Synthesis and structures of tungsten ferrocenyldiazoalkane complexes derived from a dinitrogen complex.: Part 58. Preparation and properties of molybdenum and tungsten dinitrogen complexes

Article abstract of DOI:10.1016/s0020-1693(98)00361-2

Reaction of the hydrazido(2-) complex cis, mer-[WCl₂(NNH₂)(PMe₂Ph)₃], derived from a dinitrogen complex cis-[W(N₂)₂(PMe₂Ph)₄], with formylferrocene or acetylferrocene gave ferrocenyldiazoalkane complexes cis, mer-[WCl₂(NN=CRFc)(PMe₂Ph)₃] (2: R = H, Me; Fc = (η⁵-C₅H₄)Fe(η⁵-C ₅H₅)). Treatment of 2 with π-acceptor ligands L such as CO, CH₂=CH₂, p-MeC₆H₄CHO, p-MeC₆H₄CCH and Bu^tNC afforded a series of ferrocenyldiazoalkane complexes cis, trans-[WCl₂(NN=CRFc)(L)(PMe₂Ph)₂] (4), while upon treatment with CH₂Cl₂ 2 gave the W(V) complexes mer, trans-[WCl₃(NN=CRFc)(PMe₂Ph)₂] (5). The X-ray analyses have been undertaken to determine the detailed structures for 2a (R = H) and 5b (R = Me).

Full text of DOI:10.1016/s0020-1693(98)00361-2

Inorganica Chimica Acta 285 (1999) 336±340
Note
Synthesis and structures of tungsten ferrocenyldiazoalkane
complexes derived from a dinitrogen complex.
Part 58. Preparation and properties of molybdenum and
tungsten dinitrogen complexes1
Yuji Haradaa, Yasushi Mizobea, Masanobu Hidaib,*
a Institute of Industrial Science, The University of Tokyo, Roppongi, Minato-ku, Tokyo 106-8558, Japan
b Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-8656, Japan
Received 29 May 1998; accepted 31 August 1998
Abstract
Reaction of the hydrazido(2-) complex cis, mer-[WCl2(NNH2)(PMe2Ph)3], derived from a dinitrogen complex cis-[W(N2)2(PMe2Ph)4],
with formylferrocene or acetylferrocene gave ferrocenyldiazoalkane complexes cis, mer-[WCl2(NN=CRFc)(PMe2Ph)3] (2: R ˆ H, Me;
Fc ˆ (h5-C5H4)Fe(h5-C5H5)). Treatment of 2 with p-acceptor ligands L such as CO, CH2=CH2, p-MeC6H4CHO, p-MeC6H4C>CH and
ButNC afforded a series of ferrocenyldiazoalkane complexes cis, trans-[WCl2(NN=CRFc)(L)(PMe2Ph)2] (4), while upon treatment with
CH2Cl2 2 gave the W(V) complexes mer, trans-[WCl3(NN=CRFc)(PMe2Ph)2] (5). The X-ray analyses have been undertaken to determine
the detailed structures for 2a (R ˆ H) and 5b (R ˆ Me). # 1999 Elsevier Science S.A. All rights reserved.
Keywords: Crystal structures; Tungsten complexes; Dinitrogen complexes; Diazoalkane complexes; Ferrocenyl complexes
1. Introduction
or cis, mer-[MX2(NNH2)(PMe2Ph)3], readily accessible
from the N2 complexes. Much effort has been made in quest
of the versatile methods to liberate the diazoalkane ligands
as organo-nitrogen compounds.
In this article we wish to report the syntheses, structures,
and properties of the ferrocenyldiazoalkane complexes
cis, mer-[WCl2(NN=CRFc)(PMe2Ph)3] (2a: R ˆ H; 2b:
R ˆ Me; Fc ˆ (h5-C5H4)Fe(h5-C5H5)) and their deriva-
tives, which demonstrate a new feature of the diazoalkane
ligand arising from the presence of the easily oxidizable and
sterically bulky ferrocenyl substituent.
