Binuclear 1,2-diphosphacyclopentadienyl manganese(I) complexes: Synthesis, structure and magnetic properties

Article abstract of DOI:10.1021/om900764q

The reaction of Mn(CO)₅Br with 1-trimethyltin-3,4,5-triphenyl-1, 2-diphosphacyclopenta-2,4-diene leads to formation of binuclear manganese(I) complexes with bridging 1,2-diphosphacyclopentadienyl ligands exhibiting magnetic properties apparently similar to Mn(II) compounds due to intramolecular redistribution of the electron density. Variation of peripheral ligands of binuclear complexes provides control over the magnitude of the magnetic moment, the contribution of the orbital magnetism, and the strength of the magnetic exchange.

Full text of DOI:10.1021/om900764q

Organometallics 2010, 29, 1339–1342 1339
DOI: 10.1021/om900764q
Binuclear 1,2-Diphosphacyclopentadienyl Manganese(I) Complexes:
Synthesis, Structure and Magnetic Properties
Vasili Miluykov,*,† Il’ya Bezkishko,† Dmitry Krivolapov,† Olga Kataeva,†,§
Oleg Sinyashin,† Evamarie Hey-Hawkins,‡ Anupama Parameswaran,§ Yulia Krupskaya,§
§
Vladislav Kataev, Rudiger Klingeler, and Bernd Buchner
§
§
€
€
†A.E. Arbuzov Institute of Organic and Physical Chemistry of the Russian Academy of Sciences, Arbuzov
‡
Street 8, Kazan 420088, Russian Federation, Institute of Inorganic Chemistry, Universitat Leipzig,
€
Johannisallee 29, 04103 Leipzig, Germany, and §IFW Dresden, POB 270116, D-01171, Dresden, Germany
Received September 2, 2009
The reaction of Mn(CO)5Br with 1-trimethyltin-3,4,5-triphenyl-1,2-diphosphacyclopenta-2,4-diene leads
to formation of binuclear manganese(I) complexes with bridging 1,2-diphosphacyclopentadienyl ligands
exhibiting magnetic properties apparently similar to Mn(II) compounds due to intramolecular redistribu-
tion of the electron density. Variation of peripheral ligands of binuclear complexes provides control over the
magnitude of the magnetic moment, the contribution of the orbital magnetism, and the strength of the
magnetic exchange.
Introduction
of molecular magnets by combination of Mn(I) ions with bridg-
ing ligands capable of charge transfer. In this respect the 1,2-
diphospha-3,4,5-triphenylcyclopentadienide anion5 should com-
bine the ability to bridge metal atoms with the feasibility of charge
transfer similar to pyrazolate.6
Electronic structure and magnetic properties of Mn-containing
compounds continue to be a major research area because of the
fascinating physical properties observed for these materials, such
as single-molecule magnetism of multinuclear Mn complexes1 or
colossal magnetoresistance of manganese-based perovskite oxi-
des.2 These properties are closely related to the diversity of oxida-
tion states and the effective magnetic exchange coupling between
Mn ions provided by different short bridging ligands, such as
Results and Discussion
Complexes 2a,b were prepared starting from the tin deri-
vate 1 and Mn(I) bromide complexes (eq 1). It should be
noted that formation of binuclear complexes is quite un-
expected: similar reactions of the Sn derivate of 1,2,4-tripho-
sphacyclopentadienide with [Mn(CO)5Br] resulted in 1,2,4-
triphosphacymantrene only.7
O
2-, OH-, CN-, N3-, RCOO-, C2O42- and pyrazolate.3 Sur-
prisingly, only a few data on the magnetism of complexes
containing Mn(I) ions is available, though in this oxidation state
Mn is isoelectronic to Fe2þ, which is often found in a magnetic
high-spin (HS) state. A rare example is a dimer complex of low-
coordinated Mn(I) ions4 with the open-shell configuration
4s13d5, where the 4d-electrons built up a total HS state S =
5/2. We have supposed that a Mn(I) can be used for construction
*Corresponding author. E-mail: miluykov@iopc.knc.ru.
(1) (a) Gatteschi, D.; Sessoli, R. Angew. Chem., Int. Ed. 2003, 42, 268–
297. (b) Brockman, J.; Abboud, Kh.; Hendrickson, D. N.; Christou, G.
