Reactions of Mo(II)-tetraphosphine complex [MoCl2{meso-o-C6H4(PPhCH2CH2PPh2)2}] with a series of small molecules

Article abstract of DOI:10.1016/j.jorganchem.2007.10.054

Reactions of Mo(II)-tetraphosphine complex [MoCl₂(κ⁴-P4)] (2; P4 = meso-o-C₆H₄(PPhCH₂CH₂PPh₂)₂) with a series of small molecules have been investigated. Thus, treatment of 2 with alkynes RC{triple bond, long}CR′ (R = Ph, R′ = H; R = p-tolyl, R′ = H; R = Me, R′ = Ph) in benzene or toluene gave neutral mono(alkyne) complexes [MoCl₂(RC{triple bond, long}CR′)(κ³-P4)] containing tridentate P4 ligand, which were converted to cationic complexes [MoCl(RC{triple bond, long}CR′)(κ⁴-P4)]Cl having tetradentate P4 ligand upon dissolution into CDCl₃ or CD₂Cl₂. The latter complexes were available directly from the reactions of 2 with the alkynes in CH₂Cl₂. On the other hand, treatment of 2 with 1 equiv. of XyNC (Xy = 2,6-Me₂C₆H₃) afforded a seven-coordinate mono(isocyanide) complex [MoCl₂(XyNC)(κ⁴-P4)] (7), which reacted further with XyNC to give a cationic bis(isocyanide) complex [MoCl(XyNC)₂(κ⁴-P4)]Cl (8). From the reaction of 2 with CO, a mono(carbonyl) complex [MoCl₂(CO)(κ⁴-P4)] (9) was obtained as a sole isolable product. Reaction of 9 with XyNC afforded [MoCl(CO)(XyNC)(κ⁴-P4)]Cl (10a) having a pentagonal-bipyramidal geometry with axial CO and XyNC ligands, whereas that of 7 with CO resulted in the formation of a mixture of 10a and its isomer 10b containing axial CO and Cl ligands. Structures of 7 and 9 as well as [MoCl(XyNC)₂(κ⁴-P4)][PF₆](8′) and [MoCl(CO)(XyNC)(κ⁴-P4)][PF₆] (10a′) derived by the anion metathesis from 8 and 10a, respectively, were determined in detail by the X-ray crystallography.

Full text of DOI:10.1016/j.jorganchem.2007.10.054

Available online at www.sciencedirect.com
Journal of Organometallic Chemistry 693 (2008) 269–277
www.elsevier.com/locate/jorganchem
Reactions of Mo(II)-tetraphosphine complex
[MoCl2{meso-o-C6H4(PPhCH2CH2PPh2)2}] with a series
of small molecules
Takeshi Ohnishi, Hiroko Tsuboi, Hidetake Seino, Yasushi Mizobe *
Institute of Industrial Science, The University of Tokyo, Komaba, Meguro-ku, Tokyo 153-8505, Japan
Received 26 June 2007; received in revised form 23 October 2007; accepted 30 October 2007
Available online 7 November 2007
Abstract
Reactions of Mo(II)-tetraphosphine complex [MoCl2(j4-P4)] (2; P4 = meso-o-C6H4(PPhCH2CH2PPh2)2) with a series of small mol-
ecules have been investigated. Thus, treatment of 2 with alkynes RC„CR0 (R = Ph, R0 = H; R = p-tolyl, R0 = H; R = Me, R0 = Ph) in
benzene or toluene gave neutral mono(alkyne) complexes [MoCl2(RC„CR0)(j3-P4)] containing tridentate P4 ligand, which were con-
verted to cationic complexes [MoCl(RC„CR0)(j4-P4)]Cl having tetradentate P4 ligand upon dissolution into CDCl3 or CD2Cl2. The
latter complexes were available directly from the reactions of 2 with the alkynes in CH2Cl2. On the other hand, treatment of 2 with
1 equiv. of XyNC (Xy = 2,6-Me2C6H3) afforded a seven-coordinate mono(isocyanide) complex [MoCl2(XyNC)(j4-P4)] (7), which
reacted further with XyNC to give a cationic bis(isocyanide) complex [MoCl(XyNC)2(j4-P4)]Cl (8). From the reaction of 2 with CO,
a mono(carbonyl) complex [MoCl2(CO)(j4-P4)] (9) was obtained as a sole isolable product. Reaction of 9 with XyNC afforded [MoCl-
(CO)(XyNC)(j4-P4)]Cl (10a) having a pentagonal–bipyramidal geometry with axial CO and XyNC ligands, whereas that of 7 with CO
resulted in the formation of a mixture of 10a and its isomer 10b containing axial CO and Cl ligands. Structures of 7 and 9 as well as
[MoCl(XyNC)2(j4-P4)][PF6](80) and [MoCl(CO)(XyNC)(j4-P4)][PF6] (10a0) derived by the anion metathesis from 8 and 10a, respec-
tively, were determined in detail by the X-ray crystallography.
Ó 2007 Elsevier B.V. All rights reserved.
Keywords: Mo complex; Tetraphosphine; Alkyne; Isocyanide; CO
1. Introduction
by one, two, or three molecules such as nitrile, CO, and iso-
cyanide [2] but also the C@O and C@S bond cleaving reac-
tions of CO2 and RNCS, respectively [3]. Interesting
feature observed for P4 in these reactions is its ability to
change the coordination mode readily from j4 to j3, and
even to j2.
More recently we have isolated the dihalide complexes
[MX2(j4-P4)] (M = Mo: X = Cl (2), Br; M = W: X = Br)
by treatment of 1 with PhCH2X, which are the diamagnetic
complexes having a trigonal–prismatic structure shown in
Eq. (1) with 16-electron, coordinatively unsaturated metal
centers [4]. As for the reactivities of 2, we have reported
already the reactions with diazoalkanes in a preliminary
form, which include the catalytic conversion of
N2CHCOOEt into EtOCOCH@CHCOOEt as well as
the formation of the diazoalkane complexes such as
We found previously the unexpected formation of the
tetraphosphine complexes [M(j4-P4)(dppe)] (1; M = Mo,
W; P4 = meso-o-C6H4(PPhCH2CH2PPh2)2, dppe = Ph2-
PCH2CH2PPh2) by heating the solutions of trans-[M-
(N2)2(dppe)2] in the presence of 1 equiv. of dppe, where
the unprecedent tetraphosphine P4 forms through the con-
densation of two dppe ligands in the coordination sphere of
Mo or W [1]. Subsequent studies on the reactivities toward
a series of small molecules have disclosed that 1 (M = Mo)
can undergo not only the substitutions of bound P atoms
*
Corresponding author. Fax: +81 3 5452 6361.
E-mail address: ymizobe@iis.u-tokyo.ac.jp (Y. Mizobe).
0022-328X/$ - see front matter Ó 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2007.10.054