The C±N bond formation at coordinated dinitrogen is a
crucial step to achieve synthesis of organo-nitrogen com-
pounds from molecular nitrogen under mild conditions [2±
4]. However, there is only a limited number of dinitrogen
complexes where the N2 ligand is transformed into an
organo-nitrogen ligand or released from the metal as an
organo-nitrogen compound. It is noteworthy that the Mo and
W dinitrogen complexes trans-[M(N2)2(dppe)2] (dppe ˆ
Ph2PCH2CH2PPh2) and cis-[M(N2)2(PMe2Ph)4] (M ˆ Mo,
W) exhibit exceptionally high reactivities of the coordinated
dinitrogen which result in the C±N bond formation along
with the protonation at the N2 ligand. One of the most
potential methods to convert the N2 ligand into organo-
nitrogen ligands is demonstrated by the syntheses of diazo-
2. Experimental
2.1. General methods
‡
alkane complexes such as trans-[MF(NN=CRR0)(dppe)2]
[5,6] and cis, mer-[MX2(NN=CRR0)(PMe2Ph)3] (1; X ˆ
All manipulations were performed under an atmosphere
of nitrogen using standard Schlenk techniques. Solvents
were dried and distilled by common procedures and then
degassed before use. The hydrazido(2-) complex cis, mer-
[WCl2(NNH2)(PMe2Ph)3] (3) was prepared by literature
methods [9]. Formylferrocene (FcCHO) and acetylferrocene
halogen) [7,8] via condensation of aldehydes or ketones with
the hydrazido(2-) complexes trans-[MF(NNH2)- (dppe)2]
‡
*Corresponding author. Tel.: +81-3-3812-2111; fax: +81-3-5800-6945.
1Part 57: see Ref. [1].
0020-1693/99/$ ± see front matter # 1999 Elsevier Science S.A. All rights reserved.
PII: S0020-1693(98)00361-2

Y. Harada et al. / Inorganica Chimica Acta 285 (1999) 336±340
337
(FcCOMe) were obtained from Aldrich Chemical, or Tokyo
Chemical Industry. Spectroscopic measurements and the
elemental analyses were done as described previously [1].
Electrochemical data were collected as reported elsewhere
[10]. In the H NMR data below, the signals due to the
phenyl protons are omitted.
4c (R ˆ H, L ˆ h2-p-MeC6H4CHO). Yield: 78%. Anal.
Calc. for C35H40N2OCl2P2FeW: C, 47.92; H, 4.60; N, 3.19.
Found: C, 47.97; H, 5.02; N, 2.95%. IR (KBr): ꢀ(C=N),
1543 cm . H NMR (C6D6): ꢁ 5.18 (d, 1H, J ˆ 9.9 Hz,
MeC6H4CHO), 4.26 and 4.13 (m, 1H each, C5H4), 4.10 (m,
2H, C5H4), 4.02 (s, 5H, Cp), 2.26 (s, 3H, MeC6H4CHO),
1
1
1
2.09 (d, 3H, JP±H ˆ 9.9 Hz, PMe), 2.02 (d, 6H, JP±H
ˆ
2.2. Preparation of cis, mer-[WCl2(NN=CRFc)
(PMe2Ph)3] (2a: R ˆ H; 2b: R ˆ Me)
10.2 Hz, PMe), 1.87 (d, 3H, JP±H ˆ 9.2 Hz, PMe).
4d (R ˆ H, L ˆ h2-p-MeC6H4C>CH). Yield: 63%. Anal.
Calc. for C36H40N2Cl2P2FeW: C, 49.51; H, 4.62; N, 3.21.
Found: C, 50.12; H, 5.06; N, 3.04%. IR (KBr): ꢀ(C>C),
To an orange suspension of 3 (100 mg, 0.143 mmol) in
CH2Cl2 (5 cm3) 2 equiv. of FcCHO or FcCOMe were added,
and the mixture was stirred at room temperature for 5 h in
the presence of a catalytic amount of aqueous HCl. The
resultant purple solution was evaporated to dryness in vacuo
and the residue was washed with ether to remove the
unreacted FcCHO or FcCOMe. The remaining solid was
crystallized from CH2Cl2-hexane to yield the purple crystals
of 2, which were ®ltered off, washed with hexane, and then
dried in vacuo.
1
1728; ꢀ(C=N) 1541 cm . 1H NMR (C6D6): ꢁ 9.77 (dd, 1H,
J ˆ 16.5 and 5.6 Hz, MeC6H4C>CH), 4.37 and 4.23 (m, 1H
each, C5H4), 4.08 (m, 2H, C5H4), 3.97 (s, 5H, Cp), 2.17,
2.14, 2.05 and 1.67 (d, 3H each, JP±H ˆ 9.9 Hz, PMe), 2.11
(s, 3H, MeC6H4C>CH).
