized
from para-(methyl) phenylacetylene (46 mg, 0.40 mmol) und 1.6 
butyllithium in hexane (250 µL, 0.40 mmol) at Ϫ30 °C], was added
to [{Mn(dmpe)2I}2(µ-C4)] (101 mg, 0.10 mmol) and the reaction
mixture was stirred for 6 h. The solvent was evaporated under
vacuum and washed with pentane (3 ϫ 10 mL). The solid was
extracted with diethyl ether (3 ϫ 5 mL) and filtered through Celite.
The deep red solution was evaporated under vacuum to give a dark
red solid. Yield 83 mg (0.084 mmol, 84 %). C46H78Mn2P8 (988.78):
calcd. C 55.88, H 7.95; found C 55.69, H 7.82. 1H NMR (C6D6,
200 MHz, 20 °C): δ ϭ 16.2 (s, 4 H, ArHm), 0.9 (s, 6 H, ArCH3),
Ϫ4.3 (s, 4 H, ArHo), Ϫ15.1 [s, 64 H, P(CH3)2, PCH2].
1
found C 43.65, H 5.88. H NMR ([D8]THF, 200 MHz, 22 °C): δ ϭ
18.1 (s, 2 H, ArHm), 2.32 (s, 1 H, CCH), Ϫ3.1 (s, 2 H, ArHo), Ϫ17.1
[s, 32 H, CH2P(CH3)2]. IR (ATR): ν(HϪCϵC) ϭ 3312 (m),
ν(CϪH)
ν(CϵCϪMn) ϭ 1996 (s), ν(CϭC)Ar ϭ 1593 (s), ν(PϪC) ϭ 949
(m), δ(HCϭCH)Ar ϭ 837 (m) cmϪ1
ϭ 2959 (m), 2906 (m), ν(HϪCϵC) ϭ 2104 (w),
.
{Bis-[trans-bis(1,2-bis(dimethylphosphanyl)ethane)(methyl)phenyl-
ethynylmanganese(II/III)]-(µ-1,3-butadiyne)} Hexafluorophosphate,
{[(CH3C6H4CϵC)(dmpe)2Mn]2(µ-CϵC؊CϵC)}[PF6],
{Bis-[trans-bis(1,2-bis(dimethylphosphanyl)ethane)phenyl-
ethynylmanganese(II/II)]-(µ-1,3-butadiyne)},
{[(PhCϵC)(dmpe)2-
[7b]؉:
Z. Anorg. Allg. Chem. 2009, 1391Ϫ1401
 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
1397

T. Fritz, H. W. Schmalle, O. Blacque, K. Venkatesan, H. Berke
[Cp2Fe][PF6] (17 mg, 0.051 mmol) was added to 7b (50 mg, perature for 30 min. The solvent was evaporated under vacuo,
ARTICLE
0.051 mmol) in CH2Cl2 (10 mL). After a few minutes, the color of
the reaction mixture turned to green. The solvent was evaporated
under vacuum and washed with diethyl ether (5 ϫ 10 mL) to re-
move ferrocene. The solid was extracted with THF, filtered through
Celite and the solvents were evaporated under vacuum to give a
deep green solid. Yield 53 mg (93 %). C46H78F6Mn2P9 (1133.74):
washed with diethyl ether (5 ϫ 10 mL) and a small amount of THF
(5 mL). The resulting violet product was extracted with a THF/
DCM mixture and filtered through Celite. The solvent was evapo-
rated under vacuum to give
a violet solid. Yield 68 mg
(0.049 mmol, 94 %). C54H94F12Mn2P10 (1390.92): calcd. C 46.63,
H 6.81; found C 46.39, H 6.63. 1H NMR (CD3CN, 200 MHz,
calcd. C 48.73, H 6.93; found C 48.58, H 6.69. 1H NMR ([D8]THF, 20 °C):
200 MHz, 20 °C): δ ϭ 28.1 (s, 4 H, ArHm), 0.8 (s, 6 H, ArCH3),
δ
ϭ
35.1 (s, 4 H, ArHm), 0.90Ϫ1.52 [m, 22 H,
Ar(CH2)4CH3], Ϫ29.1 (s, 16 H, PCH2), Ϫ38.4 [s, 48 H, P(CH3)2],
Ϫ21.9 (s, 16 H, PCH2), Ϫ26.3 [s, 48 H, P(CH3)2], Ϫ32.2 (s, 4 H, Ϫ56.9 (s, 4 H, ArHo).
