μ-carbon - Carbon bonds of dinuclear manganese half-sandwich complexes as electron reservoirs

Article abstract of DOI:10.1021/om049284c

The mononuclear vinylidene complexes of the type Mn(C₅H ₄R′)(R″₂PCH₂CH₂PR″ ₂)(=C= C(R¹)(SnMe₃)) were obtained by the reaction of Mn(C₅H₄R′)(η⁶- cycloheptatriene) (R′ = H, 1a; CH₃, 1b) with 1 equiv of R ¹-C≡C - SnMe₃ (R¹ = SnMe₃, C₆H₅, C₄H₃S, C₆H ₄CH₃) and R″₂PCH₂CH ₂PR″₂ (R″ = CH₃ (dmpe), C ₂H₅ (dmpe)) in toluene at 50°C for 3 h. The reactions of these tin-substituted complexes with 1 equiv of 1.0 M TBAF yielded the corresponding parent vinylidene species Mn(C₅H₄R′) (R″₂PCH₂CH₂PR″₂)(=C= C(R¹)(H)). Treatment of some of these vinylidene species with 1 equiv of [Cp₂Fe] [PF₆] led to the oxidative coupling product [(C₅H₄R′)(R″₂PCH₂CH ₂PR′₂)Mn≡C-CHR¹-CHR ¹-C≡Mn(R″₂PCH₂CH ₂PR″₂)(C₅H₄R″)]-[PF ₆]₂ (R′ = CH₃) R″ = CH₃, R1 = H; R′ = CH₃, R″ = CH₃, R¹ = C₆H₅; R′ = CH₃, R″ = CH ₃, R¹ = C₄H₃S; R′ = H, R″ = C₂H₅, R¹ = H; R′ = H, R″ = C₂H₅, R¹ = C₆H₅; R′ = H, R″ = C₂H₅, R¹ = C ₄H₃S). In some cases these products of oxidative coupling, [(C₅H₄R′)(R″₂PCH ₂CH₂-PR″₂)Mn≡C-CHR ¹-CHR¹-C≡Mn(R″₂PCH ₂CH₂PR″₂)(C₅H ₄R′)] [PF₆]₂ were accompanied by formation of dinuclear complexes of the type [(C₅H ₄R′(R″₂PCH₂CH₂PR″ ₂)Mn≡C-CR¹=CR¹- C≡Mn(R″₂PCH₂CH₂PR″ ₂(C₂H₄R′)][PF₆]₂ and of the cationic carbyne complexes [(C₅H₄R′) (R″₂PCH₂CH₂PR″₂) Mn≡C-CH₂R¹] [PF₅] obtained by proton transfer. Reduction of these dinuclear complexes with Cp₂*Co yielded back the corresponding mononuclear precursor complexes involving a reductive decoupling process. Both the reductive coupling and the oxidative coupling are fully reversible, which is supported by DFT calculations. The mononuclear and the dinuclear compounds were characterized by NMR, IR, and cyclic voltammetric studies. X-ray diffraction studies have been performed on complexes 3a, 11, 13a, 15a, and 22b.

Full text of DOI:10.1021/om049284c

920
Organometallics 2005, 24, 920-932
µ-Carbon-Carbon Bonds of Dinuclear Manganese
Half-Sandwich Complexes as Electron Reservoirs
Koushik Venkatesan, Olivier Blacque, Thomas Fox, Montserrat Alfonso,
Helmut W. Schmalle, Sohrab Kheradmandan, and Heinz Berke*
Anorganisch-Chemisches Institut der Universita¨t Zu¨rich, Winterthurerstrasse 190,
CH-8057 Zu¨rich, Switzerland
Received September 14, 2004
The mononuclear vinylidene complexes of the type Mn(C5H4R′)(R′′2PCH2CH2PR′′2)(dCd
C(R1)(SnMe3)) were obtained by the reaction of Mn(C5H4R′)(η6-cycloheptatriene) (R′ ) H,
1a; CH3, 1b) with 1 equiv of R1-CtC-SnMe3 (R1 ) SnMe3, C6H5, C4H3S, C6H4CH3) and
R′′2PCH2CH2PR′′2 (R′′ ) CH3 (dmpe), C2H5 (depe)) in toluene at 50 °C for 3 h. The reactions
of these tin-substituted complexes with 1 equiv of 1.0 M TBAF yielded the corresponding
parent vinylidene species Mn(C5H4R′)(R′′2PCH2CH2PR′′2)(dCdC(R1)(H)). Treatment of some
of these vinylidene species with 1 equiv of [Cp2Fe][PF6] led to the oxidative coupling product
[(C5H4R′)(R′′2PCH2CH2PR′′2)MntC-CHR1-CHR1-CtMn(R′′2PCH2CH2PR′′2)(C5H4R′)]-
[PF6]2 (R′ ) CH3, R′′ ) CH3, R1 ) H; R′ ) CH3, R′′ ) CH3, R1 ) C6H5; R′ ) CH3, R′′ ) CH3,
R1 ) C4H3S; R′ ) H, R′′ ) C2H5, R1 ) H; R′ ) H, R′′ ) C2H5, R1 ) C6H5; R′ ) H, R′′ ) C2H5,
R1 ) C4H3S). In some cases these products of oxidative coupling, [(C5H4R′)(R′′2PCH2CH2-
PR′′2)MntC-CHR1-CHR1-CtMn(R′′2PCH2CH2PR′′2)(C5H4R′)][PF6]2, were accompanied by
formation of dinuclear complexes of the type [(C5H4R′)(R′′2PCH2CH2PR′′2)MntC-CR1dCR1-
CtMn(R′′2PCH2CH2PR′′2)(C5H4R′)][PF6]2 and of the cationic carbyne complexes [(C5H4R′)(R′′2-
PCH2CH2PR′′2)MntC-CH2R1][PF6] obtained by proton transfer. Reduction of these dinuclear
complexes with Cp2*Co yielded back the corresponding mononuclear precursor complexes
involving a reductive decoupling process. Both the reductive coupling and the oxidative
coupling are fully reversible, which is supported by DFT calculations. The mononuclear and
the dinuclear compounds were characterized by NMR, IR, and cyclic voltammetric studies.
X-ray diffraction studies have been performed on complexes 3a, 11, 13a, 15a, and 22b.
Introduction
crucial components of such devices.14-32 One could
certainly envisage the possibility of utilizing the process
of formation and cleavage of chemical bonds for this
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motifs of a single-electron device, which can store and
release electrons in a reversible fashion, thereby forming
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* To whom correspondence should be addressed. E-mail: hberke@
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10.1021/om049284c CCC: $30.25 © 2005 American Chemical Society
Publication on Web 02/01/2005

µ-C-C Bonds of Dinuclear Manganese Complexes
Organometallics, Vol. 24, No. 5, 2005 921
purpose.33-43 Two complementary electron-storage and
-releasing units are the fundamental constituents of
storage cells.44-48 Coupling a metal and an independent
electron reservoir in the same molecule opens attractive
perspectives in the design of molecules devoted to
energy storage (molecular batteries). The most common
mechanisms by which electrons can be stored and
released can be classified into three categories. The most
obvious involves the change in the oxidation of the
metal, thereby a number of electrons are made available
at different potentials. Another originating from organic
chemistry perspective involves the use of polyaromatic
systems able to accept electrons in the π* orbitals,
and reductive decoupling process.43 We present here a
detailed account of the investigations carried out on the
electron-rich manganese(I) systems of the type Mn-
(C5H4R′)(R′′2PCH2CH2PR′′2)(dCdCR3R4) and their tun-
ing. A first conclusion of a previous study was that
vinylidene complexes gained considerable stability
through the presence of the phosphane ligand (dmpe)57-59
in comparison with the reported CO-substituted species
Mn(Cp)L1L2(CdCR2), where L1 ) L2 ) CO, or L1 ) CO,
L2 ) PR3.60
Results and Discussion
although this is limited in its storage capacity.49,50
A
I. Stannyl-Substituted Vinylidene Complexes. A
common method to obtain vinylidene complexes is
making use of the high propensity of terminal acetylene
derivatives to rearrange to vinylidene compounds.61-78
For such a process to be initiated in the realm of half-
sandwich MnI chemistry, we thought the complexes Mn-
(C5H4R′)(η6-cycloheptatriene) (R′ ) H, 1a; CH3, 1b)79 to
be excellent starting materials, since facile cyclohepta-
triene (CHT) exchange was expected to occur with
donating ligands, such as phosphanes or acetylenes.43,59
Conversions with tin mono- or disubstituted acetylenes
were anticipated to finally lead to the desired vinylidene
species. Stirring Mn(C5H4R′)(CHT) (R′ ) H, 1a; CH3,
1b) with 1 equiv of R1-CtC-SnMe3 (R1 ) SnMe3, C6H5,
C4H3S, CH3, C6H4CH3) and R′′2PCH2CH2PR′′2 (R′′ )
CH3 (dmpe), C2H5 (depe)) in toluene at 50 °C for 3 h
gave the corresponding vinylidene complexes of the type
Mn(C5H4R′)(R′′2PCH2CH2PR′′2)(dCdC(R1)(SnMe3)) (R′′
) CH3, R1 ) SnMe3, R′ ) H 2a, CH3 2b; R′′ ) C2H5, R1
third possibility concerns the formation and cleavage
of chemical bonds. The latter mechanism would nor-
mally make available electrons in pairs and relatively
large in number. Very rarely does the redox chemistry
of ligands in complexes have chemical consequences
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very few systems exhibit reactions in both directions.
Floriani and co-workers have reported one such sys-
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of novel half-sandwich manganese(I) vinylidene systems
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922 Organometallics, Vol. 24, No. 5, 2005
Venkatesan et al.
Scheme 1
) SnMe3, R′ ) H 7a, CH3 7b; R′′ ) CH3, R1 ) C6H5, R′
) H 3a, CH3 3b; R′′ ) C2H5, R1 ) C6H5, R′ ) H 8a,
CH3 8b; R′′ ) CH3, R1 ) C6H4CH3, R′ ) H 4a, CH3 4b;
R′′ ) C2H5, R1 ) C6H4CH3, R′ ) H 9a, CH3 9b; R′′ )
CH3, R1 ) C4H3S, R′ ) H 5a, CH3 5b; R′′ ) C2H5, R1 )
C4H3S, R′ ) H 10a, CH3 10b; R′′ ) CH3, R1 ) Si(t-Bu)-
(Me)2, R′ ) CH3 6b) in quantitative yields (Scheme 1).
This reaction seems to require the initial formation
of a Mn-π-alkyne species.63 However, NMR studies of
the reaction carried out in the range -70 to 20 °C did
not reveal any intermediate. The 13C NMR spectra of
complexes 2-10 show the CR and the Câ resonances at
around 321 and 114 ppm, respectively. The 31P NMR
resonances appear between 92 and 93 ppm for com-
plexes 2-6, which are comparable to those obtained for
the related Mn(C5H4R′)((H3C)2PCH2CH2P(CH3)2)(dCd
CR′′H) complexes.43,59,63,80-82 However the resonances
were shifted further downfield between 110 and 115
ppm for complexes 7-10. The 119Sn resonances corre-
sponding to the trimethyl tin groups were observed as
a triplet between -16 and -20 ppm. The structure of
3a was additionally confirmed by an X-ray diffraction
analysis (Figure 1). The bond lengths of 1.761(6) and
1.344(8) Å for Mn1-C1 and C1-C2, respectively, con-
firm the double-bond character of the two bonds.43,59,80,81
Reaction of 1a with 1 equiv of Me3Sn-CtC-C6H5
and depe yields a mixture of the corresponding vi-
nylidene complex 8a and the bis-acetylide MnII complex
Mn(depe)2(CtC-C6H5)2, 11. The 1H NMR spectrum of
11 shows two broad signals in the high-field region at
-13.7 and -9.8 ppm corresponding to the depe protons.
The resonances for the aromatic protons were observed
as broad signals both in the downfield region at 16.9
ppm and in the high-field region at -4.9 and -1.1 ppm.