4e (R ˆ H, L ˆ ButNC). Yield: 94%. Anal. Calc. for
C32H44N3Cl2P2FeW: C, 45.74; H, 4.92; N, 5.00. Found: C,
45.12; H, 5.15; N, 4.86%. IR (KBr): ꢀ(C>N), 2127 and 1910
1
(br);ꢀ(C=N),1545 cm . 1HNMR(C6D6):ꢁ 4.31and4.09(t,
2a. Yield: 84%. Anal. Calc. for C35H43N2Cl2P3FeW: C,
46.96; H, 4.84; N, 3.13. Found: C, 46.86; H, 4.89; N, 3.19%.
2Heach, J ˆ 2.0 Hz, C5H4), 3.93(s, 5H, Cp), 2.09and2.07(t,
6H each, JP±H ˆ 4.2 Hz, PMe), 1.06 (s, 9H, ButNC).
4f (R ˆMe, L ˆ CO). Yield: 77%. Anal. Calc. for
C28H32N2OCl2P2FeW: C, 43.59; H, 4.29; N, 3.51. Found:
1
IR (KBr): ꢀ(C=N), 1551 cm . 1H NMR (C6D6): ꢁ 4.40 and
4.13 (t, 2H each, J ˆ 2.0 Hz, C5H4), 3.99 (s, 5H, Cp), 2.11
and 1.74 (t, 6H each, JP±H ˆ 3.6 Hz, PMe), 1.58 (d, 6H,
JP±H ˆ 8.6 Hz, PMe). The methine resonance seems to be
overlapping with the signals of the phenyl protons.
C, 43.80; H, 4.33; N, 3.58%. IR (KBr): ꢀ(CO), 1920;
1
ꢀ(C=N), 1510 cm
.
1H NMR (C6D6): ꢁ 4.33 and 4.06
(m, 2H each, C5H4), 3.81 (s, 5H, Cp), 1.94 (t, 12H,
JP±H ˆ 4.0 Hz, PMe), 1.48 (s, 3H, NN=CMe).
2b. Yield: 88%. Anal. Calc. for C36H45N2P3Cl2FeWÁ
0.5CH2Cl2: C, 46.06; H, 4.87; N, 2.94. Found: C, 46.68;
4g (R ˆ Me, L ˆ h2-CH2=CH2). Yield: 80%. Anal. Calc.
1
H, 5.07; N, 3.02%. IR (KBr): ꢀ(C=N), 1530 cm . 1H NMR
for C30H38N2P2Cl2FeW: C, 45.09; H, 4.79; N, 3.51. Found:
1
(C6D6): ꢁ 4.53 and 4.14 (m, 2H each, C5H4), 3.97 (s, 5H,
Cp), 2.02 (s, 3H, NN=CMe), 1.97 and 1.81 (t, 6H each,
JP±H ˆ 3.6 Hz, PMe), 1.60 (d, 6H, JP±H ˆ 8.6 Hz, PMe).
C, 44.78; H, 4.78; N, 3.51%. IR (KBr): ꢀ(C=N), 1518 cm
.
1H NMR (C6D6): ꢁ 4.40 and 4.10 (t, 2H each, J ˆ 2.0 Hz,
C5H4), 3.92 (s, 5H, Cp), 2.13±2.03 (m, 4H, C2H4), 2.03 and
1.92 (t, 6H each, JP±H ˆ 4.3 Hz, PMe), 1.59 (s, 3H,
NN=CMe).
2.3. Preparation of cis, trans-[WCl2(NN=CRFc)(L)
(PMe2Ph)2](4)
4h (R ˆMe, L ˆ h2-p-MeC6H4C>CH). Yield: 63%.
Anal. Calc. for C36H40N2Cl2P2FeWÁCH2Cl2: C, 46.95; H,
4.56; N, 2.88. Found: C, 47.55; H, 4.73; N, 2.67%. IR (KBr):
On treatment with CO (1 atm), CH2=CH2 (1 atm), p-
MeC6H4CHO (4 equiv.), p-MeC6H4C>CH (1 equiv.) or
ButNC (1 equiv.) in THF at 558C for 16±24 h, the purple
solution of 2 turned dark purple. The resulting solution was
dried up in vacuo and the residue was crystallized from
CH2Cl2-hexane to give purple crystals of 4, which were
®ltered off, washed with hexane, and then dried in vacuo.