ArHo).
{Bis-[trans-bis(1,2-bis(dimethylphosphanyl)ethane)(fluoro)phenyl-
ethynylmanganese(II/II)]-(µ-1,3-butadiyne)}, {[(FC6H4CϵC)-
(dmpe)2Mn]2(µ-CϵC؊CϵC)} (7d): Lithium(para-fluorophen-
{Bis-[trans-bis(1,2-bis(dimethylphosphanyl)ethane)(methyl)phenyl-
ethynylmanganese(III/III)]-(µ-1,3-butadiyne)} Bis(hexafluoro-
phosphate), {[(CH3C6H4CϵC)(dmpe)2Mn]2(µ-CϵC؊CϵC)}[PF6]2, yl)acetylide (0.32 mmol), synthesized in situ from para-fluorophen-
[7b]2؉: [Cp2Fe][PF6] (34 mg, 0.104 mmol) was added to 7b (51 mg,
ylacetylene (38 mg, 0.32 mmol) and 1.6  Butyllithium (200 µL,
0.052 mmol) in CH2Cl2 (10 mL) and the reaction mixture was
0.32 mmol) at Ϫ30 °C, in THF (15 mL) was added to
stirred at room temperature for 30 min. The solvent was evaporated [{Mn(dmpe)2I}2(µ-C4)] (108 mg, 0.11 mmol) in THF and the reac-
under vacuum and the solid was washed with diethyl ether tion mixture was stirred at room temperature for 3 h. The solvent
(5 ϫ 10 mL) to remove ferrocene. Further, the solid was washed was evaporated under vacuum to a brown solid, which was washed
with THF (5 mL), extracted with a THF/DCM mixture and filtered
through Celite. Afterwards, the solvent was evaporated under vac-
with pentane (3 ϫ 10 mL) extracted with diethyl ether (2 ϫ 5 mL)
and filtered through Celite. The solvent was evaporated under vac-
uum to give a violet solid. Yield 64 mg (0.050 mmol, 96 %). uum to give a red brown solid. Yield 70 mg (0.070 mmol, 64 %).
C46H78F12Mn2P10 (1278.71): calcd. C 43.21, H 6.14; found C 43.00,
C44H72F2Mn2P8 (996.71): calcd. C 53.02, H 7.28; found C 52.91,
H 5.95. 1H NMR (CD3CN, 200 MHz, 20 °C): δ ϭ 34.3 (s, 4 H, H 7.20. 1H NMR (C6D6, 200 MHz, 20 °C): δ ϭ 16.4 (s, 4 H, ArHm),
ArHm), 0.9 (s, 6 H, ArCH3), Ϫ29.3 (s, 16 H, PCH2), Ϫ38.5 [s, 48 H, Ϫ5.7 (s, 4 H, ArHo), Ϫ13.8 (s, 16 H, PCH2), Ϫ15.1 [s, 48 H,
P(CH3)2], Ϫ57.1 (s, 4 H, ArHo).
P(CH3)2].
{Bis-[trans-bis(1,2-bis(dimethylphosphanyl)ethane)(n-pentyl)phenyl- {Bis-[trans-bis(1,2-bis(dimethylphosphanyl)ethane)(fluoro)phenyl-
ethynylmanganese(II/II)]-(µ-1,3-butadiyne)}, {[(CH3(CH2)4C6H4- ethynylmanganese(II/III)]-(µ-1,3-butadiyne)} Hexafluorophos-
CϵC)(dmpe)2Mn]2(µ-CϵC؊CϵC)} (7c): Lithium-(n-pentyl)phen-
phate, {[(FC6H4CϵC)(dmpe)2Mn]2(µ-CϵC؊CϵC)}[PF6], [7d]؉:
ylacetylide (0.40 mmol) in THF (15 mL) [synthesized from (n-pen- [Cp2Fe][PF6] (17 mg, 0.051 mmol) was added to 7d (52 mg,
tyl)phenylacetylene (52 mg, 0.40 mmol) and 1.6  butyllithium 0.052 mmol) in CH2Cl2 (10 mL) and the reaction mixture was
(250 µL, 0.40 mmol)], was added to [{Mn(dmpe)2I}2(µ-C4)] stirred at room temperature for 30 min. After the solvent was eva-
(101 mg, 0.10 mmol) in THF (10 mL) at Ϫ30 °C and the reaction porated under vacuum, the residue was washed with diethyl ether
mixture was stirred at room temperature for 6 h. The reaction mix-
ture was evaporated under vacuum; the resulting residue was ex-
tracted with pentane (3 ϫ 10 mL) and filtered through Celite. The
dark red solution was cooled to Ϫ30 °C to give dark red crystals.