Both the vinylidene complexes 8a and 11 could be
separated and characterized due to their different
solubilities. The formation of 11 is believed to pass
through a half-sandwich MnII monoacetylide followed
by the displacement of the cyclopentadienyl ring with
a depe and an acetylide. The axial symmetry of these
Figure 1. Molecular structure of 3a (30% probability
displacement ellipsoids). Selected bond lengths (Å) and
angles (deg): Mn1-C1 1.761(6), C1-C2 1.344(8), C2-Sn1
2.139(6), Mn1-P1 2.1895(17), Mn1-P2 2.1877(17); Mn1-
C1-C2 172.9(5), C1-C2-Sn1 115.2(4), C1-C2-C3 123.8-
(5), C3-C2-Sn1 120.9(4). All hydrogen atoms have been
omitted for clarity.
species was corroborated by an X-ray study (Figure 2).
The structure of 11 shows the manganese in a pseudo-
octahedral environment with the phenyl alkynyl ligands
in trans position. The Mn-C11 bond distance of 1.978-
(2) Å is in the same range as those found for similar
symmetric trans-bis-alkynyl complexes, while the bond
distance of 1.211(3) Å for C11-C12 indicates clearly a
triple-bond character of the alkynyl ligand. These values
are characteristic for this type of low-spin d5 com-
plexes.57,83,84
II. Vinylidene Complexes via Removal of the
Stannyl Group(s). It has been observed earlier43,60 that
the substituents on the â carbon of the vinylidene
complexes have a great effect on the stability of these
complexes and also on the further reactivity. The
reaction of the species Mn(C5H4R′)(R′′2PCH2CH2PR′′2)-
(dCdC(R1)(SnMe3)) (R′′ ) CH3, R1 ) SnMe3, R′ ) H
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µ-C-C Bonds of Dinuclear Manganese Complexes
Organometallics, Vol. 24, No. 5, 2005 923
Figure 2. Molecular structure of 11 (30% probability
displacement ellipsoids). Selected bond lengths (Å) and
angles (deg): Mn1-C11 1.978(2), C11-C12 1.211(3), C12-
C13 1.439(3); Mn1-C11-C12 171.7(2), C11-C12-C13
176.7(3), C11-Mn1-C11a 180.0. All hydrogen atoms have
been omitted for clarity.
Figure 3. Molecular structure of 15a (30% probability
displacement ellipsoids). Selected bond lengths (Å) and
angles (deg): Mn1-C12 1.739(3), C12-C13 1.336(4); Mn1-
C12-C13 174.5(3), C12-C13-C14 123.9(3). Selected hy-
drogen atoms and the disordered atoms are omitted for
clarity.
2a, CH3 2b; R′′ ) C2H5, R1 ) SnMe3, R′ ) H 7a, CH3
7b; R′′ ) CH3, R1 ) C6H5, R′ ) H 3a, CH3 3b; R′′ )
C2H5, R1 ) C6H5, R′ ) H 8a, CH3 8b; R′′ ) CH3, R1 )
C6H4CH3, R′ ) H 4a, CH3 4b; R′′ ) C2H5, R1 ) C6H4-
CH3, R′ ) H 9a, CH3 9b; R′′ ) CH3, R1 ) C4H3S, R′ )
H 5a, CH3 5b; R′′ ) C2H5, R1 ) C4H3S, R′ ) H 10a,
CH3 10b; R′′ ) CH3, R1 ) Si(t-Bu)(Me)2, R′ ) CH3 6b)
with 1 equiv of NBu4F (5% H2O) yields the correspond-
ing parent vinylidene species Mn(C5H4R′)(R′′2PCH2CH2-
PR′′2)(dCdC(R1)(H)) (R′′ ) CH3, R1 ) H, R′ ) H 12a,
CH3 12b; R′′ ) C2H5, R1 ) H, R′ ) H 17a, CH3 17b; R′′
) CH3, R1 ) C6H5, R′ ) H 13a, CH3, 13b; R′′ ) C2H5,
R1 ) C6H5, R′ ) H 18a, CH3 18b; R′′ ) CH3, R1 ) C6H4-
CH3, R′ ) H 14a, CH3 14b; R′′ ) C2H5, R1 ) C6H4CH3,
R′ ) H 19a, CH3 19b; R′′ ) CH3, R1 ) C4H3S, R′ ) H
15a, CH3 15b; R′′ ) C2H5, R1 ) C4H3S, R′ ) H 20a,
CH3 20b; R′′ ) CH3, R1 ) Si(t-Bu)(Me)2, R′ ) CH3 16b)
by the nucleophilic substitution of the SnMe3 groups
(Scheme 2). Complexes 12 and 17 constitute the finest
examples of thermally stable half-sandwich MnI vi-
nylidene complexes with phosphine ligands and two
hydrogen atoms at the Câ atom.
already reported.43,59,80,84 We could also obtain an X-ray
diffraction analysis for 13a (Figure 4). The structure of
both independent molecules revealed bond lengths very
similar to 15a and 3a. However, the Mn-CR-Câ angles
of 179.5(3)° and 177.9(3)° show almost linearity of the
C2 chain in comparison to the slightly bent Mn-C2 chain
in 15a and 3a at 174.5(3)° and 172.9(5)°, respectively.
III. Reversible Oxidative Coupling of Vinylidene
Complexes. A major route to dinuclear manganese
systems bearing cumulene bridges utilizes coupling
processes of appropriate mononuclear species.43,80-82,85
Our observations show that the oxidation products of
the parent vinylidene complexes depend on the type of
substituents on the cyclopentadienyl ring and the Câ
atom. Oxidation of complexes 12b, 13b, 15b, 17a, 18a,
and 20a with 1 equiv of [Cp2Fe][PF6] in CH2Cl2 after 1
h yields the corresponding dinuclear carbyne complexes
of the type [(C5H4R′)(R′′2PCH2CH2PR′′2)MntC-CHR1-
CHR1-CtMn(R′′2PCH2CH2PR′′2)(C5H4R′)][PF6]2 (R′ )
CH3, R′′ ) CH3, R1 ) H 21b; R′ ) CH3, R′′ ) CH3, R1 )
C6H5 22b; R′ ) CH3, R′′ ) CH3, R1 ) C4H3S 23b; R′ )
H, R′′ ) C2H5, R1 ) H 24a; R′ ) H, R′′ ) C2H5, R1 )
C6H5 25a; R′ ) H, R′′ ) C2H5, R1 ) C4H3S 26a), which
The structure of 15a in the solid state was confirmed
by an X-ray diffraction study (Figure 3). The Mn1-C12
and C12-C13 bond distances are 1.739(3) and 1.336(4)
Å, quite similar to those of the related complexes
1
are the obvious coupling products (Scheme 3). The H
Scheme 2

924 Organometallics, Vol. 24, No. 5, 2005
Venkatesan et al.
12a, 13a, 14a, 14b, 15a, 16b, 17b, 18b, 19a, 19b, and
20b with 1 equiv of [Cp2Fe][PF6] in CH2Cl2 was much
less selective and after 1 h yielded complicated mixtures,
for which the separation could not be accomplished, but
NMR spectroscopic characterization was performed.
We describe here the oxidation of the parent vi-
nylidene complexes Mn(C5H4R′)(R′′2PCH2CH2PR′′2)(d
CdC(R1)(H)) (R′′ ) CH3, R1 ) H, R′ ) H 12a; R′′ ) CH3,
R1 ) C6H5, R′ ) H 13a; R′′ ) CH3, R1 ) C6H4CH3, R′ )
H 14a; R′′ ) CH3, R1 ) C4H3S, R′ ) H 15a; R′′ ) C2H5,
R1 ) H, R′ ) CH3 17b; R′′ ) C2H5, R1 ) C6H5, R′ ) CH3
18b; R′′ ) C2H5, R1 ) C6H4CH3, R′ ) CH3 19b; R′′ )
C2H5, R1 ) C4H3S, R′ ) CH3 20b) with 1 equiv of [Cp2-
Fe][PF6], which yielded in each case a mixture contain-
ing the corresponding dinuclear carbyne complex Mn-
(C5H4R′)(R′′2PCH2CH2PR′′2)MntC-CHR1-CHR1-
CtMn(R′′2PCH2CH2PR′′2)(C5H4R′)][PF6]2 (R′′ ) CH3, R1
) H, R′ ) H 27a; R′′ ) CH3, R1 ) C6H5, R′ ) H 28a; R′′
) CH3, R1 ) C6H4CH3, R′ ) H 29a; R′′ ) CH3, R1 )
C4H3S, R′ ) H 30a; R′′ ) C2H5, R1 ) H, R′ ) CH3 31b;
R′′ ) C2H5, R1 ) C6H5, R′ ) CH3 32b; R′′ ) C2H5, R1 )
C6H4CH3, R′ ) CH3 33b; R′′ ) C2H5, R1 ) C4H3S, R′ )
CH3 34b), the dehydrogenative coupling µ-vicinal alky-
lidene type product [(C5H4R′)(R′′2PCH2CH2PR′′2)Mnt
C-CR1dCR1-CtMn(R′′2PCH2CH2PR′′2)(C5H4R′)]-
[PF6]2 (R′′ ) CH3, R1 ) H, R′ ) H 35a; R′′ ) CH3, R1 )
C6H5, R′ ) H 36a; R′′ ) CH3, R1 ) C6H4CH3, R′ ) H
37a; R′′ ) CH3, R1 ) C4H3S, R′ ) H 38a; R′′ ) CH3, R1
) Si(t-Bu)(Me)2, R′ ) CH3 39b; R′′ ) C2H5, R1 ) H, R′
) CH3 40b; R′′ ) C2H5, R1 ) C6H5, R′ ) CH3 41b; R′′ )
C2H5, R1 ) C6H4CH3, R′ ) CH3 42b; R′′ ) C2H5, R1 )
C4H3S, R′ ) CH3 43b), and additionally the protonation
product of the vinylidenes producing the mononuclear
carbyne species [(C5H4R′)(R′′2PCH2CH2PR′′2)MntC-
CH3][PF6] (R′′ ) CH3, R1 ) H, R′ ) H 44a; R′′ ) CH3,
R1 ) C6H5, R′ ) H 45a; R′′ ) CH3, R1 ) C6H4CH3, R′ )
H 46a; R′′ ) CH3, R1 ) C4H3S, R′ ) H 47a; R′′ ) CH3,
R1 ) Si(t-Bu)(Me)2, R′ ) CH3 48b; R′′ ) C2H5, R1 ) H,
R′ ) CH3 49b; R′′ ) C2H5, R1 ) C6H5, R′ ) CH3 50b;
R′′ ) C2H5, R1 ) C6H4CH3, R′ ) CH3 51b; R′′ ) C2H5,
R1 ) C4H3S, R′ ) CH3 52b) (Scheme 4). In an exemplary
Figure 4. Molecular structure of 13a (only one of the two
independent molecules is shown with 30% probability
displacement ellipsoids). Selected bond lengths (Å) and
angles (deg): Mn1-C1 1.737(4), C1-C2 1.351(6); Mn1-
C1-C2 179.5(3), C1-C2-C3 127.1(4) (the following values
are the corresponding bond parameters for the second
independent molecule: Mn2-C20 1.726(4), C20-C21 1.361-
(6); Mn2-C20-C21 177.9(3), C20-C21-C22 125.8(4)).
Selected hydrogen atoms and the disordered atoms have
been omitted for clarity.
NMR spectra show characteristic multiplet signals at
around 2.72 ppm for complexes 21b and 24a and at 4.39
ppm for complexes 22b, 23b, 25a, and 26a. The 31P
NMR resonances appear as a broad singlet at 81.1 ppm
(21b) and 100.1 ppm (24a) for the dmpe ligand and the
depe ligand, respectively. However, two multiplets were
observed between 79 and 80 ppm for complexes 22b and
23b and between 100 and 101 ppm for 25a and 26a.
Further, a septet was observed at -145.4 ppm for the
[PF6] anion for all complexes 21b, 22b, 23b, and 24a.