4a (R ˆ H, L ˆ CO). Yield: 92%. Anal. Calc. for
C28H32N2OCl2P2FeW: C, 42.84; H, 4.11; N, 3.57. Found:
1
ꢀ(C>C), 1736; ꢀ(C=N), 1510 cm . 1H NMR (C6D6): ꢁ 9.63
(dd, 1H, J ˆ 16.5 and 5.8 Hz, MeC6H4C>CH), 4.49 and
4.41 (m, 1H each, C5H4), 4.14 (m, 2H, C5H4), 3.97 (s, 5H,
Cp), 2.21±1.82 (total 18H, MeC6H4C>CH, PMe, and
NN=CMe).
4i (R ˆ Me, L ˆ ButNC). Yield: 70%. Anal. Calc. for
C32H44N3Cl2P2FeW: C, 46.40; H, 5.07; N, 4.92. Found: C,
46.01; H, 5.21; N, 4.62%. IR (KBr): ꢀ(C>N), 2091; ꢀ(C=N)
1
C, 42.96; H, 4.05; N, 3.88%. IR (KBr): ꢀ(CO), 1934;
1
1518 cm . 1H NMR (C6D6): ꢁ 4.46 and 4.09 (m, 2H each,
ꢀ(C=N), 1541 cm
.
1H NMR (C6D6): ꢁ 4.11 and 3.99
C5H4), 3.89 (s, 5H, Cp), 2.08 and 2.05 (t, 6H each,
JP±H ˆ 4.0 Hz, PMe), 1.70 (s, 3H, NN=CMe), 1.05 (s,
9H, ButNC).
(m, 2H each, C5H4), 3.73 (s, 5H, Cp), 1.87 and 1.85 (t,
6H each, JP±H ˆ 4.0 Hz, PMe).
4b (R ˆ H, L ˆ h2-CH2=CH2). Yield: 88%. Anal. Calc.
for C29H36N2OP2Cl2FeW: C, 44.36; H, 4.62; N, 3.57.
Found: C, 43.83; H, 4.76; N, 3.51%. IR (KBr): ꢀ(C=N),
2.4. Preparation of mer, trans-[WCl3(NN=CRFc)
(PMe2Ph)2](5)
1
1
1551 cm . H NMR (C6D6): ꢁ 4.26 and 4.11 (t, 2H each,
J ˆ 2.0 Hz, C5H4), 3.90 (s, 5H, Cp), 2.18±1.94 (m, 4H,
C2H4), 2.11 and 1.90 (t, 6H each, JP±H ˆ 4.3 Hz, PMe).
A purple solution of 2 in THF (5 cm3)-CH2Cl2 (3 cm3)
kept at 558C gradually turned dark purple. After 16 h, the

338
Y. Harada et al. / Inorganica Chimica Acta 285 (1999) 336±340
Table 1
5b (R ˆ Me). Yield: 69%. Anal. Calc. for C28H34N2Cl3-
P2FeW: C, 41.69; H, 4.25; N, 3.47. Found: C, 41.64; H,
X-ray crystallographic data for 2a and 5b
1
4.30; N, 3.41%. IR (KBr): ꢀ(C=N) 1510 cm
.
2a
5b
Crystal data
Empirical formula
Formula weight
Crystal color
C35H43N2Cl2P3FeW C28H34N2P2Cl3FeW
2.5. X-ray crystallographic studies of 2a and 5b
895.26
806.59
red±purple
0.2 Â 0.3 Â 0.6
monoclinic
C2/c (no. 15)
25.893(3)
9.959(5)
28.825(3)
91.015(8)
7431(3)
8
purple
Crystal dimension (mm)
Crystal system
0.5 Â 0.7 Â 0.7
monoclinic
P21/n (no. 14)
13.318(2)
12.467(2)
19.068(2)
103.589(7)
3077.4(6)
4
The X-ray diffraction studies were undertaken as
described in the previous paper [1]. The crystallographic
data for 2a and 5b are summarized in Table 1.