(5 ϫ 10 mL) to remove ferrocene. The solid was extracted with
THF, filtered through Celite and the solvent was evaporated to give
a
dark green solid. Yield 56 mg (0.049 mmol, 96 %).
C44H72F8Mn2P9 (1141.67): calcd. C 46.29, H 6.36; found C 46.42,
Yield 90 mg (0.082 mmol, 82 %). C54H94Mn2P8 (1100.99): calcd. C H 6.31. 1H NMR ([D8]THF, 200 MHz, 20 °C): δ ϭ 27.2 (s, 4 H,
1
58.91, H 8.61; found C 58.56, H 8.43. H NMR (C6D6, 200 MHz,
ArHm), Ϫ21.8 (s, 16 H, PCH2), Ϫ26.0 [s, 48 H, P(CH3)2], Ϫ33.3 (s,
4 H, ArHo).
20 °C):
δ ϭ 16.2 (s, 4 H, ArHm), 0.98Ϫ1.42 [m, 22 H,
Ar(CH2)4CH3], Ϫ4.0 (s, 4 H, ArHo), Ϫ14.9 [s, 64 H, P(CH3)2,
PCH2].
{Bis-[trans-bis(1,2-bis(dimethylphosphanyl)ethane)(fluoro)phenyl-
ethynylmanganese(III/III)]-(µ-1,3-butadiyne)} Bis(hexafluorophos-
{Bis-[trans-bis(1,2-bis(dimethylphosphanyl)ethane)-(n-pentyl)phenyl-
ethynylmanganese(II/III)]-(µ-1,3-butadiyne)} Hexafluorophosphate,
phate), {[(FC6H4CϵC)(dmpe)2Mn]2(µ-CϵC؊CϵC)}[PF6]2, [7d]2؉
:
[Cp2Fe][PF6] (34 mg, 0.104 mmol) was added to 7d (52 mg,
{[(CH3(CH2)4C6H4
CϵC)(dmpe)2Mn]2(µ-CϵC؊CϵC)}[PF6],
0.052 mmol) in CH2Cl2 (10 mL) and the reaction mixture was
[7c]؉: [Cp2Fe][PF6] (17 mg, 0.051 mmol) was added to 7c (57 mg, stirred at room temperature for 30 min. Afterwards, the solvent was
0.052 mmol) in CH2Cl2 (10 mL), and the reaction mixture was evaporated under vacuum and the residue was washed with diethyl
stirred for a few minutes. After the solvent was evaporated, the
residue was washed with diethyl ether (5 ϫ 10 mL) and the solid
was extracted with THF. The THF extract was filtered through
Celite and evaporated to give a solid. Yield 62 mg (0.050 mmol,
ether (5 ϫ 10 mL) to remove ferrocene. The violet solid was ex-
tracted with CH2Cl2, filtered through Celite and the solvents were
evaporated under vacuum to give the title compound. yield 60 mg
(0.047 mmol, 90 %). C44H72F14Mn2P10 (1286.63): calcd. C 41.07,
96 %). C54H94F6Mn2P9 (1245.95): calcd. C 52.05, H 7.60; found C H 5.64; found C 41.28, H 5.63. 1H NMR (CD3CN, 200 MHz,
1
52.00, H 7.56. H NMR ([D8]THF, 200 MHz, 20 °C): δ ϭ 28.5 (s,
20 °C): δ ϭ 34.6 (s, 4 H, ArHm), Ϫ29.0 (s, 16 H, PCH2), Ϫ38.3 [s,
4 H, ArHm), 0.79Ϫ1.38 [m, 22 H, Ar(CH2)4CH3], Ϫ22.2 (s, 16 H, 48 H, P(CH3)2], Ϫ56.7 (s, 4 H, ArHo).
PCH2), Ϫ26.6 [s, 48 H, P(CH3)2], Ϫ32.8 (s, 4 H, ArHo).