Additionally, the 13C NMR spectrum shows the CR atom
between 330 and 340 ppm for all complexes and Câ
between 46 and 50 ppm for 21b and 24a, and between
72 and 90 ppm for complexes 22b, 23b, 25a, and 26a,
which is characteristic for these kinds of carbyne
complexes.81,82 The formation of complexes 21b, 24a,
22b, 23b, 25a, and 26a implies highly selective oxida-
tive C-C coupling processes starting from mononuclear
cationic radicals as intermediates. The coupling process
is believed to go through a radical cationic species, which
consequently undergoes a dimerization to yield the
coupling product. However, the oxidation of complexes
1
fashion we describe here the H NMR spectrum of the
mixture obtained from the oxidation of 12a, which
shows a characteristic multiplet at 2.72 ppm for the CH2
4
groups of 27a, a triplet at 6.33 ppm with JP-H ) 6.0
Hz for the vinylidene protons of 28a, and a multiplet
at 2.10 ppm for the terminal CH3 group of 29a. The 31
P
NMR spectrum revealed broad resonances at 78.9 (27a),
Scheme 3

µ-C-C Bonds of Dinuclear Manganese Complexes
Organometallics, Vol. 24, No. 5, 2005 925
Scheme 4
77.8 (28a), and 81.5 ppm (29a) corresponding to the
dmpe ligands. The 13C spectra showed resonances for
CR at 325.0 ppm for 27a, 317.2 ppm for 28a, and 300.5
ppm for 29a, respectively. The reason for the formation
of this complex series is due to a too slow oxidation of
the starting vinylidene complex by [FeCp2][PF6], which
leaves the radical cation of the vinylidene species
enough time to undergo proton transfer to the residual
vinylidene complex, which can act as base and form the
generally quite stable carbyne complexes.84 The remain-
ing (C5H4R′)(R′′2PCH2CH2PR′′2)Mn-CtC-R1 complexes,
being radicals as well, undergo self-coupling to the
µ-vicinal alkylidene type bridged compounds (Scheme
4).
PH2)MndCdCHR]•+ (R ) H 12b-H, Me, C6H5 13b-H,
C6H4CH3 14b-H, Si(t-Bu)(CH3)2 16b-H) and the corre-
sponding dinuclear products [(C5H4Me)(H2PCH2CH2-
PH2)MntC-CHR-CHR-CtMn(H2PCH2CH2PH2)(C5H4-
Me)]2+ (R ) H 21b-H, Me, C6H5 22b-H, C6H4CH3, Si(t-
Bu)(CH3)2), for which the dHpe ligands have been used
instead of the dmpe ligands. In the selected molecules
only the dimer complexes 21b (R ) H) and 22b (R )
C6H5) have been formed and experimentally character-
ized without ambiguity, while the reaction starting from
14b (R ) C6H4CH3) or 16b (R ) Si(t-Bu)(CH3)2) led to
(85) Beevor, R. G.; Freeman, M. J.; Green, M.; Morton, C. E.; Orpen,
A. G. J. Chem. Soc., Chem. Commun. 1985, 68-70.
(86) ADF2002.02,SCM; Theoretical Chemistry, Vrije Universiteit:
Amsterdam, The Netherlands, http://www.scm.com.
(87) Guerra, C. F.; Snijders, J. G.; te Velde, G.; Baerends, E. J. Theor.
Chem. Acc. 1998, 99, 391-403.
(88) te Velde, G.; Bickelhaupt, F. M.; Baerends, E. J.; Guerra, C.
F.; Van Gisbergen, S. J. A.; Snijders, J. G.; Ziegler, T. J. Comput. Chem.
2001, 22, 931-967.
To investigate the role of substituents on the Câ atom
in the coupling process leading to dinuclear manganese
systems, we carried out density functional calcula-
tions86-88 on various model compounds: the mono-
nuclear cationic radical systems [(C5H4Me)(H2PCH2CH2-

926 Organometallics, Vol. 24, No. 5, 2005
Venkatesan et al.
Figure 6. Calculated LUMO of the dinuclear model
complex 22b-H showing the π-type antibonding interac-
tions between Mn and CR and between Câ and Câ′.
Me)]2+ (R ) Me and C6H5) confirmed the assumption
that the selectivity arises from an appropriate sterically
enforced structure of the radical cation appearing during
the dimerization process. Indeed, full geometry optimi-
zations carried out for both configurations of the com-
plexes studied led to differences of energy between the
true minima in favor of the (R, S) diastereomer by 4.5
and 19.3 kJ/mol for compounds with R ) Me and C6H5,
respectively.
Figure 5. Molecular structure of 22b (50% probability
displacement ellipsoids). Selected bond lengths (Å) and
angles (deg): Mn1-C1 1.653(4), C1-C2 1.493(6), C2-C2a
1.503(9); Mn1-C1-C2 176.0(4), C1-C2-C2a 114.6(5),
C1-C2-C3 108.2(4). Selected hydrogen atoms and the
-
PF6 anions have been omitted for clarity.
complicated mixtures. The model complex with R ) Me
has also been chosen, because it is sterically and
electronically intermediate between R ) H and R )
C6H5. The optimized mononuclear cationic radical sys-
tems showed spin densities located at the manganese
and the Câ atoms. The probability of finding the un-
paired electron of the system on the terminal carbon
atom Câ decreases following the order R ) H (+0.367R)
> Me (+0.366R) > C6H5 (+0.358R) > C6H4CH3 (+0.344R)
> Si(t-Bu)(CH3)2 (+0.332R). Furthermore, single-point
calculations including a model for solvation effects
performed on the gas-phase geometries of the mono-
nuclear and dinuclear model complexes led to dimer-
ization energies ∆E of -24.2 (R ) H), -12.3 (R ) Me),
-3.9 (R ) C6H5), -2.1 (R ) C6H4CH3), and +12.1 kcal/
mol (R ) Si(t-Bu)(CH3)2), following the same order as
the Câ spin density (∆E ) Edimer - 2Emonomer). These
calculations suggest that the dimerization process to
generate a C-C-coupled dinuclear product should be
easier for [(C5H4Me)(dHpe)MndCdCH2]•+ in compari-
son to the last one of the series, [(C5H4Me)(dHpe)Mnd
CdCH(Si(t-Bu)(CH3)2)]•+, which is in very good agree-
ment with the experimental observations. Nevertheless,
for all studied systems the negative dimerization ener-
gies indicate that the formation of the dinuclear com-
pounds are more or less thermodynamically favored,
and consequently we believe that such reactions can be
tuned toward obtaining single products taking into
account the oxidation potential of the complexes by
using powerful oxidizing agents, and this kind of study
is currently being investigated.
The cyclic voltammetric studies of 12b and 13b show
quasi-reversible behavior. The first oxidation step is a
relatively slow step at -0.246 V, but the dimerization
occurs very rapidly and was observed at 0.368 V.
Further, the dinuclear complex can be re-reduced, and
thus, the whole process turns out to be quasi-reversible.
The reduction of the dinuclear carbyne complexes 21b,
22b, 23b, 24a, 25a, and 26a with Cp2*Co yielded
quantitatively the corresponding mononuclear vinylidene
complexes 12b, 13b, 15b, 17a, 18a, and 20a, respec-
tively. The reversibility of this process can be explained
and is highlighted by the shape of the LUMO of the low-
spin dinuclear model complex 22b-H (Figure 6). The
vacant orbital is mainly of π-type antibonding character
between Mn and CR and σ-antibonding between Câ and
Câ′. The reduction of the dinuclear compound resulting
formally from an addition of two electrons into the
LUMO destabilizes the MntCR and the Câ-Câ′ bonds
and leads back to the mononuclear vinylidene systems.
Single-point calculations on the gas-phase geometries
with a model for solvation effects performed on the
selected dinuclear model complexes gave the energy
level of the corresponding LUMO at -5.26 (R ) H),
-5.14 (R ) Me), -4.85 (R ) C6H5), and -4.75 (R ) C6H4-
CH3). The energy difference between the HOMO and
the LUMO follows the same order with ∆E(HOMO-LUMO)
) 2.16 (R ) H), 2.18 (R ) Me), 2.29 (R ) C6H5), and
2.33 (R ) C6H4CH3) to indicate that the reduction of
the dinuclear carbyne complexes should be the easiest
in the case of R ) H because the LUMO is in this case
more accessible to add two electrons to it. The complex
[(C5H4Me)(dHpe)MntC-CH(Si(t-Bu)(CH3)2)CH(Si(t-Bu)-
(CH3)2)CtMn(dHpe)(C5H4Me)]2+ should be treated sepa-
rately from the others because it seems clear that the
very positive dimerization energy of ∆E ) +12.1 kcal/
mol is due to the very bulky ligand Si(t-Bu)(CH3)2, which
prevents the formation of the dimer. Nevertheless, the
It is also noteworthy that the oxidation of complexes
13b, 15b, 18a, and 20a gives specifically only one
diastereomer in each case: the meso (R, S) isomer 22b,
23b, 25a, and 26a. In the case of complex 22b the (R,
S) configuration has been characterized spectroscopi-
cally as well as crystallographically (Figure 5). DFT
calculations performed on the dinuclear products [(C5H4-
Me)(dHpe)MntC-CHR-CHR-CtMn(dHpe)(C5H4-

µ-C-C Bonds of Dinuclear Manganese Complexes
Organometallics, Vol. 24, No. 5, 2005 927
stirred at 50 °C for 3 h to give a dark red solution. The solvent
was removed under vacuum to afford a dark red oil. Then the
oil was extracted with pentane and filtered through Celite.
The pentane fraction was evaporated to give a orange-red solid.
Crystallization from pentane at -35 °C gave single orange-
red crystals. Yield: 292 mg, 98%. Anal. Calcd for C19H39MnP2-
energy difference ∆E(HOMO-LUMO) of 2.33 eV (the largest
one calculated together with R ) C6H4CH3) makes this
dicationic dinuclear complex the last complex of the
series.
The observation of reactions described above is sig-
nificant in many respects: (i) the C-C bond formation
and cleavage are reversible, (ii) the C-C bond cleavage
acts as a shuttle of two electrons, and (iii) such an
electron transfer can occur intermolecularly. On the
whole, these systems would function as a device for
storing and releasing two electrons involving the fol-
lowing balance: 4eπ f 2eσ + 2e. On a reversible basis
one could certainly envisage using these molecules as
electron reservoirs.14-32
1
Sn2 (621.81): C, 36.69; H, 6.32. Found: C, 36.76; H, 6.42. H
NMR (C6D6, 300 MHz, 20 °C): δ 4.12 (5H, C5H5), 1.42 (2H,
PCH2), 1.31 (3H, P(CH3)3), 1.16 (2H, PCH2), 0.87 (3H, P(CH3)3),
0.32(3H, Sn(CH3)3). 31P{1H} NMR (C6D6, 121.5 MHz, 20 °C):
δ 91.3 (s, 2P). 13C NMR (C6D6, 125 MHz, 20 °C): δ 321.4 (m,
Mn-CR), 114.8 (m, dCâ), 83.8 (Cp), 30.8 (PCH2), 23.5 (P(CH3)3),
21.3 (P(CH3)3), -8.1 (Sn(CH3)3). 119Sn NMR (C6D6, 186.4 MHz,
20 °C): δ -20 (t, 77.0 Hz, Sn(CH3)3). IR (CH2Cl2, 20 °C): 1598
cm-1 ν(CdC), 1550 cm-1 ν(CdC).
[(MeC5H4)Mn(dmpe)dCdC(SnMe3)2], 2b. The same pro-
cedure was adopted as above using 1b as the starting
component. Crystallization from pentane at -35 °C gave single
orange-red crystals. Yield: 270 mg, 96%. Anal. Calcd for
C20H41MnP2Sn2 (635.84): C, 37.77; H, 6.49. Found: C, 37.65;
Conclusion
In conclusion, a series of mononuclear half-sandwich
complexes of the type Mn(C5H4R′)(R′′2PCH2CH2PR′′2)-
(dCdC(R1)(H)) have been prepared. Coupling and the
reverse decoupling processes of these complexes have
been investigated. The influence exerted by the sub-
stituents of the Câ atom of the vinylidene system on the
oxidative coupling and the reductive decoupling pro-
cesses investigated by DFT calculations corroborates
that of the experimental findings. This study highlights
the potential of utilizing the ubiquitous C-C bonds in
organometallic systems as electron reservoirs, thereby
allowing further development of molecular batteries,
which could find application as components in nanode-
vices.