Space group
Ê
a (A)
Ê
b (A)
Ê
c (A)
ꢂ (8)
V (A )
3. Results and discussion
Ê 3
Z
3
3.1. Preparation of ferrocenyldiazoalkane complexes 2
Dcalc. (g cm
)
1.60
1.741
1
ꢃ (Mo Ka) (cm
F (000)
)
37.86
45.95
3568
1588
Reaction of the hydrazido(2-)complex 3, readily derived
from cis-[W(N2)2(PMe2Ph)4], with 2 equiv. of FcCHO or
FcCOMe in CH2Cl2 proceeded smoothly at room tempera-
ture in the presence of a catalytic amount of aqueous HCl to
give the purple ferrocenyldiazoalkane complexes 2a and 2b
in 84 and 88% yields, respectively (Scheme 1). This pro-
cedure is essentially similar to that for preparing 1 (X ˆ Cl)
by condensation between 3 and common aldehydes or
ketones [7,8]. In the IR spectra, the intense bands assignable
to ꢀ(C=N) appeared at 1551 and 1530 cm 1 for 2a and 2b,
respectively, which are comparable to the values observed
for 1 (R ˆ Ph, R0 ˆ H or Me), e.g. cis, mer-[WCl2(NN=
Data collection
Radiation (ꢄ)
Monochromator
Temperature
Scan method
Scan rate (8 min
2ꢅmax (8)
Ê
Ê
Mo Ka (0.7107 A)
graphite
room temperature
Mo Ka (0.7107 A)
graphite
room temperature
!/2ꢅ
16
!/2ꢅ
16
1
)
55
55
No. of unique reflections
9008
7395
Transmission factors
1.003±1.075
0.4138±1.000
Structure solution and refinements
No. of data used
No. of variables
R, Rw
5718 (I > 5ꢆ(I))
397
5423 (I > 3ꢆ(I))
335
1
CHPh)(PMe2Ph)3]: 1535 cm [10] and cis, mer-[WBr2-
0.033, 0.022
0.032, 0.023
1
1
(NN=CMePh)(PMe2Ph)3]: 1537 cm [7]. The H NMR
spectra of 2 show the resonances due to the ferrocenyl group
in addition to the signals ascribable to the three PMe2Ph
ligands. Appearance of the methyl protons in these PMe2Ph
ligands as two triplets and one doublet indicates the mer-
idional con®guration of the three PMe2Ph ligands. These
spectroscopic data suggest that complexes 2 have the struc-
ture shown in Scheme 1, which has been further con®rmed
by the X-ray analysis of 2a (vide infra).
resultant solution was evaporated to dryness and the residue
was crystallized from CH2Cl2-hexane to give purple crystals
of 5, which were ®ltered off, washed with hexane, and then
dried in vacuo.
5a (R ˆ H). Yield: 54%. Anal. Calc. for C27H32N2Cl3-
P2FeW: C, 40.92; H, 4.07; N, 3.53. Found: C, 40.40; H,
.
1
4.23; N, 3.56%. IR (KBr): ꢀ(C=N) 1541 cm
Scheme 1.

Y. Harada et al. / Inorganica Chimica Acta 285 (1999) 336±340
339
3.2. Reactions of ferrocenyldiazoalkane complexes 2
In the course of our study to clarify the reactivities of 1,
we have previously found that new diazoalkane complexes
such as cis, trans-[MX2(NN=CRR0)(L)(PMe2Ph)2] [10,11]
and mer, trans-[WX3(NN=CRR0)(PMe2Ph)2] [12] are
further available from 1, although the diazoalkane ligands
are left intact in these complexes in spite of either the
coordination of various p-acceptor ligands L in the cis
position for the former or the oxidation of the W center
for the latter. It has been shown that 2 reacts analogously
with various p-acceptor ligands L (L ˆ CO, C2H4, p-
MeC6H4CHO, p-MeC6H4C>CH, or ButNC) to give a series
of diazoalkane complexes cis, trans-[WCl2(NN=CRFc)-
(L)(PMe2Ph)2] (4) in moderate to high yields, where the
PMe2Ph ligand being cis to the diazoalkane ligand and trans
to one Cl in 2 is selectively replaced by L (Scheme 1). The
spectroscopic data observed for 4 are comparable to those of
similar compounds cis, trans-[WCl2(NN=CRMe)(L)-
(PMe2Ph)2] (R ˆ Me, Ph) reported previously [10].