Crystal Structure Determinations: Suitable crystals of 1c, 2a-1, 2a-
{Bis-[trans-bis(1,2-bis(dimethylphosphanyl)ethane)(n-pentyl)phenyl- 2, 4, [4]ϩ and 6 were mounted on the tip of a glass fiber using
ethynylmanganese(III/III)]-(µ-1,3-butadiyne)} Bis(hexafluorophos- polybutene oil as protecting agent. The crystals were cooled to
phate),
{[(CH3(CH2)4C6H4CϵC)(dmpe)2Mn]2(µ-CϵC؊CϵC)}- 183(2) K (1c, 2a-1, 4 and 6), 153(2) K (2a-2) or 297(2) K ([4]ϩ) by
[PF6]2, [7c]2؉: [Cp2Fe][PF6] (34 mg, 0.104 mmol) was added to 7c
(57 mg, 0.052 mmol) in CH2Cl2 (10 mL) and stirred at room tem-
an Oxford cryogenic system. Totals of 43025, 56255, 75402, 54578,
116947 and 29044 reflections were collected [61] for 1c, 2a-1, 2a-2,
1398
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 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2009, 1391Ϫ1401

Synthesis and Characterization of Manganese Bis-acetylide Complexes
4, [4]ϩ and 6 and resulted in 3697 (Rint ϭ 0.077), 16424 (Rint
0.177), 23018 (Rint ϭ 0.141), 5332 (Rint ϭ 0.122), 29657 (Rint
0.070) and 6586 (Rint ϭ 0.056) unique reflections, respectively. Nu-
merical absorption corrections [62] based on 23, 9, 9, 6, 8 and 17
crystal faces, respectively, were applied with FACEitVIDEO and
XRED [61]. The structures were solved by direct methods using
the program SHELXS-97 [63]. The full-matrix least-squares refine-
ϭ
ϭ
The small size of the plate-like crystals of 2a-1, 2a-2 and [4]ϩ re-
sulted in low diffraction power, only 21 % to 25 % of the unique
intensity reflections were considered observed by criterion I > 2σ(I)
in spite of high generator power and long exposure time of the
image plate contributing to the relatively high Rint, Rσ, and wR and
R1 values. Crystallographic details are presented in Table 1 and in
the deposited CIF files. The absolute structure parameter [65] was
ments (based on F2) were carried out with SHELXL-97 [63]. The finally refined to Ϫ0.01(3). Crystals of 6 were found to be all
plots of the structures were generated by using ORTEP [64]. twinned when examined by using a polarizing microscope. A twin
Table 1. Summary of the X-ray diffraction studies of 1c, 2a-1, 2a-1, 4, [4]ϩ and 6.