1
H, 6.25. H NMR (C6D6, 300 MHz, 20 °C): δ 4.04 (2H, C5H4-
Me), 3.77 (2H, C5H4Me), 2.06 (3H, C5H4Me), 1.51 (2H, PCH2),
1.31 (3H, PMe3), 1.22 (2H, PCH2), 0.88 (3H, PMe3) 0.32 (3H,
SnMe3). 31P{1H} NMR (C6D6, 121.5 MHz, 20 °C): δ 91.2 (s,
2P). 13C NMR (C6D6, 125 MHz, 20 °C): δ 321.6 (m, Mn-CR),
114.8 (m, dCâ), 84.2 (C5H4Me), 77.8 (C5H4Me), 31.8 (PCH2),
21.5 (PMe3), 14.8 (PMe3), 14.5 (1C, C5H4Me), -4.9 (SnMe3).
119Sn NMR (C6D6, 186.4 MHz, 20 °C): δ -20 (t, 77.0 Hz,
Sn(CH3)3). IR (CH2Cl2, 20 °C): 1594 cm-1 ν(CdC), 1552 cm-1
ν(CdC).
[(C5H5)Mn(dmpe)dCdC(Ph)(SnMe3)], 3a. To a toluene
solution (10 mL) of (C5H5)Mn(CΗΤ) (100 mg, 0.48 mmol) was
added a toluene solution (10 mL) of dmpe (70 mg, 0.48 mmol)
and Ph-CtC-SnMe3 (130 mg, 0.48 mmol). The solution was
stirred at 50 °C for 3 h to give a dark red solution. The solvent
was removed under vacuum to afford a dark red oil. Then the
oil was extracted with pentane and filtered through Celite.
The pentane fraction was evaporated to give an orange-red
solid. Crystallization from pentane at -35 °C gave single
orange-red crystals. Yield: 250 mg, 98%. Anal. Calcd for
C22H35MnP2Sn (535.10): C, 49.38; H, 6.59. Found: C, 49.43;
H, 6.97. 1H NMR (C6D6, 300 MHz, 20 °C): δ 7.25 (2H, m, C6H5),
7.16 (2H, m, C6H5), 6.83 (1H, m, C6H5), 4.31 (5H, C5H5), 1.42
(2H, PCH2), 1.18 (3H, P(CH3)3), 0.96 (2H, PCH2), 0.87 (3H,
P(CH3)3), 0.35 (3H, Sn(CH3)3). 31P{1H} NMR (C6D6, 121.5 MHz,
20 °C): δ 93.1 (s, 2P). 13C NMR (C6D6, 125 MHz, 20 °C): δ
329.4 (m, Mn-CR), 145.8 (m, dCâ), 136.7 (s, 1C, Cipso(C6H5)),
122.2 (s, 1C, C6H5), 120.5 (s, 2C, C6H5), 120.2 (s, 2C, C6H5),
84.3 (5C, C5H5), 31.1 (PCH2), 24.1 (PCH2), 23.2 (P(CH3)3), 21.3
(P(CH3)3), -6.3 (Sn(CH3)3). 119Sn NMR (C6D6, 186.4 MHz, 20
°C): δ -16.32 (t, 71.0 Hz, Sn(CH3)3). IR (CH2Cl2, 20 °C): 1596
cm-1 ν(CdC), 1549 cm-1 ν(CdC).
[(MeC5H4)Mn(dmpe)dCdC(Ph)(SnMe3)], 3b. The same
procedure was adopted as above using 1b as the starting
component. Crystallization from pentane at -35 °C gave single
orange-red crystals. Yield: 240 mg, 98%. Anal. Calcd for
C23H37MnP2Sn (549.15): C, 50.30; H, 6.79. Found: C, 49.94;
H, 6.75. 1H NMR (C6D6, 300 MHz, 20 °C): δ 7.25 (2H, m, C6H5),
7.16 (2H, m, C6H5), 6.83 (1H, m, C6H5), 4.27 (2H, C5H4Me),
3.91 (2H, C5H4Me), 2.04 (3H, C5H4CH3), 1.40 (2H, PCH2), 1.11
(3H, P(CH3)3), 0.92 (2H, PCH2), 0.75 (3H, P(CH3)3) 0.31 (3H,
Sn(CH3)3). 31P{1H} NMR (C6D6, 121.5 MHz, 20 °C): δ 92.8 (s,
2P). 13C NMR (C6D6, 125 MHz, 20 °C): δ 329.6 (m, Mn-CR),
143.8 (m, dCâ), 137.7 (s, 1C, Cipso(C6H5)), 122.6 (s, 1C, C6H5),
121.1 (s, 2C, C6H5), 121.7 (s, 2C, C6H5), 98.4 (s, Cipso(MeC5H4)),
81.3 (C5H4Me), 80.2 (C5H4Me), 31.8 (PCH2), 24.1 (PCH2), 21.5
(P(CH3)3), 14.8 (P(CH3)3), 14.5 (s, C5H4CH3), -6.1 (Sn(CH3)3).
119Sn NMR (C6D6, 186.4 MHz, 20 °C): δ -17.2 (t, 77.0 Hz,
Sn(CH3)3). IR (CH2Cl2, 20 °C): 1596 cm-1 ν(CdC), 1548 cm-1
ν(CdC).
Experimental Section
General Procedures. Reagent grade benzene, toluene,
hexane, pentane, diethyl ether, and tetrahydrofuran were
dried and distilled from sodium benzophenone ketyl prior to
use. Dichloromethane was distilled first from P2O5, and then
prior to use from CaH2. Literature procedures were used to
prepare the following compounds: 1,2-bis(dimethylphosphino)-
ethane (dmpe),89 1,2-bis(diethylphosphino)ethane (depe),89 (η5-
C5H4R′)Mn(CΗΤ),79 Me3Sn-CtC-SnMe3,90 C6H5-CtC-
SnMe3,90 CH3C6H4-CtC-SnMe3,90 SC4H3-CtC-SnMe3, (t-
Bu)(Me)2Si-CtC-SnMe3,90 [Cp2Fe][PF6].91 [Cp2*Co], n-BuLi
(1.6 M in hexane), MeLi‚LiBr (1.5 M in diethyl ether), Me3-
SnCl, tetrabutylammonium fluoride (1.0 M in tetrahydrofu-
ran), C6H5-CtC-H, CH3C6H4-CtC-H, SC4H3-CtC-H,
and (t-Bu)(Me)2Si-CtC-H were used as received. All the
manipulations were carried out under a nitrogen atmosphere
using Schlenk techniques or a drybox. IR spectra were
obtained on a Bio-Rad FTS-45 instrument. NMR spectra were
measured on a Varian Gemini-2000 spectrometer at 300 MHz
for H and 121.5 MHz for 31P{1H} and on a Bruker-DRX-500
1
spectrometer at 125.8 MHz for 13C{1H} and 186.5 MHz for 119
-
1
Sn, respectively. Chemical shifts for H and 13C are given in
ppm relative to the solvent signals. The 31P{1H} NMR spectra
were referenced to 98% external H3PO4 and the 119Sn{1H}
NMR spectra to SnBu4.
[(C5H5)Mn(dmpe)dCdC(SnMe3)2], 2a. To a toluene solu-
tion (10 mL) of (C5H5)Mn(CΗΤ) (100 mg, 0.48 mmol) was added
a toluene solution (10 mL) of dmpe (70 mg, 0.48 mmol) and
Me3Sn-CtC-SnMe3 (170 mg, 0.48 mmol). The solution was
(89) Burt, R. J.; Chatt, J.; Hussain, W.; Leigh, G. J. J. Organomet.
Chem. 1979, 182, 203-206.
(90) Brandsma, L. Preparative Acetylenic Chemistry; Elsevier: Am-
sterdam, 1988.
(91) Hendrick, D. N.; Sohn, Y. S.; Gray, H. B. Inorg. Chem. 1971,
10, 1550.

928 Organometallics, Vol. 24, No. 5, 2005
Venkatesan et al.
[(C5H5)Mn(dmpe)dCdC(C6H4CH3)(SnMe3)], 4a. To a
toluene solution (10 mL) of (C5H5)Mn(CΗΤ) (100 mg, 0.48
mmol) was added a toluene solution (10 mL) of dmpe (70 mg,
0.48 mmol) and CH3C6H4-CtC-SnMe3 (130 mg, 0.48 mmol).
The solution was stirred at 50 °C for 3 h to give a dark red
solution. The solvent was removed under vacuum to afford a
dark red oil. Then the oil was extracted with pentane and
filtered through Celite. The pentane fraction was evaporated
to give an orange-red solid. Crystallization from pentane at
-35 °C gave single orange-red crystals. Yield: 255 mg, 98%.
Anal. Calcd for C23H37MnP2Sn (549.13): C, 50.30; H, 6.79.
Found: C, 50.63; H, 6.87. 1H NMR (C6D6, 300 MHz, 20 °C): δ
7.26 (2H, m, C6H4CH3), 7.10 (2H, m, C6H4CH3), 4.32 (5H,
C5H5), 2.23 (3H, C6H4CH3), 1.42 (2H, PCH2), 1.18 (3H, P(CH3)3),
0.96 (2H, PCH2), 0.79 (3H, P(CH3)3), 0.37 (9H, Sn(CH3)3). 31P-
{1H} NMR (C6D6, 121.5 MHz, 20 °C): δ 94.5 (s, 2P). 13C NMR
(C6D6, 125 MHz, 20 °C): δ 343.5 (m, Mn-CR), 139.2 (m, dCâ),
130.8 (s, 1C, Cipso(C6H4CH3)), 129.5 (s, 2C, C6H4CH3), 123.1
(s, 2C, C6H4CH3), 122.7 (s, 1C, C6H4CH3), 82.9 (5C, C5H5), 31.2
(PCH2), 23.7 (PCH2), 22.1 (P(CH3)3), 21.7 (P(CH3)3), 21.3 (1C,
C6H4CH3), -6.3 (Sn(CH3)3). 119Sn NMR (C6D6, 186.4 MHz, 20
°C): δ -16.5 (t, 71.0 Hz, Sn(CH3)3). IR (CH2Cl2, 20 °C): 1596
cm-1 ν(CdC), 1549 cm-1 ν(CdC).
[(MeC5H4)Mn(dmpe)dCdC(C6H4CH3)(SnMe3)], 4b. The
same procedure was adopted as above using 1b as the starting
component. Crystallization from pentane at -35 °C gave single
orange-red crystals. Yield: 235 mg, 93%. Anal. Calcd for
C24H39MnP2Sn (563.16): C, 51.18; H, 6.98. Found: C, 51.34;
H, 6.82. 1H NMR (C6D6, 300 MHz, 20 °C): δ 7.21 (2H, m, C6H4-
CH3), 7.14 (2H, m, C6H4CH3), 4.27 (2H, C5H4CH3), 3.91 (2H,
C5H4CH3), 2.21 (3H, C6H4CH3), 2.03 (3H, C5H4CH3), 1.40 (2H,
PCH2), 1.11 (3H, P(CH3)3), 0.92 (2H, PCH2), 0.75 (3H, P(CH3)3)
0.28 (9H, Sn(CH3)3). 31P{1H} NMR (C6D6, 121.5 MHz, 20 °C):
δ 93.1 (s, 2P). 13C NMR (C6D6, 125 MHz, 20 °C): δ 329.6 (m,
Mn-CR), 143.8 (m, dCâ), 130.8 (s, 1C, Cipso(C6H4CH3)), 129.5
(s, 2C, C6H4CH3), 123.1 (s, 2C, C6H4CH3), 122.7 (s, 1C, C6H4-
CH3), 98.4 (s, Cipso(MeC5H4)), 81.3 (C5H4Me), 80.1 (C5H4Me),
31.4 (PCH2), 24.1 (PCH2), 21.3 (1C, C6H4CH3), 21.2 (P(CH3)3),
14.6 (P(CH3)3), 14.5 (s, C5H4CH3), -5.8 (Sn(CH3)3). 119Sn NMR
(C6D6, 186.4 MHz, 20 °C): δ -17.2 (t, 71.0 Hz, Sn(CH3)3). IR
(CH2Cl2, 20 °C): 1596 cm-1 ν(CdC), 1548 cm-1 ν(CdC).