€
ꢀ
Polyhedron 2003, 22, 1765–1769. (c) von Hanisch, C.; Weigend, F.; Clerac,
R. Inorg. Chem. 2008, 47, 1460–1464.
(2) Dagotto E. Nanoscale Phase Separation and Colossal Magnetore-
sistance; Springer-Verlag: Berlin, 2002.
ꢀ
(3) (a) Brandmayer, M.;Clerac, R.; Weigend, F.; Dehnen, S. Chem.;Eur.
J. 2004, 10, 5147–5157. (b) Escuer, A.; Aromí, G. Eur. J. Inorg. Chem. 2006,
4721–4736.
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Bencini, A.; Caneschi, A.; Gatteschi, D. J. Am. Chem. Soc. 2005, 127,
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W.; Chai, J.; Stuck, A. C. Inorg. Chem. 2006, 45, 395–400.
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€
O.; Lonnecke, P.; Hey-Hawkins, E. Organometallics 2005, 24, 2233–2236. (c)
Bezkishko, I.; Miluykov, V.; Kataev, A.; Krivolapov, D.; Litvinov, I.; Sinyashin, O.;
Hey-Hawkins, E. J. Organomet. Chem. 2008, 693, 3318–3320.
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Sakaki, S. Chem.;Eur. J. 2006, 12, 6521–6527. (b) Ranjan, S.; Lin, S.-Y.;
Hwang, K.-C.; Chi, Y.; Ching, W.-L.; Liu, C.-S. Inorg. Chem. 2003, 42, 1248–
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Inorg. Chem. 2008, 47, 7695–7702. (d) Huang, H.-P.; Li, S.-H.; Yu, S.-Y.; Li,
Y.-Z.; Jiao, Q.; Pan, Y.-J. Inorg. Chem. Commun. 2005, 8, 656–660.
Acetonitrile ligands in 2b can be further easily replaced by
PPh3 to form 2c (eq 1).
(7) Clark, T.; Elvers, A.; Heinemann, F. W.; Hennemann, M.; Zeller,
M.; Zenneck, U. Angew. Chem., Int. Ed. 2000, 39, 2087–2091.
r
2010 American Chemical Society
Published on Web 02/19/2010
pubs.acs.org/Organometallics

1340 Organometallics, Vol. 29, No. 6, 2010
Miluykov et al.
Figure 1. ORTEP view of bis(μ:η1,η1-1,2-diphospha-3,4,5-triphenylcyclopentadienyl)bis(manganesetetracarbonyl) (2a). Thermal
˚
ellipsoids are drawn at 50% probability. Selected bonds lengths (A) and angles (deg): Mn(1)-P(102) 2.3655(12), Mn(1)-P(1)
2.3710(11), Mn(2)-P(101) 2.3758(11), Mn(2)-P(2) 2.3746(11), P(1)-P(2) 2.1103(13), P(101)-P(102) 2.1087(14), P(1)-C(5) 1.741(4),
P(2)-C(7) 1.736(4), P(101)-C(105) 1.759(4), P(102)-C(107) 1.755(4), C(5)-C(6) 1.392(5), C(6)-C(7) 1.418(5), C(105)-C(106)
1.413(5), C(106)-C(107) 1.414(5); P(1)-Mn(1)-P(102) 84.64(4), P(2)-Mn(2)-P(101) 84.73(4), C(5)-P(1)-P(2) 94.78(13), P(2)-P-
(1)-Mn(1) 122.41(5), C(7)-P(2)-P(1) 94.39(12), C(105)-P(101)-P(102) 94.93(13), C(107)-P(102)-P(101) 94.81(13).