1c
2a-1
2a-2
Empirical formula
Formula weight /g·molϪ1
Temperature /K
C14H36Br2MnP4
543.07
183(2)
C50H82MnP4Si2
918.16
183(2)
C50H82MnP4Si2
918.16
153(2)
˚
Wavelength /A
0.71073
0.71073
0.71073
triclinic, P1
¯
Crystal system, space group
orthorhombic, Pbca
13.290(2)
13.6837(16)
13.475(2)
90
90
90
2450.6(6)
4, 1.472
4.055
orthorhombic, P212121
15.0234(10)
15.4419(7)
23.4842(11)
90
90
90
5448.1(5)
4, 1.119
0.434
˚
a /A
11.0365(17)
19.435(3)
20.336(3)
105.930(18)
97.968(18)
90.255(18)
4149.7(12)
3, 1.102
˚
b /A
˚
c /A
Ͱ /°
β /°
γ /°
3
˚
Volume /A
Z, density (calcd.) /Mg·mϪ3
Absorbtion coefficient /mmϪ1
F(000)
0.427
1485
1100
1980
Crystal size /mm
0.42 ϫ 0.32 ϫ 0.31
2.62 to 30.42
43025
3697 [Rint ϭ 0.077]
99.4
0.3617/0.2833
3697/0/101
0.780
0.0507, 0.113
0.0933, 0.121
0.21 ϫ 0.18 ϫ 0.07
2.71 to 30.47
56255
16424 [Rint ϭ 0.177]
99.2
0.9754/0.9244
16424/10/514
0.473
0.0413, 0.0667
0.2166, 0.1136
0.28 ϫ 0.17 ϫ 0.04
2.88 to 30.53
75402
23018 [Rint ϭ 0.141]
90.8
0.9814/0.9084
23018/2/802
0.560
0.0508, 0.0951
0.2150, 0.1265
θ Range /°
Reflections collected
Reflections unique
Completeness to θ /%
Max/min transmission
Data/restraints/parameters
Goodness-of-fit on F2
Final R1 and wR2 indices [I > 2σ(I)]
R1 and wR2 indices (all data)
4
[4]ϩ
6
Empirical formula
Formula weight /g·molϪ1
Temperature /K
C28H40F2MnP4
593.42
183(2)
C28H40F8MnP5
738.39
297(2)
C22H37IMnP4
607.24
183(2)
˚
Wavelength /A
0.71073
0.71073
triclinic, P1
0.71073
¯
Crystal system, space group
monoclinic, P21/c
12.3182(18)
13.6885(15)
18.935(3)
90
108.889(17)
90
3020.9(7)
4, 1.305
0.677
monoclinic, P21/c
9.1395(5)
13.0655(7)
23.2824(15)
90
99.239(7)
90
2744.1(3)
4, 1.470
1.846
˚
a /A
12.5139(8)
21.0539(15)
23.0029(14)
107.594(7)
105.814(7)
99.765(8)
5344.4(8)
6, 1.377
0.654
2280
˚
b /A
˚
c /A
Ͱ /°
β /°
γ /°
3
˚
Volume /A
Z, density (calcd.) /Mg·mϪ3
Absorbtion coefficient /mmϪ1
F(000)
1244
1228
Crystal size /mm
0.21 ϫ 0.20 ϫ 0.14
2.72 to 25.00
54578
5332 [Rint ϭ 0.122]
99.9
0.9335/0.8528
5332/0/332
0.678
0.0339, 0.0655
0.0668, 0.0690
0.40 ϫ 0.36 ϫ 0.08
2.80 to 30.55
116947
29657 [Rint ϭ 0.070]
90.5
0.9525/0.7978
29657/6/1162
0.680
0.0620, 0.1442
0.1699, 0.1676
0.39 ϫ 0.36 ϫ 0.27
2.64 to 28.08
29044
6586 [Rint ϭ 0.056]
94.7
0.6881/0.5496
6586/0/252
0.912
0.0567, 0.1523
0.0761, 0.1606
θ Range /°
Reflections collected
Reflections unique
Completeness to θ /%
Max/min transmission
Data/restraints/parameters
Goodness-of-fit on F2
Final R1 and wR2 indices [I > 2σ(I)]
R1 and wR2 indices (all data)
The unweighted R-factor is R1 ϭ Σ(Fo Ϫ Fc)/ΣFo; I > 2 σ(I) and the weighted R-factor is wR2 ϭ {Σw(Fo Ϫ Fc ) /Σw(Fo ) }1/2
.
2
2 2
2 2
Z. Anorg. Allg. Chem. 2009, 1391Ϫ1401
 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
1399

T. Fritz, H. W. Schmalle, O. Blacque, K. Venkatesan, H. Berke
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Ϫ
Ϫ
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formally six.
Crystallographic data (excluding structure factors) for the
structures given in this paper have been deposited with the
Cambridge Crystallographic Data Centre as supplementary publi-
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([4]ϩ), and CCDC-713980 (6). Copies of the data can be obtained
free of charge on application to CCDC, 12 Union Road,
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deposit@ccdc.cam.ac.uk].
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Acknowledgement
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Received: December 30, 2008
Published Online: March 17, 2009
Z. Anorg. Allg. Chem. 2009, 1391Ϫ1401
 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
1401