[(C5H5)Mn(dmpe)dCdC(C4H3S)(SnMe3)], 5a. To a tolu-
ene solution (10 mL) of (C5H5)Mn(CΗΤ) (100 mg, 0.48 mmol)
was added a toluene solution (10 mL) of dmpe (70 mg, 0.48
mmol) and SC4H3-CtC-SnMe3 (155 mg, 0.48 mmol). The
solution was stirred at 50 °C for 3 h to give a dark red solution.
The solvent was removed under vacuum to afford a dark red
oil. Then the oil was extracted with pentane and filtered
through Celite. The pentane fraction was evaporated to give
an orange-red solid. Crystallization from pentane at -35 °C
gave single orange-red crystals. Yield: 245 mg, 95%. Anal.
Calcd for C20H33MnP2SSn (541.13): C, 44.39; H, 6.14. Found:
C, 44.43; H, 6.37. 1H NMR (C6D6, 300 MHz, 20 °C): δ 7.08
(1H, m, C4H3S), 6.79 (1H, m, C4H3S), 6.41 (1H, m, C4H3S), 4.35
(5H, C5H5), 1.41 (2H, PCH2), 1.20 (3H, P(CH3)3), 0.94 (2H,
PCH2), 0.82 (3H, P(CH3)3), 0.05 (3H, Sn(CH3)3). 31P{1H} NMR
(C6D6, 121.5 MHz, 20 °C): δ 93.1 (s, 2P). 13C NMR (C6D6, 125
MHz, 20 °C): δ 329.6 (m, Mn-CR), 144.8 (m, dCâ), 136.7 (s,
1C, Cipso(C6H5)), 125.1 (s, 1C, C4H3S), 122.3 (s, 1C, C4H3S),
110.5 (s, 1C, C4H3S), 84.1 (5C, C5H5), 31.4 (PCH2), 24.5 (PCH2),
23.3 (P(CH3)3), 21.3 (P(CH3)3), -6.4 (Sn(CH3)3). 119Sn NMR
(C6D6, 186.4 MHz, 20 °C): δ -17.1 (t, 74.5 Hz, Sn(CH3)3). IR
(CH2Cl2, 20 °C): 1594 cm-1 ν(CdC), 1543 cm-1 ν(CdC).
[(MeC5H4)Mn(dmpe)dCdC(C4H3S)(SnMe3)], 5b. The
same procedure was adopted as above using 1b as the starting
component. Crystallization from pentane at -35 °C gave single
orange-red crystals. Yield: 240 mg, 96%. Anal. Calcd for
C21H35MnP2SSn (555.16): C, 45.43; H, 6.35. Found: C, 45.67;
H, 6.59. 1H NMR (C6D6, 300 MHz, 20 °C): δ 7.08 (1H, m,
C4H3S), 6.79 (1H, m, C4H3S), 6.41 (1H, m, C4H3S), 4.31 (2H,
C5H4Me), 4.01 (2H, C5H4Me), 2.01 (3H, C5H4CH3), 1.38 (2H,
PCH2), 1.13 (3H, P(CH3)3), 0.90 (2H, PCH2), 0.74 (3H, P(CH3)3)
0.13 (3H, Sn(CH3)3). 31P{1H} NMR (C6D6, 121.5 MHz, 20 °C):
δ 95.3 (s, 2P). 13C NMR (C6D6, 125 MHz, 20 °C): δ 329.6 (m,
Mn-CR), 144.8 (m, dCâ), 136.7 (s, 1C, Cipso(C4H3)), 125.1 (s,
1C, C4H3S), 122.3 (s, 1C, C4H3S), 110.5 (s, 1C, C4H3S), 98.3 (s,
C
ipso(MeC5H4)), 81.1 (C5H4Me), 80.5 (C5H4Me), 31.7 (PCH2),
24.1 (PCH2), 21.5 (P(CH3)3), 14.8 (P(CH3)3), 14.5 (s, C5H4CH3),
-6.4 (Sn(CH3)3). 119Sn NMR (C6D6, 186.4 MHz, 20 °C): δ -17.2
(t, 75.0 Hz, Sn(CH3)3). IR (CH2Cl2, 20 °C): 1592 cm-1 ν(CdC),
1551 cm-1 ν(CdC).
[(MeC5H4)Mn(dmpe)dCdC(Si(t-Bu)(Me)2)(SnMe3)], 6b.
To a toluene solution (10 mL) of (MeC5H4)Mn(CΗΤ) (100 mg,
0.45 mmol) was added a toluene solution (10 mL) of dmpe (70
mg, 0.45 mmol) and (t-Bu)(Me)2Si-CtC-SnMe3 (140 mg, 0.45
mmol). The solution was stirred at 50 °C for 3 h to give a dark
red solution. The solvent was removed under vacuum to afford
a dark red oil. Then the oil was extracted with Et2O and
filtered through Celite. The Et2O fraction was evaporated to
give an orange-red oil. Crystallization from pentane at -35
°C gave single orange-red crystals. Yield: 250 mg, 96%. Anal.
Calcd for C23H47MnP2SiSn (587.30): C, 47.03; H, 8.06.
Found: C, 47.31; H, 8.39. 1H NMR (C6D6, 300 MHz, 20 °C): δ
4.03 (2H, C5H4CH3), 3.78 (2H, C5H4CH3), 2.05 (3H, C5H4CH3),
1.40 (2H, PCH2), 1.11 (3H, P(CH3)3), 1.03 (9H, Si(t-C4H9)(Me)2),
0.92 (2H, PCH2), 0.75 (3H, P(CH3)3) 0.54 (6H, Si(t-C4H9)(CH3)2),
0.23 (9H, Sn(CH3)3). 31P{1H} NMR (C6D6, 121.5 MHz, 20 °C):
δ 94.6 (s, 2P). 13C NMR (C6D6, 125 MHz, 20 °C): δ 327.7 (m,
Mn-CR), 142.2 (m, dCâ), 98.4 (s, Cipso(MeC5H4)), 81.3 (C5H4-
Me), 80.1 (C5H4Me), 35.2 (3C, Si(t-C4H9)(Me)2), 28.3 (3C, Si-
(t-C4H9)(Me)2), 31.4 (PCH2), 24.1 (PCH2), 21.2 (P(CH3)3), 14.6
(P(CH3)3), 14.5 (s, C5H4CH3), -1.2 (2C, Si(t-C4H9)(CH3)2), -3.6
(3C, Sn(CH3)3). 29Si NMR (C6D6, 99.4 MHz, 20 °C): δ -3.2 (t,
5.0 Hz, Si(t-C4H9)(Me)2). 119Sn NMR (C6D6, 186.4 MHz, 20
°C): δ -20.8 (t, 84.1 Hz, Sn(CH3)3). IR (CH2Cl2, 20 °C): 1573
cm-1 ν(CdC), 1553 cm-1 ν(CdC).
[(MeC5H4)Mn(depe)dCdC(C4H3S)(SnMe3)], 10b. The
same procedure was adopted as above using 1b as the starting
component. Crystallization from pentane at -35 °C gave single
orange-red crystals. Yield: 250 mg, 98%. Anal. Calcd for
C25H43MnP2SSn (611.27): C, 49.12; H, 7.09. Found: C, 49.27;
H, 7.43. 1H NMR (C6D6, 300 MHz, 20 °C): δ 7.08 (1H, m,
C4H3S), 6.79 (1H, m, C4H3S), 6.41 (1H, m, C4H3S), 4.38 (2H,
C5H4Me), 3.86 (2H, C5H4Me), 2.11 (3H, C5H4CH3), 1.71 (m, 2H,
PCH2), 1.45 (m, 4H, PCH2CH3), 1.22 (m, 4H, PCH2CH3), 1.03
(m, 2H, PCH2), 0.85 (m, 6H, PCH2CH3), 0.78 (m, 6H, PCH2CH3),
0.20 (9H, Sn(CH3)3). 31P{1H} NMR (C6D6, 121.5 MHz, 20 °C):
δ 116.0 (s, 2P). 13C NMR (C6D6, 125 MHz, 20 °C): δ 326.6 (m,
Mn-CR), 136.7 (s, 1C, Cipso(C4H3)), 125.1 (s, 1C, C4H3S), 122.3
(s, 1C, C4H3S), 110.5 (s, 1C, C4H3S), 98.4 (s, 1C, ipso-C
MeC5H4), 95.4 (m, 1C, dCâ), 81.1 (2C, C5H4Me), 80.0 (2C, C5H4-
Me), 31.9 (1C, PCH2), 24.3 (PCH2CH3), 24.1 (2C, PCH2CH3),
23.6 (1C, PCH2), 14.5 (s, C5H4CH3), 8.6 (2C, PCH2CH3), 9.8
(PCH2CH3), -6.7 (3C, Sn(CH3)3). 119Sn NMR (C6D6, 186.4 MHz,
20 °C): δ -16.2 (t, 74.0 Hz, Sn(CH3)3). IR (CH2Cl2, 20 °C):
1592 cm-1 ν(CdC), 1548 cm-1 ν(CdC).
[Mn(depe)2(CtC-Ph)2], 11. To a toluene solution (10 mL)
of (C5H5)Mn(CΗΤ) (100 mg, 0.48 mmol) was added a toluene
solution (10 mL) of depe (100 mg, 0.48 mmol) and Ph-CtC-
SnMe3 (130 mg, 0.48 mmol). The solution was stirred at 50 °C
for 3 h to give a dark red solution. The solvent was removed
under vacuum to afford a dark red oil. Then the oil was
extracted with pentane and filtered through Celite. The
pentane fraction was evaporated to give an orange-red solid.
The pentane insoluble was then extracted with ether and
filtered through Celite. The Et2O was then evaporated to give
a red solid. Crystallization from ether at -35 °C gave single
orange-red crystals. Yield: 64 mg, 20%. Anal. Calcd for C36H58-
MnP4 (669.69): C, 64.57; H, 8.73. Found: C, 64.92; H, 8.59.
1H NMR (THF-d8, 300 MHz, 20 °C): δ 16.9 (2H, Hmeta, C6H5),
0.5 (24H, PCH2CH3), -1.1 (2H, Hpara, C6H5), -4.9 (1H, Hortho
,

µ-C-C Bonds of Dinuclear Manganese Complexes
Organometallics, Vol. 24, No. 5, 2005 929
C6H5), -9.8 (16H, PCH2CH3), -13.7 (8H, PCH2CH2P). IR (CD2-
Cl2, 20 °C): 2006 cm-1 (s), 1980 cm-1 (s) ν(CtC), 1027 cm-1(s)
ν(P-C).
[(C5H5)Mn(dmpe)dCdC(C6H4CH3)(H)], 14a. To a toluene
solution (10 mL) of (C5H5)Mn(dmpe)dCdC(C6H4CH3)(SnMe3)
(4a) (100 mg, 0.18 mmol) was added 1 equiv of 1.0 M TBAF
(0.18 mL, 0.18 mmol). The solution was stirred at room
temperature for 2 h to give a dark red solution. The solvent
was removed under vacuum to afford a dark red oil. Then the
oil was extracted with pentane and filtered through Celite.
The pentane fraction was evaporated to give an orange-red
solid. Crystallization from pentane at -35 °C gave single
orange-red crystals. Yield: 68 mg, 98%. Anal. Calcd for C20H29-
MnP2 (386.32): C, 62.17; H, 7.56. Found: C, 62.03; H, 7.43.