Table 1. Fit Parameters of the Static Magnetic Susceptibility
According to X-ray single-crystal diffraction, binuclear
complex 2a (Figure 1) has two Mn atoms doubly bridged by
3,4,5-triphenyl-1,2-diphosphacyclopentadienyl ligands in an
μ:η1,η1-fashion. Only two examples of such coordination
mode were described earlier for 1,2,4-triphosphacyclopenta-
dienyl ligands with nickel and copper.8 Each manganese
atom has a slightly distorted octahedral environment. The
geometry of the 3,4,5-triphenyl-1,2-diphosphacyclopenta-
dienide ligand in the complex and in sodium salt5b is nearly
the same, except for the slightly shorter P-C bonds in 2a. All
four Mn-P bonds in 2a are equal within experimental error,
L
C, emu/K
θ, K
peff, μB per one Mn
(2a) CO
(2b) MeCN
(2c) PPh3
0.6
1.21
1.79
1
17
18
1.55
2.20
2.67
˚
single bond, which varies from 2.259 to 2.365 A for P-P
fragments bridging two Mn atoms.12 The sums of angles at
phosphorus atoms are around 340ꢀ, which are more typical
for phosphorus in sp3 hybridization. Together with the C-C
intra-ring distances typical of aromatic C-C bonds, this
indicates a significant delocalization of the π-electrons,
though the phosphorus centers are both pyramidal. The
formal oxidation states of both Mn ions calculated from
the nominal charge of the ligands are þ1.
˚
and the average value is 2.372 A, which is within the range
˚
2.34-2.38 A for the majority of Mn(I) complexes with
trivalent phosphorus ligands9 and is shorter than the P-
Mn(II) bond, e.g., 2.430(1) A, in manganese clusters.
1c
˚
The sum of the covalent radii of phosphorus and Mn in a
low-spin state10 is 2.46 A and is significantly larger for Mn in
˚
The static magnetic susceptibility χ of the powder samples
of 2a-c, measured at temperatures between 2 and 300 K,
follows closely the Curie-Weiss law (Figure S1, Supporting
Information). Generally, the effective moment peff (Table 1)
for all studied complexes is significantly smaller than that of
Mn(I) in the high-spin state (S = 2, g = 2, peff = 4.9 μB) and
is rather close to the effective moment of Mn(II) in the low-
spin state (S = 1/2, g = 2, peff = 1.73 μB). Remarkably, peff
of Mn continuously increases from 2a to 2b and further to 2c.
Since from the ESR data presented below the g-factor for all
samples has the same value of g ≈ 2, the growth of peff can be
phenomenologically treated as an increase of an “effective”
spin value from Seff ≈ 0.4 to Seff ≈ 0.9 when going from 2a to
2c. The observed systematic changes of peff give clear evi-
dence of its dependence on the nature of the ligand at the
manganese atom: complex 2a, containing a strong π-accep-
tor such as CO, has the lowest peff, while the largest value of
peff is found for complex 2c, containing the good σ-donor
PPh3. Such a tendency gives strong indications that the
redistribution of the electron density in the complex con-
trolled by the ligand substitution affects the magnetic state of
˚
a high-spin state (2.68 A). The P-C bond lengths in complex
1a vary from 1.736(4) to 1.759(4) A and are shorter than the
˚
2
˚
sum of the covalent radii P-C(sp ), 1.80 A. The P-P bonds
˚
are equal at 2.110(1) A, which is between the P-P double
11
˚
bond (2.02-2.04 A in coordination compounds) and a
(8) (a) Heinemann, F.; Pritzkow, H.; Zeller, M.; Zenneck, U. Orga-
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Murray, B. D.; Olmstead, M. M.; Power, P. P. J. Am. Chem. Soc. 1987,
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H.-G. J. Organomet. Chem. 1992, 439, 279–301. (c) Yoshifuji, M.;
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Article
Organometallics, Vol. 29, No. 6, 2010 1341
However, a more complex ESR spectrum arises if the spins
S1 and S2 of the two Mn ions in the complex are exchange
coupled in a spin dimer. The relevant spin Hamiltonian H =
JS1S2 þ S1 D S2 þ gμB(S1 þ S2)H includes the isotropic and
3
3
anisotropic exchange interaction, as well as the Zeeman
interaction, first, second, and third terms, respectively.16
The energy scale on the order of ∼10 K for the isotropic
Mn-Mn magnetic interaction J is suggested by the observed
Curie-Weiss temperatures (Table 1). Since usually |J| . |D|,
the strength of the anisotropic part of the magnetic exchange
is likely to be comparable with the Zeeman interaction (∼0.5
K). In this regime the otherwise “pure” spin triplet states
|Sztot> = |þ1æ, |0æ, and |-1æ can be substantially mixed.