Treatment of 2 with excess CH2Cl2 in THF at 558C
yielded the paramagnetic 5a and 5b in 54 and 69% yields,
respectively (Scheme 1). The presence of the diazoalkane
ligands is implicated by the ꢀ(C=N) bands at 1541 and
1510 cm 1 in the IR spectra. The X-ray diffraction study of
5b has been carried out to con®rm the structure as described
below.
Fig. 1. Molecular structure of 2a. Carbon atoms in the PMe2Ph ligands
and all hydrogen atoms are omitted for clarity.
3.3. Structures of 2a and 5b
The detailed structures of 2a and 5b have been deter-
mined by X-ray crystallography. The ORTEP drawings are
depicted in Figs. 1 and 2, while the selected bond distances
and angles are listed in Table 2. Both complexes have a
slightly distorted octahedral structure, in which the dia-
zoalkane ligand occupies the position trans to one of the Cl
ligands. In 2a three PMe2Ph ligands are mutually meridio-
nal, whereas 5b has a structure resulting from the replace-
ment of the unique PMe2Ph ligand in 2a by the Cl ligand.
The W±Cl bond lengths in the W(V) complex 5b (2.400(1),
Ê
2.465(1), and 2.408 A) are slightly shorter than those in the
Ê
W(IV) complex 2a (2.466(1) and 2.533 A), while the W±P
Ê
distances in the former (2.549(1) and 2.565(1) A) are some-
what elongated from those in the latter (2.492(2), 2.454(1),
Ê
and 2.527(1) A). Pertinent bonding parameters in the fer-
Fig. 2. Molecular structure of 5b. Carbon atoms in the PMe2Ph ligands
and all hydrogen atoms are omitted for clarity.
rocenyldiazoalkane ligand are similar to each other for 2a
and 5b; the W±N±N linkage is essentially linear (2a:
173.3(1)8, 5b: 169.3(3)8), while the N±N±C moiety is bent
with the angles of 115.4(4)8 for 2a and 119.2(4)8 for 5b. In
both complexes, the ferrocenyl group is bound to the C=N
bond so as to be oriented to the exo direction presumably
because of the steric bulkyness. The W, N(1), N(2), and
C(25) (in 2a) or C(2) (in 5b) atoms, together with the Cp
ring attached to this C atom are essentially coplanar. The
observed N±N and N±C bond lengths, viz. d (N±N): 2a,
Ê
1.298(5) A, are almost comparable to those of the related
diazoalkane ligands reported previously; e.g. d (N±N):
Ê
1.29(2) and d (N±C): 1.27(2) A in cis, trans-[WCl2(NN=
CMePh)(h2-p-MeC6H4CHO)(PMe2Ph)2] [10] and d (N±N):
Ê
1.27(1) and d (N±C): 1.30(2) A in mer, trans-[WBr3(NN=
CMePh)(PMe2Ph)2] [12], although the N±N distance in 2a
is somewhat longer. By comparison, the values observed in
the hydrazones of FcCHO relevant to 2a and 5b are, e.g.,
FcCH=NNH(C5H4N-2): d (N±N), 1.368(5); d (N±C),
Ê
Ê
Ê
1.360(5) A; 5b, 1.313(5) A and d (N±C): 2a, 1.284(5) A; 5b,

340
Y. Harada et al. / Inorganica Chimica Acta 285 (1999) 336±340
Table 2
Table 3
Oxidation potentials of diazoalkane complexesa
Ê
Selected bond lengths (A) and angles (8) in 2a and 5b
2a
W±Cl(1)
W±P(1)
L
WCl2(NN=CHFc)-
(L)(PMe2Ph)2
WCl2(NN=CMe2)-
c
(L)(PMe2Ph)2
2.466(1)
2.492(2)
2.527(1)
1.360(5)
W±Cl(2)
W±P(2)
2.533(1)
2.454(1)
1.736(4)
1.284(5)
PMe2Ph
CO
0.15 (r), 1.13 (ir)
0.68, 1.05 (ir)
1.15 (ir)b
0.13 (r)
0.98 (ir)
1.20 (ir)
W±P(3)
W±N(1)
N(1)±N(2)
N(2)±C(25)
C2H4
a In CH2Cl2±0.1 M ‰nBu4NŠ[BF4]. Peak oxidation potential vs. SCE at a
Cl(1)±W±Cl(2)
Cl(1)±W±P(2)
Cl(1)±W±N(1)
Cl(2)±W±P(2)
Cl(2)±W±N(1)
P(1)±W±P(3)
P(2)±W±P(3)
P(3)±W±N(1)
N(1)±N(2)±C(25)
88.04(5)
86.83(5)
174.3(1)
174.48(5)
97.6(1)
Cl(1)±W±P(1)
Cl(1)±W±P(3)
Cl(2)±W±P(1)
Cl(2)±W±P(3)
P(1)±W±P(2)
P(1)±W±N(1)
P(2)±W±N(1)
W±N(1)±N(2)
N(2)±C(25)±C(26)
87.03(5)
84.61(5)
80.82(5)
84.69(5)
96.91(5)
92.9(1)
scan rate 200 mV s 1. (r)ˆreversible and (ir)ˆirreversible process.