1H NMR (C6D6, 300 MHz, 20 °C): δ 7.33 (2H, m, C6H4CH3),
7.10 (2H, m, C6H4CH3), 5.98 (1H, t, 4JPH ) 8.7 Hz, dCHC6H4-
CH3), 4.47 (5H, C5H5), 2.18 (3H, s, C6H4CH3), 1.39 (2H, PCH2),
1.12 (3H, P(CH3)3), 0.80 (2H, PCH2), 0.71 (3H, P(CH3)3). 31P-
{1H} NMR (C6D6, 121.5 MHz, 20 °C): δ 94.2 (s, 2P). 13C NMR
(C6D6, 125 MHz, 20 °C): δ 339.4 (m, Mn-CR), 138.9 (m, dCâ),
130.8 (s, 1C, Cipso(C6H4CH3)), 128.7 (s, 2C, C6H4CH3), 123.1
(s, 2C, C6H4CH3), 121.6 (s, 1C, C6H4CH3), 82.3 (5C, C5H5), 30.9
(PCH2), 23.4 (PCH2), 22.1 (s, 1C, C6H4CH3), 21.3 (PMe3), 19.4
(PMe3). IR (CH2Cl2, 20 °C): 1583 cm-1 ν(CdC), 1559 cm-1 ν-
(CdC).
[(MeC5H4)Mn(dmpe)dCdC(C6H4CH3)(H)], 14b. The same
procedure was adopted as above using 4b as the starting
component. Crystallization from pentane at -35 °C gave single
orange-red crystals. Yield: 65 mg, 91%. Anal. Calcd for C21H31-
MnP2 (400.35): C, 63.00; H, 7.80. Found: C, 63.25; H, 7.63.
1H NMR (C6D6, 300 MHz, 20 °C): 7.31 (2H, m, C6H4CH3), 7.07
(2H, m, C6H4CH3), 5.98 (1H, t, 4JPH ) 8.7 Hz, dCHC6H4CH3),
4.41 (2H, C5H4Me), 3.95 (2H, C5H4Me), 2.21 (3H, C6H4CH3),
1.91 (3H, C5H4CH3), 1.43 (2H, PCH2), 1.14 (3H, P(CH3)3), 1.10
(2H, PCH2), 0.74 (3H, P(CH3)3). 31P{1H} NMR (C6D6, 121.5
MHz, 20 °C): δ 94.7 (s, 2P). 13C NMR (C6D6, 125 MHz, 20 °C):
δ 341.5 (m, Mn-CR), 141.9 (m, dCâ), 130.8 (s, 1C, Cipso(C6H4-
CH3)), 127.9 (s, 2C, C6H4CH3), 123.6 (s, 2C, C6H4CH3), 121.6
(s, 1C, C6H4CH3), 98.4 (s, Cipso(MeC5H4)), 81.3 (C5H4Me), 80.2
(C5H4Me), 30.9 (PCH2), 23.4 (PCH2), 22.7 (s, 1C, C6H4CH3),
21.3 (P(CH3)3), 19.4 (P(CH3)3), 14.5 (s, C5H4CH3). IR (CH2Cl2,
20 °C): 1597 cm-1 ν(CdC), 1555 cm-1 ν(CdC).
[(C5H5)Mn(dmpe)dCdC(H)2], 12a. To a THF solution (10
mL) of (C5H5)Mn(dmpe)dCdC(SnMe3)2 (2a) (100 mg, 0.16
mmol) was added tetrabutylammonium fluoride (0.16 mL, 0.16
mmol). The solution was stirred at room temperature for 2 h
to give a dark red solution. The solvent was removed under
vacuum to afford a dark red oil. Then the oil was extracted
with pentane and filtered through Celite. The pentane fraction
was evaporated to give an orange-red solid. Crystallization
from pentane at -35 °C gave single orange-red crystals.
Yield: 44 mg, 92%. Anal. Calcd for C13H23MnP2 (296.20): C,
1
52.71; H, 7.82. Found: C, 53.10; H, 7.46. H NMR (THF-d8,
300 MHz, 20 °C): δ 4.3 (5Η, C5H5), 3.77 (2H, t, 4JPH ) 9.0 Hz,
dCH2), 1.96 (2H, PCH2), 1.67 (2H, PCH2), 1.31 (3H, P(CH3)3),
1.26 (3H, P(CH3)3). 31P{1H} NMR (C6D6, 121.5 MHz, 20 °C): δ
95.5 (s, 2P). 13C NMR (C6D6, 125 MHz, 20 °C): δ 341.9 (m,
Mn-CR), 97.3 (m, dCâ), 83.1 (5C, C5H5), 31.2 (PCH2), 22.4
(PCH2), 20.6 (P(CH3)3), 19.7 (P(CH3)3). IR (CH2Cl2, 20 °C):
1594 cm-1 ν(CdC), 1556 cm-1 ν(CdC).
[(MeC5H4)Mn(dmpe)dCdC(H)2], 12b. The same proce-
dure was adopted as above using 2b as the starting component.
Crystallization from pentane at -35 °C gave single orange-
red crystals. Yield: 42 mg, 92%. Anal. Calcd for C14H25MnP2
(310.23): C, 54.20; H, 8.12. Found: C, 54.36; H, 8.24. 1H NMR
(C6D6, 300 MHz, 20 °C): δ 4.34 (2H, t, 4JPH ) 9.0 Hz, dCH2),
4.28 (2H, C5H4Me), 3.94 (2H, C5H4Me), 2.13 (3H, C5H4CH3),
1.82 (2H, PCH2), 1.28 (2H, PCH2), 1.21 (3H, P(CH3)3), 0.87 (3H,
P(CH3)3). 31P{1H} NMR (C6D6, 121.5 MHz, 20 °C): δ 95.6 (s,
2P). 13C NMR (C6D6, 125 MHz, 20 °C): δ 341.9 (m, Mn-CR),
97.2 (m, dCâ), 95.4 (s, Cipso(MeC5H4)), 84.3 (C5H4Me), 80.3
(C5H4Me), 30.8 (PCH2), 22.2 (PCH2), 21.8 (P(CH3)3), 19.7
(P(CH3)3), 14.5 (s, C5H4CH3). IR (CH2Cl2, 20 °C): 1598 cm-1
ν(CdC), 1550 cm-1 ν(CdC).
[(C5H5)Mn(dmpe)dCdC(Ph)(H)], 13a. To a toluene solu-
tion (10 mL) of (C5H5)Mn(dmpe)dCdC(Ph)(SnMe3) (3a) (100
mg, 0.19 mmol) was added an excess of MeOH. The solution
was stirred at room temperature for 2 h to give a dark red
solution. The solvent was removed under vacuum to afford a
dark red oil. Then the oil was extracted with pentane and
filtered through Celite. The pentane fraction was evaporated
to give an orange-red solid. Crystallization from pentane at
-35 °C gave single orange-red crystals. Yield: 69 mg, 98%.
Anal. Calcd for C19H27MnP2 (372.30): C, 61.29; H, 7.30.
Found: C, 61.65; H, 7.53. 1H NMR (C6D6, 300 MHz, 20 °C): δ
7.39 (2H, m, C6H5), 7.30 (2H, m, C6H5), 6.95 (1H, m, C6H5),
[(C5H5)Mn(dmpe)dCdC(C4H3S)(H)], 15a. To a toluene
solution (10 mL) of (C5H5)Mn(dmpe)dCdC(C4H3S)(SnMe3) (5a)
(100 mg, 0.18 mmol) was added 1 equiv of TBAF (0.18 mL,
0.18 mmol). The solution was stirred at room temperature for
2 h to give a dark red solution. The solvent was removed under
vacuum to afford a dark red oil. Then the oil was extracted
with pentane and filtered through Celite. The pentane fraction
was evaporated in vacuo to give an orange-red solid. Crystal-
lization from pentane at -35 °C gave single orange-red
crystals. Yield: 62 mg, 92%. Anal. Calcd for C17H25MnP2S
(378.33): C, 53.96; H, 6.66. Found: C, 53.67; H, 6.53. 1H NMR
(C6D6, 300 MHz, 20 °C): δ 7.06 (1H, m, C4H3S), 6.77 (1H, m,
4
6.0 (1H, t, JPH ) 8.7 Hz, dCHC6H5), 4.34 (5H, C5H5), 1.45
(2H, PCH2), 1.12 (3H, P(CH3)3), 0.80 (2H, PCH2), 0.71 (3H,
P(CH3)3). 31P{1H} NMR (C6D6, 121.5 MHz, 20 °C): δ 94.0 (s,
2P). 13C NMR (C6D6, 125 MHz, 20 °C): δ 342.4 (m, Mn-CR),
141.9 (m, dCâ), 137.7 (s, Cipso(C6H5)), 122.6(s, C6H5), 121.1 (s,
C6H5), 121.7 (s, C6H5), 82.3 (5C, C5H5), 30.9 (PCH2), 23.4
(PCH2), 21.3 (PMe3), 19.4 (PMe3). IR (CH2Cl2, 20 °C): 1596
cm-1 ν(CdC), 1553 cm-1 ν(CdC).
4
C4H3S), 6.38 (1H, m, C4H3S), 6.10 (1H, t, JPH ) 9 Hz,
dCHC4H3S), 4.32 (5H, C5H5), 1.43 (2H, PCH2), 1.14 (3H,
P(CH3)3), 0.85 (2H, PCH2), 0.73 (3H, P(CH3)3). 31P{1H} NMR
(C6D6, 121.5 MHz, 20 °C): δ 94.8 (s, 2P). 13C NMR (C6D6, 125
MHz, 20 °C): δ 342.4 (m, Mn-CR), 141.9 (m, dCâ), 136.7 (s,
1C, Cipso(C4H3S)), 125.1 (s, 1C, C4H3S), 122.3 (s, 1C, C4H3S),
110.5 (s, 1C, C4H3S), 82.3 (5C, C5H5), 30.9(PCH2), 23.4 (PCH2),
21.3 (PMe3), 19.4 (PMe3). IR (CH2Cl2, 20 °C): 1597 cm-1 ν-
(CdC), 1548 cm-1 ν(CdC).
[(MeC5H4)Mn(dmpe)dCdC(Ph)(H)], 13b. The same pro-
cedure was adopted as above using 3b as the starting
component. Crystallization from pentane at -35 °C gave single
orange-red crystals. Yield: 68 mg, 98%. Anal. Calcd for C20H29-
MnP2 (386.33): C, 61.17; H, 7.56. Found: C, 61.35; H, 7.53.
1H NMR (C6D6, 300 MHz, 20 °C): δ 7.25 (2H, m, C6H5), 7.16
(2H, m, C6H5), 6.83 (1H, m, C6H5), 5.82 (1H, t, 4JPH ) 8.7 Hz,
dCHC6H5), 4.30 (2H, C5H4Me), 3.86 (2H, C5H4Me), 1.94(3H,
C5H4CH3), 1.46 (2H, PCH2), 1.14 (3H, P(CH3)3), 1.10 (2H,
PCH2), 0.74 (3H, P(CH3)3). 31P{1H} NMR (C6D6, 121.5 MHz,
20 °C): δ 94.5 (s, 2P). 13C NMR (C6D6, 125 MHz, 20 °C): δ
342.5 (m, Mn-CR), 142.2(m, dCâ), 137.7 (s, Cipso(C6H5)), 122.6-
[(MeC5H4)Mn(dmpe)dCdC(C4H3S)(H)], 15b. The same
procedure was adopted as above using 5b as the starting
component. Crystallization from pentane at -35 °C gave single
orange-red crystals. Yield: 68 mg, 97%. Anal. Calcd for C18H27-
MnP2S (392.35): C, 55.10; H, 6.93. Found: C, 55.23; H, 6.67.