Thus in addition to the allowed ESR transitions ΔSztot = (1
the formerly forbidden transitions ΔSztot = (2 may occur as
well, yielding an intense half-field signal with the “doubled”
effective g-factor geff = g|ΔSz| ≈ 2g. Interestingly, its
intensity increases concomitantly with the increase of the
Mn magnetic moment upon changing the ligand (Figure 2).
Since the anisotropy of exchange arises due to relativistic
spin-orbit coupling effects, one may conjecture that tuning
the electron density in the complexes by the ligand substitu-
tion enhances the orbital contribution to the magnetism of
the binuclear complex when passing from a strong π-accep-
tor in 2a to a σ-donor one in 2c.
Thus, we have for the first time demonstrated that bimetallic
manganese(I) complexes with bridging 3,4,5-triphenyl-1,2-di-
phosphacyclopentadienyl ligands possess a magnetic behavior
that might be attributed to the intramolecular charge transfer
from the metal atoms to the diphosphacyclopentadienyl ring
similar to the redistribution of electron density observed in
complexes with noninnocent ligands.17 Furthermore, we find
that the fine-tuning of the electron density at the core of the
molecular complex by variation of peripheral ligands provides
control over the magnitude of the magnetic moment, the
contribution of the orbital magnetism, and the strength of
the intramolecular magnetic exchange realized through the
1,2-diphosphacyclopentadienyl ligand.
Figure 2. ESR spectra of powder samples of 2a-c and a
calculated spectrum (bottom) at ν = 9.56 GHz and T = 3.4 K.
the transition metal ions. Moreover, the decrease of the
strength of the π-acceptor and increase of the σ-donor yields
an enhancement of the antiferromagnetic interactions in the
complexes, which is reflected in the increase of θ (Table 1).
Thus the susceptibility data clearly suggest that in binuclear
manganese complexes 2a-c the metal-to-ligand charge
transfer (MLCT) takes place with the formation of Mn(II)
species, which causes antiferromagnetic interactions ob-
served in a broad temperature range. Due to the long
˚
distance between both manganese atoms (5.200 A), this
interaction can be realized only through the 1,2-diphospha-
cyclopentadienide rings.
The ESR powder spectrum of each complex (2) consists of
two structured signals, one centered about the field H
corresponding to the g-factor value of ∼2.0 and the other
centered about approximately half of that field value corre-
sponding to the g-factor of ∼4.2 (see Figure 2). Each signal
contains six partially resolved lines with a separation about
∼80 Oe, which is typical for low-spin Mn(II),13 due to the
hyperfine interaction HHF = S A I of the electron spin S
Experimental Section
All reactions and manipulations were carried out under dry,
pure nitrogen in standard Schlenk apparatus. All solvents were
distilled from sodium/benzophenone and stored under nitrogen
before use. The NMR spectra were recorded on a Bruker MSL-
400 (1H 400 MHz, 31P 121.7 MHz, 13C 100.6 MHz). SiMe4 was
used as internal reference for 1H and 13C NMR chemical shifts,
and 85% H3PO4 as external reference for 31P. IR spectra were
recorded on a Bruker Vector-22 in the range 4000-400 cm-1 at a
resolution of 4 cm-1. Static magnetic susceptibility has been
measured with a superconducting quantum interference device
(SQUID) magnetometer from Quantum Design. The ESR
measurements have been performed with an X-Band (10 GHz)
Bruker EMX spectrometer.
3
3
with the nuclear spin I of Mn (IMn = 5/2). The result of the
simulation of such hyperfine split signal with the EasySpin
toolbox for Matlab14 (Figure 2, bottom spectrum) agrees
reasonably well with the experimental one, yielding a tensor
of the hyperfine interaction A[Ax; Ay; Az] = [280; 280; 120]
MHz = [93; 93; 40] ꢀ 10-4 cm-1
.
The occurrence of the half-field signal in the ESR spectrum
of the studied complexes is remarkable. An isolated low-spin
(S = 1/2) Mn2þ ion in the low-symmetry ligand coordina-
tion is characterized by a nearly isotropic g-factor close to a
value of 2.15 Thus only a single (hyperfine split) line due to
the resonance transition þ1/2 S -1/2 (ΔSz = (1) within the
Kramers spin doublet is expected at a “full” resonance field
value Hres = hν/gμB|ΔSz|.