b The peaks due to W(IV)/W(V) and Fe(II)/Fe(III) couples are over-
lapping.
c Ref. [10].
163.64(5)
96.85(5)
96.5(1)
87.5(1)
173.3(1)
121.8(4)
4. Supplementary material
115.5(4)
Detailed data of the X-ray crystallographic studies for 2a
and 5b, which include Tables of atomic coordinates, aniso-
tropic temperature factors of non-hydrogen atoms, and
extensive bond distances and angles, together with Figures
showing their full view, are available from the authors (Y.M.
or M.H.) upon request.
5b
W±Cl(1)
W±Cl(3)
W±P(2)
N(1)±N(2)
2.400(1)
2.408(1)
2.565(1)
1.313(5)
W±Cl(2)
W±P(1)
2.465(1)
2.549(1)
1.763(4)
1.298(5)
W±N(1)
N(2)±C(2)
Cl(1)±W±Cl(2)
Cl(1)±W±P(1)
Cl(1)±W±N(1)
Cl(2)±W±P(1)
Cl(2)±W±N(1)
Cl(3)±W±P(2)
P(1)±W±P(2)
86.60(5)
88.24(4)
98.2(1)
Cl(1)±W±Cl(3)
Cl(1)±W±P(2)
Cl(2)±W±Cl(3)
Cl(2)±W±P(2)
Cl(3)±W±P(1)
Cl(3)±W±N(1)
P(1)±W±N(1)
W±N(1)±N(2)
N(2)±C(2)±C(1)
C(1)±C(2)±C(3)
170.82(5)
81.75(4)
85.04(5)
87.52(4)
87.17(5)
90.1(1)
84.39(4)
175.1(1)
101.66(5)
167.48(5)
93.4(1)
Acknowledgements
Financial support by Grant-in-Aid for Specially Pro-
moted Research (No. 09102004) from the Ministry of
Education, Science, Sports, and Culture of Japan is appre-
ciated.
94.6(1)
P(2)±W±N(1)
N(1)±N(2)±C(2)
N(2)±C(2)±C(3)
169.3(3)
123.8(5)
119.7(4)
119.2(4)
116.5(4)
Ê
1.274(5) A [13] and FcCH=NN=CHC6H4NO2-p: d (N±N),
References
Ê
1.410(6); d (N±C), 1.272(7) A [14].
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3.4. Electrochemical properties of 2 and 4
The cyclic voltammogram of 2a exhibits a reversible
oxidation wave due to the W(IV)/W(V) couple at the anodic
peak potential Epox at 0.15 V versus SCE together with an
irreversible oxidation wave attributable to the Fe(II)/Fe(III)
couple at Epox ˆ 1.13 V. The former value is in good agree-
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process of 0.13 V observed for 1a (X ˆ Cl, R ˆ R0 ˆ
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in the x±y plane with p-acceptor ligands L such as CO and
CH2=CH2, resulting in the shift of the E1o=x2 values to the
positive direction in these derivatives cis, trans-
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was also observed for the potential due to the W(IV)/
W(V) couple in 4, as summarized in Table 3. On the other
hand, the oxidation wave arising from the process
Fe(II) ! Fe(III) in 4 appeared at the same potential as in 2.
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