1H NMR (C6D6, 300 MHz, 20 °C): δ 7.03 (1H, m, C4H3S), 6.73
4
(1H, m, C4H3S), 6.35 (1H, m, C4H3S), 6.06 (1H, t, JPH ) 9.0
(s, C6H5), 121.1 (s, C6H5), 121.7 (s, C6H5), 98.4 (s, Cipso
-
Hz, dCHC4H3S), 4.37 (2H, C5H4Me), 3.94 (2H, C5H4Me), 2.01
(3H, C5H4CH3), 1.43 (2H, PCH2), 1.11 (3H, P(CH3)3), 1.08 (2H,
PCH2), 0.70 (3H, P(CH3)3). 31P{1H} NMR (C6D6, 121.5 MHz,
20 °C): δ 94.8 (s, 2P). 13C NMR (C6D6, 125 MHz, 20 °C): δ
(MeC5H4)), 81.3 (C5H4Me), 80.2 (C5H4Me), 30.9 (PCH2), 23.4
(PCH2), 21.3 (P(CH3)3), 19.4 (P(CH3)3), 14.5 (s, C5H4CH3). IR
(CH2Cl2, 20 °C): 1597 cm-1 ν(CdC), 1555 cm-1 ν(CdC).

930 Organometallics, Vol. 24, No. 5, 2005
Venkatesan et al.
342.9 (m, Mn-CR), 142.8(m, dCâ), 136.5 (s, 1C, Cipso(C4H3S)),
125.3 (s, 1C, C4H3S), 122.5 (s, 1C, C4H3S), 110.6 (s, 1C, C4H3S),
98.4 (s, Cipso(MeC5H4)), 81.1 (C5H4Me), 80.3 (C5H4Me), 30.7
(PCH2), 23.4 (PCH2), 21.3 (P(CH3)3), 19.2 (P(CH3)3), 14.3 (s,
C5H4CH3). IR (CH2Cl2, 20 °C): 1595 cm-1 ν(CdC), 1558 cm-1
ν(CdC).
(2 × 2H, PCH2), 1.41 (2 × 2H, PCH2), 1.33 (2 × 3H, P(CH3)3),
1.08 (2 × 3H, P(CH3)3). 31P{1H} NMR (CD3CN, 121.47 MHz,
20 °C): δ -145.4 (sept.,1JPF ) 719 Hz, PF6-), 80.9 (m, 2P),
78.7 (m, 2P). 19F NMR (CD3CN, 282.32 MHz, 20 °C): δ -74.0
(d, 719 Hz, PF6-). 13C NMR (C6D6, 125 MHz, 20 °C): δ 323.1
(m, Mn-CR), 102.9 (s, Cipso(MeC5H4)), 136.5 (s, 1C, Cipso
-
(C4H3S)), 125.3 (s, 1C, C4H3S), 122.5 (s, 1C, C4H3S), 110.6 (s,
1C, C4H3S), 92.1 (C5H4Me), 90.3 (C5H4Me), 87.3 (C5H4Me), 86.7
(C5H4Me), 71.9 (MntC-CH(C4H3S)), 31.4 (PCH2), 30.6 (PCH2),
21.8 (P(CH3)3), 20.3 (P(CH3)3), 15.9 (s, C5H4CH3).
[(MeC5H4)Mn(dmpe)dCdC[Si(t-Bu)(Me)2](H)], 16b. To
a toluene solution (10 mL) of (MeC5H4)Mn(dmpe)dCdC(Si(t-
Bu)(Me)2)(SnMe3) (6b) (100 mg, 0.17 mmol) was added an
excess of MeOH. The solution was stirred at room temperature
for 2 h to give a dark red solution. The solvent was removed
under vacuum to afford a dark red oil. Then the oil was
extracted with pentane and filtered through Celite. The
pentane fraction was evaporated to give an orange-red solid.
Crystallization from pentane at -35 °C gave single orange-
red crystals. Yield: 60 mg, 93%. Anal. Calcd for C17H33MnP2-
Reduction of 21b. To a CH2Cl2 solution (10 mL) of
[(MeC5H4)Mn(dmpe)tC-CH2]2[PF6]2 (100 mg, 0.10 mmol) was
added Cp2*Co(36 mg, 0.10 mmol). The solution turned from
red to green and back to red during the reaction. The solution
was stirred at room temperature for 1 h. Then the solvent was
evaporated and was extracted with ether and filtered through
Celite. The ether fraction was evaporated to give quantitative
yield of the pure orange-red solid of 12b.
Reduction of 22b. To a CH2Cl2 (10 mL) solution of
[(MeC5H4)Mn(dmpe)tC-CHPh]2 (110 mg, 0.10 mmol) was
added Cp2*Co (36 mg, 0.10 mmol). The solution turned from
red to green and back to red during the reaction. The solution
was stirred at room temperature for 1 h. Then the solvent was
evaporated and was extracted with ether and filtered through
Celite. The ether fraction was evaporated to give quantitative
yield of the pure orange red solid of 13b.
Reduction of 23b. To a CH2Cl2 (10 mL) solution of
[(MeC5H4)Mn(dmpe)tC-CHC4H3S]2 (110 mg, 0.10 mmol) was
added Cp2*Co (36 mg, 0.10 mmol). The solution turned from
red to green and back to red during the reaction. The solution
was stirred at room temperature for 1 h. Then the solvent was
evaporated and was extracted with ether and filtered through
Celite. The ether fraction was evaporated to give quantitative
yield of the pure orange red solid of 15b.
Oxidation of (C5H5)Mn(dmpe)dCdCH2 (12a). To a THF
solution (10 mL) of (MeC5H4)Mn(dmpe)dCdCH2 (12a) (100
mg, 0. 34 mmol) was added [Cp2Fe][PF6] (110 mg, 0.34 mmol).
The solution turned from red to green and back to red during
the reaction. The solution was stirred at room temperature
for 1 h to give a red precipitate. Then the solvent was
evaporated and was washed with ether. The precipitate was
extracted with acetonitrile and filtered through Celite. The
CH3CN fraction was evaporated to give an orange-red solid,
which was composed of three compounds. The NMR data of
these compounds have been provided below.
1
Si (382.41): C, 53.39; H, 8.69. Found: C, 53.23; H, 8.32. H
NMR (C6D6, 300 MHz, 20 °C): δ 4.13 (2H, C5H4CH3), 4.05 (1H,
t, 4JPH ) 9.0 Hz, dCH(Si(t-Bu)(Me)2)), 3.78 (2H, C5H4CH3), 2.05
(3H, C5H4CH3), 1.40 (2H, PCH2), 1.11 (3H, P(CH3)3), 1.03 (9H,
Si(t-C4H9)(Me)2), 0.91 (2H, PCH2), 0.73 (3H, P(CH3)3) 0.48 (6H,
Si(t-C4H9)(CH3)2). 31P{1H} NMR (C6D6, 121.5 MHz, 20 °C): δ
95.9 (s, 2P). 13C NMR (C6D6, 125 MHz, 20 °C): δ 332.4 (m,
Mn-CR), 142.3 (m, dCâ), 98.1 (s, Cipso(MeC5H4)), 81.5 (C5H4-
Me), 80.1 (C5H4Me), 35.2 (3C, Si(t-C4H9)(Me)2), 28.3 (3C, Si-
(t-C4H9)(Me)2), 31.4 (PCH2), 24.1 (PCH2), 21.2 (P(CH3)3), 14.6
(P(CH3)3), 14.5 (s, C5H4CH3), -1.2 (2C, Si(t-C4H9)(CH3)2). 29Si
NMR (C6D6, 99.4 MHz, 20 °C): δ -2.1 (t, 9.9 Hz, Si(t-C4H9)-
(Me)2). IR (CH2Cl2, 20 °C): 1573 cm-1 ν(CdC), 1553 cm-1 ν-
(CdC).
[(MeC5H4)Mn(dmpe)tC-CHPh]2[PF6]2, 22b. To a THF
solution (10 mL) of (MeC5H4)Mn(dmpe)dCdCPh(H) (100 mg,
0.25 mmol) was added [Cp2Fe][PF6] (82 mg, 0.25 mmol). The
solution turned from red to green and back to red during the
reaction. The solution was stirred at room temperature for 1
h to give a red precipitate. Then the solvent was evaporated
and was washed with Et2O. The precipitate was extracted with
CH3CN and filtered through Celite. The CH3CN fraction was
evaporated to give an orange-red solid. Crystallization from a
mixture of CH3CN-Et2O at room temperature gave red
crystals. Yield: 120 mg, 91%. Anal. Calcd for C40F12H58Mn2P6
(1062.59): C, 45.21 H, 5.50. Found: C, 45.34 H, 5.72. 1H NMR
(CD3CN, 300 MHz, 20 °C): δ 4.39 (2H, -CHC6H5), 4.32 (2H,
C5H4Me), 4.19 (2H, C5H4Me), 4.12 (2 × 2H, C5H4Me), 1.93 (2
× 3H, C5H4CH3), 1.83 (2 × 2H, PCH2), 1.42 (2 × 2H, PCH2),
1.35 (2 × 3H, P(CH3)3), 1.14 (2 × 3H, P(CH3)3). 31P{1H} NMR
(CD3CN, 121.47 MHz, 20 °C): δ -145.4 (sept.,1JPF ) 719 Hz,
PF6-), 80.4 (m, 2P) 79.2 (m, 2P). 19F NMR (CD3CN, 282.32
MHz, 20 °C): δ -74.0 (d, 719 Hz, PF6-). 13C NMR (C6D6, 125
MHz, 20 °C): δ 324.4 (m, Mn-CR), 103.2 (s, Cipso(MeC5H4)),
137.4 (s, Cipso(C6H5)), 131.2 (s, C6H5), 129.8 (s, C6H5), 92.1
(C5H4Me), 90.4 (C5H4Me), 87.5 (C5H4Me), 86.2 (C5H4Me), 72.3
(MntC-CHPh), 31.4 (PCH2), 30.6 (PCH2), 21.8 (P(CH3)3), 20.3
(P(CH3)3), 15.9 (s, C5H4CH3).
[(MeC5H4)Mn(dmpe)tC-CH(C4H3S)]2[PF6]2, 23b. To a
THF solution (10 mL) of (MeC5H4)Mn(dmpe)dCdC(C4H3S)-
(H) (100 mg, 0.25 mmol) was added [Cp2Fe][PF6] (82 mg, 0.25
mmol). The solution turned from red to green and back to red
during the reaction. The solution was stirred at room temper-
ature for 1 h to give a red precipitate. Then the solvent was
evaporated and was washed with Et2O. The precipitate was
extracted with CH3CN and filtered through Celite. The CH3-
CN fraction was evaporated to give an orange-red solid.
Crystallization from a mixture of CH3CN-Et2O at room
temperature gave red crystals. Yield: 125 mg, 93%. Anal.
Calcd for C36F12H54Mn2P6S2 (1074.64): C, 40.23 H, 5.06.
Found: C, 40.34; H, 5.43. 1H NMR (CD3CN, 300 MHz, 20 °C):
δ 7.79 (1H, m, C4H3S), 7.46 (1H, m, C4H3S), 7.24 (1H, m,
C4H3S), 7.12 (1H, m, C4H3S), 6.95 (1H, m, C4H3S), 6.48 (1H,
m, C4H3S), 4.43 (2H, -CHC4H3S), 4.30 (2H, C5H4Me), 4.19 (2H,
C5H4Me), 4.12 (2 × 2H, C5H4Me), 1.91 (2 × 3H, C5H4CH3), 1.81
NMR Data for [(C5H5)Mn(dmpe)tC-CH2]2[PF6]2, 27a.
1H NMR (CD3CN, 300 MHz, 20 °C): δ 4.83 (5H, C5H5), 2.72 (2
× 2H, t, 4JPH ) 9.0 Hz, -CH2), 1.75 (2 × 2H, PCH2), 1.38 (2 ×
2H, PCH2), 1.27 (2 × 3H, P(CH3)3), 1.08 (2 × 3H, P(CH3)3) 31P-
{1H} NMR (CD3CN, 121.5 MHz, 20 °C): δ -145.4 (sept.,1JPF
) 719 Hz, PF6-), 79.5 (s, 2 × 2P). 19F NMR (CD3CN, 282.3
MHz, 20 °C): δ -74.0 (d, 719 Hz, PF6-). 13C NMR (C6D6, 125
MHz, 20 °C): δ 328.3 (m, Mn-CR), 92.1 (C5H5) 50.3 (MntC-
CH2), 31.4 (PCH2), 30.6 (PCH2), 21.8 (P(CH3)3), 20.3 (P(CH3)3).