X-ray Single-Crystal Diffraction. The data set for 2a was
collected on a Bruker AXS Kappa APEX II CCD diffract-
ometer with graphite-monochromated Mo KR radiation (λ =
18
˚
0.71073 A). The data collection was performed with APEX2,
data reduction with SAINT,19 absorption correction with
(16) Kahn O. Molecular Magnetism; VCH Publishers: New York, 1993.
(17) (a) Jorgensen, C. K. Oxidation Numbers and Oxidation States;
Springer: Berlin, 1969. (b) Butin, K.; Beloglazkina, E.; Zyk, N. Russ. Chem.
Rev. 2005, 74, 531–553.
e
(13) Livorness, J.; Smith, T. D.; Pilbrow, J. R.; Sinclair, G. R. J.
Chem. Soc., Faraday Trans. 2 1984, 80, 425–436.
(14) Stoll, S.; Schweiger, A. J. Magn. Reson. 2006, 178, 42–55.
(15) Pilbrow J. R. Transition Ion Electron Paramagnetic Resonance;
Clarendon Press: Oxford, 1990.
(18) APEX2 v2, 1-4; Bruker AXS, 2005-2007.
(19) Bruker, SMART, SAINT, and XPREP; Bruker Analytical
X-ray Instruments Inc.: Madison, WI, 1995.

1342 Organometallics, Vol. 29, No. 6, 2010
Miluykov et al.
SADABS,20 structure solution with SHELXS97,21 and struc-
ture refinement by full-matrix least-squares against F2 using
SHELXL-9722 and WinGX.23 The picture was generated using
phosphacyclopentadiene (1) (0.89 g, 1.8 mmol) in 50 mL of THF
was stirred for 3 h at 65 ꢀC. The solvent was reduced to 10 mL
under vacuum and cooled to -10 ꢀC to form red crystals, which
were collected, washed with n-hexane (3 ꢀ 25 mL), and dried
under vacuum to give 1.42 g (79.5%) of bis(μ,η1:η1-3,4,5-
triphenyl-1,2-diphosphacyclopentadienyl)bis(tetracarbonyl-
manganese) (2a) as a red powder with a melting point of 138 ꢀC
(dec).
ORTEP-3.24 Crystal data for 2a: formula C50H30Mn2O8P4 1.5-
3
˚
C4H8O, M = 1100.66, a = 9.2604(3) A, b = 19.1526(6) A, c =
˚
ꢀ
3
˚
˚
15.0979(4) A, β = 99.859(2) , V = 2638.2(1) A , Fcalc = 1.386 g
cm-3, μ = 0.656 mm-1, empirical absorption correction
(0.698 e T e 0.968), Z = 2, monoclinic, space group P21
(No. 4), T = 198 K, ω and j scans, 145 301 reflections collected
=
IR (n-hexane, cm-1): 1986 (CO), 2004 (CO), 2014 (CO), 2051
(CO). Anal. Calcd for C50H30Mn2O8P4 (991.97): C 60.50; H
3.05; P 12.48. Found: C 59.81; H 3.13; P 12.73.
((h, ( k, ( l), [(sin θ)/λ] = 0.75 A-1, 18 367 independent (Rint
˚
0.089) and 10 061 observed reflections [I g 2 σ(I)], 617 refined
parameters, R = 0.052, wR2 = 0.127, max. residual electron
Crystals suitable for X-ray analysis were obtained from a
saturated solution of 2a in THF at RT.
density 1.20 (-0.43) e A-3. CCDC 734772 (2b) contains the
˚
supplementary crystallographic data for this paper. These data
can be obtained free of charge from The Cambridge Crystallo-
graphic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
1-Trimethyltin-3,4,5-triphenyl-1,2-diphosphacyclopentadiene
(1). Solid Me3SnCl (1.08 g, 5.4 mmol) was added at -78 ꢀC to a
suspension of sodium 1,2-diphospha-3,4,5-triphenylcyclopen-
tadienide5c (1.9 g, 5.4 mmol) in 25 mL of toluene. The reaction
mixture was stirred at RT for 6 h. The solvent was evaporated,
and the residue was extracted with n-hexane (3 ꢀ 25 mL),
filtered, and dried under vacuum to give 1.75 g (66%) of
1-trimethyltin-3,4,5-triphenyl-1,2-diphosphacyclopentadiene
(1) as light yellow oil, which solidified on standing.