NMR Data for [(C5H5)Mn(dmpe)tC-CH3][PF6], 35a. 1H
NMR (CD3CN, 300 MHz, 20 °C): δ 4.72 (5H, C5H5), 1.40 (2H,
PCH2), 1.11 (3H, P(CH3)3), 0.91 (2H, PCH2), 0.73 (3H, P(CH3)3).
31P{1H} NMR (CD3CN, 121.5 MHz, 20 °C): δ -145.4 (sept.,1JPF
) 719 Hz, PF6-), 81.3 (s, 2P). 19F NMR (CD3CN, 282.3 MHz,
20 °C): δ -74.0 (d, 719 Hz, PF6-). 13C NMR (C6D6, 125 MHz,
20 °C): δ 300.5 (m, Mn-CR), 87.3 (C5H5), 48.3 (MntC-CH3),
31.4 (PCH2), 30.6 (PCH2), 21.8 (P(CH3)3), 20.3 (P(CH3)3).
NMR Data for [(C5H5)Mn(dmpe)dCdCH]2[PF6]2, 43a.
4
1H NMR (CD3CN, 300 MHz, 20 °C): δ 6.33 (2H, t, JPH ) 6.0
Hz, -C(H)), 4.72 (5H, C5H5), 1.40 (2 × 2H, PCH2), 1.11 (2 ×
3H, P(CH3)3), 0.91 (2 × 2H, PCH2), 0.73 (2 × 3H, P(CH3)3).
31P{1H} NMR (CD3CN, 121.5 MHz, 20 °C, 85% H3PO4 ext): δ
-145.44 (sept.,1JPF ) 719 Hz, PF6-), 83. 7 (s, 2 × 2P). 19F NMR
(CD3CN, 282.3 MHz, 20 °C): δ -74.0 (d, 719 Hz, PF6-). 13C
NMR (CD3CN, 125 MHz, 20 °C): δ 321.3 (m, Mn-CR), 149.7
(MndCdCH), 89.7 (C5H5), 31.1 (PCH2), 30.6 (PCH2), 21.4

µ-C-C Bonds of Dinuclear Manganese Complexes
Organometallics, Vol. 24, No. 5, 2005 931
Table 1. Crystallographic Details of 3a, 11, and 13a
3a
11
13a
empirical formula
color
C
22H35MnP2Sn
C36H58MnP4
red
C19H27MnP2
red block
372.29
red block
535.07
Mr [g mol-1
]
669.64
cryst size [mm]
T [K]
λ(Mo KR) [Å]
cryst syst
space group
a [Å]
0.12 × 0.17 × 0.26
0.24 × 0.38 × 0.55
0.12 × 0.17 × 0.26
183(2)
183(2)
183(2)
0.71073
0.71073
orthorhombic
Pbca
0.71073
triclinic
monoclinic
P21/n
16.2767(11)
14.4759(7)
16.3697(9)
90
P1h
11.8039(6)
17.3012(8)
23.6718(14)
90
90
90
9.9971(8)
10.1842(8)
19.3926(17)
96.467(10)
101.506(10)
109.279(9)
1791.9(3)
2
b [Å]
c [Å]
R [deg]
â [deg]
102.370(7)
90
γ [deg]
V [Å3]
4834.3(4)
8
3767.5(4)
8
Z
F
calcd [g cm-3
]
1.470
1.241
1.313
µ [mm-1
F(000)
transmn range
2θ range [deg]
]
1.692
0.570
0.865
2176
718
1568
0.7120-0.8401
6.64 < 2θ < 30.70
34 289
0.7388-0.8721
4.96 < 2θ < 56.16
17 364
0.8378-0.9118
4.88 < 2θ < 56.00
35 645
no. of measd reflns
no. of unique reflns
I > 2σ(I) reflns
6638
7982
9023
2863
4800
3809
no. of params
237
381
405
Gof (for F2)
0.694
1.030
0.790
R1[I > 2σ(I)], R1 all data
wR2[I > 2σ(I)], wR2 all data
0.0410, 0.1076
0.0895, 0.1058
0.765, -1.447
0.0358, 0.0694
0.0628, 0.0657
0.566, -0.555
0.0480, 0.1254
0.0807, 0.0878
0.918, -1.058
∆F max/min [e- Å-3
]
2
2
a R1 ) ∑(Fo - Fc)/∑Fo; I > 2σ(I); wR2 ) {∑w(Fo - Fc )2/∑w(Fo2)2}1/2
.
(P(CH3)3), 20.1 (P(CH3)3). IR (CH2Cl2, 20 °C): 1543 cm-1 ν-
(CdC), 848 cm-1 ν(P-F).
observed. The corrected formula was then used for the final
absorption correction. All these procedures were calculated by
using the Stoe IPDS software.92
X-ray Crystal Structure Analyses. The X-ray diffraction
data were collected at 183(1) K for compounds 3a, 11, 13a,
15a, and 22b using an imaging plate detector system (Stoe
IPDS)92 with graphite-monochromated Mo KR radiation. A
total of 200, 200, 167, 300, and 182 images were exposed at
constant times of 3.00, 5.00, 3.00, 3.00, and 2.30 min per image
for the four structures, respectively. The crystal-to-image
distances were set to 50, 60, 60, 50, and 56 mm (θmax: 30.35°,
28.08°, 28.00°, 30.30°, and 28.97°). φ-Oscillation (for 3a, 11,
13a, and 15a) and rotation modes (for 22b) were used with
increments of 1.0°, 1.0°, 1.2°, 0.8°, and 1.1° per exposure in
each case. Total exposure times were 24, 30, 20, 36, and 20 h.
The intensities were integrated by using a dynamic peak
profile analysis, and an estimated mosaic spread (EMS) check
was performed to prevent overlapping intensities. For the cell
parameter refinements 7998 (15a) to 8000 (3a, 11, 13a, and
22b) reflections were selected out of the whole limiting spheres
with intensities I > 6σ(I) for all structures. A total of 34 289,
17 364, 35 645, 24 322, and 48 650 reflections were collected,
of which 6638, 7982, 9023, 5414, and 11 757 were unique after
data reduction (Rint ) 0.1289, 0.0498, 0.1324, 0.0784, and
0.1150). For the numerical absorption corrections 12, 7, 14,
14, and 13 indexed crystal faces were used.
All crystals were embedded in polybutene oil within the
glovebox. The crystal quality was then examined by using a
polarizing microscope. Sometimes, crystals with intrusions
(holes or solvent) or with tiny intergrown pieces had to be
accepted for the X-ray experiment. In general, the structures
were solved with an incomplete data set (50% or less complete-
ness) while the measurement was still being performed,
because the correct chemical formula cannot always be pre-
dicted when solvent molecules cocrystallize with the complex,
or, as in the case of 11 and 13a, two independent complexes
(Z′ ) 2) were found. For structure 11, two independent
complexes with central Mn atoms on centers of inversion were
The structures were solved with the merged unique data
set after checking for correct space groups. The Patterson
method was used to solve the crystal structures by applying
the software options of the program SHELXS-97.93 The
structure refinements were performed with the program
SHELXL-97.94 The programs PLATON95 and PLUTON96 were
used to check the results of the X-ray analyses; they are helpful
for the interpretation of the initially determined structural
models. Relevant crystallographic data are collected in Tables
1 and 2. All five structures crystallize in centrosymmetric space
groups.
Computational Details
Density functional theory (DFT) calculations were carried
out using the Amsterdam Density Functional program package
ADF, release 2002.02.97 We used the Vosko-Wilk-Nusair98
local density approximation (LDA) and the generalized gradi-
ent approximation (GGA) with corrections for exchange and
correlation according to Becke99 and Perdew,100 respectively
(BP86). The valence shells of all non-hydrogen atoms were
described by triple-ú basis sets augmented by one polarization
function (ADF database TZP), while a standard double-ú basis
set was applied for hydogen atoms (ADF database DZP). The
frozen-core approximation was applied for the 1s electrons of
(93) Sheldrick, G. M. Acta Crystallogr. 1990, A46, 467.
(94) Sheldrick, G. M. SHELXL-97, Program for Refinement of
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932 Organometallics, Vol. 24, No. 5, 2005
Venkatesan et al.
Table 2. Crystallographic Details of 15a and 22b
calculations have been performed. The solvation energies
based on gas-phase geometries were calculated by the conduc-
tor-like screening model (COSMO) suggested by Klamt and
Schuurmann101 and implemented in ADF by Pye and Zie-
gler.102 The solvent-accessible surface was chosen and con-
structed using the following radii: H 1.16, C 2.00, P 1.70, Si
2.20, and Mn 2.40 Å. A dielectric constant of 7.58 was used
for THF.
Crystallographic data (excluding structure factors) for the
structures given in this paper have been deposited with the
Cambridge Crystallographic Data Centre as supplementary
publication nos. CCDC 244878, 244879, 244880, 244881, and
214889. Copies of the data can be obtained free of charge on
application to CCDC, 12 Union Road, Cambridge CB2 1EZ,
UK (fax: (+44) 1223-336033; e-mail: deposit@ccdc.cam.ac.uk).
15a
22b
empirical formula
color
C
17H25MnP2S
C40H58F12Mn2P6
red block
red block
378.31
Mr [g mol-1
]
1062.56
cryst size [mm]
T [K]
0.15× 0.16 × 0.20 0.11× 0.28 × 0.30
183(2)
183(2)
λ(Mo KR) [Å]
cryst syst
space group
a [Å]
0.71073
monoclinic
C2/c
0.71073
monoclinic
P21/c
25.115(4)
8.1122(8)
18.432(3)
90
17.0339(14)
16.5851(12)
18.4605(16)
90
b [Å]
c [Å]
R [deg]
â [deg]
103.249(17)
90
116.873(9)
90
γ [deg]
V [Å3]
3655.2(8)
8
4652.1(6)
4
Z
F
calcd [g cm-3
]
1.375
1.517
µ [mm-1
F(000)
]
1.003
0.827
Acknowledgment. Funding from the Swiss Na-
tional Science Foundation (SNSF) and from the Uni-
versity of Zu¨rich is gratefully acknowledged.
1584
2184
transmn range
0.8299-0.9048
5.3 < 2θ < 60.60
24 322
0.7749-0.9093
4.92 < 2θ < 57.94
48 650
2θ range [deg]
no. of measd reflns
no. of unique reflns
I > 2σ(I) reflns
5414
4220
11757
Supporting Information Available: Cartesian coordi-
nates of optimized geometries, computed total bonding ener-
gies, and solvation energies are given. Experimental details
and details of crystal structure determination for compounds.
This material is available free of charge via the Internet at
http://pubs.acs.org.
4465
no. of params refined 184
568
goodness-of-fit
R1[I > 2σ(I)], R1 all
data [%]a
1.144
0.777
0.0624, 0.0787
0.1294, 0.1336
1.025, -0.696
0.0781, 0.1542
wR2[I > 2σ(I)], wR2
all data [%]
0.1967, 0.2176
∆F max/min [e- Å-3
]
3.188, -0.859
OM049284C
2
2
a R1 ) ∑(Fo - Fc)/∑Fo; I > 2σ(I); wR2 ) {∑w(Fo - Fc )2/
∑w(Fo2)2}1/2
.
(100) (a) Perdew, J. P. Phys. Rev. B 1986, 33, 8822. (b) Perdew, J.
P. Phys. Rev. B 1986, 34, 7406.
carbon atoms, and for the 1s-2p electrons of silicon, phospho-
rus, and manganese. For the mononuclear cationic radical
model systems with an odd electron count, spin-unrestricted
(101) Klamt, A.; Schuurmann, G. J. Chem. Soc., Perkin Trans. 1993,
2, 799.
(102) Pye, C. C.; Ziegler, T. Theor. Chem. Acta 1999, 101, 396.