Bis(μ,η1:η1-3,4,5-triphenyl-1,2-diphosphacyclopentadienyl)-
bis(tricarbonyl(acetonitrile)manganese) (2b) was obtained in a
similar manner from [Mn2(CO)6(MeCN)2Br2]25 (0.39 g, 0.75
mmol) and 1-trimethyltin-3,4,5-triphenyl-1,2-diphosphacyclo-
pentadiene (1) (0.74 g, 1.5 mmol). Yield: 0.43 g (56%), red
powder, mp 92 ꢀC (dec).
IR (n-hexane, cm-1): 1918 (CO), 2001 (CO), 2048 (CO), 3124
(CN). Anal. Calcd for C52H36Mn2N2O6P4 (1018.62): C 61.31; H
3.56; N 2.75; P 12.16. Found: C 61.52; H3.27; N 2.16; P 12.54.
Bis(μ,η1:η1-3,4,5-triphenyl-1,2-diphosphacyclopentadienyl)-
bis(tricarbonyl(triphenylphosphine)manganese) (2c). A mixture
of bis(μ,η1:η1-3,4,5-triphenyl-1,2-diphosphacyclopentadienyl)-
bis(tricarbonyl(acetonitrile)manganese) (2b) (0.81 g, 0.79 mmol)
and triphenylphosphine (0.41 g, 1.58 mmol) in 50 mL of THF
was stirred for 12 h at room temperature. The solvent was
evaporated and the residue washed with n-hexane (2 ꢀ 25 mL)
and dried under vacuum to give 1.1 g (95%) of 2c as a red
powder; mp 125 ꢀC (dec).
1H NMR (C6D6): δ -0.005 (t, 9H, Me, 2JSn-H = 26.9 Hz),
6.89 (t, 3H, Hp, Ph, 3JH-H = 3.18 Hz), 6.94-7.02 (m, 8H, Ph),
3
7.24 (d, 4H, Ho, Ph, JH-H = 6.36 Hz). 31P NMR (C6D6): δ
1
116.4 (s). 13C NMR (C6D6): δ -5.7 (Me, JSn-C= 324.4 Hz),
127.30 (s, Cp, Ph), 127.57 (s, Cp, Ph), 128.76 (s, Cm, Ph), 128.86
(s, Cm, Ph), 130.28 (s, Co, Ph), 132.20 (s, Co, Ph), 140.04 (s, Cipso
,
2
Ph), 142.92 (t, Cipso, Ph, JC-P = 7.03 Hz), 154.65 (t, C2-Cp,
IR (n-hexane, cm-1): 1907 (CO), 1933 (CO), 2020 (CO). Anal.
Calcd for C84H60Mn2O6P6 (1461.09): C 69.05; H 4.14; P 12,72.
Found: C 68.87; H 4.03; P 12.17.
2JC-P = 4.96 Hz), 181.06 (t, C1-Cp, 1JC-P = 21.71 Hz). 119Sn
1
NMR (C6D6) δ 50.8 (t, JSn-P = 276 Hz). Anal. Calcd for
C24H24P2Sn (492.04): C 58.46; H 4.91; P 12.56. Found: C 58.35;
Acknowledgment. The authors thank the Deutsche
Forschungsgemeinschaft (KL1824/2, HE1376-27-1) and
Russian Foundation for Basic Research (07-03-91556)
for financial support of this work. A.P. acknowledges
support by the IMPRS “Dynamical Processes in Atoms,
Molecules and Solids” Dresden.
H 4.81; P 13.01.
Bis(μ,η1:η1-3,4,5-triphenyl-1,2-diphosphacyclopentadienyl)-
bis(tetracarbonylmanganese) (2a). A mixture of [MnBr(CO)5]
(0.495 g, 1.8 mmol) and 1-trimethyltin-3,4,5-triphenyl-1,2-di-
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€
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Supporting Information Available: Details of magnetic mea-
surement and crystallographic information of 2a are available
free of charge via the Internet at http://pubs.acs.org or from the
authors.
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