270
T. Ohnishi et al. / Journal of Organometallic Chemistry 693 (2008) 269–277
[MoCl2(NN = CHSiMe3)(j3-P4)] and [MoCl(NN = CHSi-
Me3)(j4-P4)][PF6] [4]. Quite recently, it has also been dem-
onstrated that 2 facilitates the N–N bond cleavage of
organohydrazines to give nitrido and imido complexes
[MoCl(N)(j4-P4)] and [MoCl(NR)(j4-P4)][PF6] (R = Me,
Ph). From the former nitrido complex, acylimido com-
plexes of two types [MoCl2(NCOMe)(j3-P4)] (3a) and
[MoCl(NCOMe)(j4-P4)][PF6] (3b) have been derivatized
by treatment with MeCOCl and fully characterized by X-
ray diffraction [5]. In this paper, we wish to describe the
details of the reactions of 2 with other selected small mol-
ecules, forming a series of new P4 complexes
18-electron count of the Mo center may be satisfied by this
six-coordinate, octahedral geometry. In the 1H NMR spec-
trum, the alkynic proton resonates at d 11.4 as the doublet
of doublets of doublets.
Interestingly, upon dissolution into CDCl3, 4a is readily
transformed into
a cationic mono(alkyne) complex
[MoCl(PhC„CH)(j4-P4)]Cl (4b), as indicated by the
31P{1H} NMR spectrum exhibiting only two signals com-
parable to that of the X-ray analyzed 3b [5]. The alkynic
1
proton appears in the H NMR spectrum at d 12.4 as the
triplet of triplets. As expected, the reaction of 2 with
PhC„CH conducted in CH2Cl2 also gave 4b as a green
solid in moderate yield upon precipitation from CH2Cl2-
hexane. When 4b was redissolved in C6D6, the NMR spec-
tra coincide with those of 4a, indicating that the structures
of 4 change reversibly, depending upon the polarity of the
solvents. The structure proposed for 4b on the basis of the
X-ray structure of 3b is shown in Scheme 1. This is sup-
ported quite recently by the X-ray analysis of the alkyne
complex [MoI(MeC„CCOOMe)(j4-P4)]I derived by oxi-
dizing the Mo(0) mono(alkyne) complex [Mo(MeC„
CCOOMe)(j4-P4)] with I2, which will be reported sepa-
rately elsewhere [6]. It is also to be noted that the analo-
gous structure was previously disclosed for the related
diphosphine complexes trans-[MoF(PhC„CH)(dppe)2]-
[BF4] [7] and trans-[MoF(MeNHC„CNHMe)(dppe)2]-
[BF4] [8].
Ph
Ph
P
P
X
P
P
P
PhCH X
P
P
2
M
M
P
Ph
P
ð1Þ
X
P
Ph
P = PPh
2
1
M = Mo, X = Cl (2)
M = Mo, X = Br
M = W, X = Br
2. Results and discussion
2.1. Reactions of 2 with alkynes
Reactions of 2 with TolC„CH (Tol = p-tolyl) took
place similarly at room temperature to give the correspond-
ing [MoCl2(TolC„CH)(j3-P4)] (5a) and [MoCl(TolC„
CH)(j4-P4)]Cl (5b), although the reaction to prepare the
former proceeded more cleanly when conducted in toluene
at 60 °C. The inner alkyne MeC„CPh also reacted with 2
at 60 °C in toluene or at room temperature in CH2Cl2,
yielding [MoCl2(MeC„CPh)(j3-P4)] (6a) and [MoCl(-
MeC„CPh)(j4-P4)]Cl (6b), respectively. On the other
hand, from the reactions with alkynes such as RC„CH
(R = MeOCO, n-Bu, t-Bu) and PhC„CPh, formations of
the alkyne-containing complexes were inferred spectro-
scopically but the isolation of analytically pure products
was unsuccessful.
When reacted with PhC„CH in benzene at room tem-
perature, 2 was converted into a neutral mono(alkyne)
complex [MoCl2(PhC„CH)(j3-P4)] (4a), which was iso-
lated as a green solid in moderate yield (Scheme 1). The
31P{1H} NMR spectrum of a C6D6 solution shows four sig-
nals including one high-field doublet at d ꢀ10.4, which is
characteristic of the free P atom of P4. This spectral feature
is in good agreement with that of the crystallographically
characterized 3a [5], suggesting that 4a also has the octahe-
dral geometry with the j3-P4 ligand as observed for 3a. By
the donation of 4 electrons from the side-on bound alkyne,
R'
P4
Cl
C
CR
Ph
Ph
2.2. Reactions of 2 with isocyanide and CO
P3
P2
RC≡CR'
Mo
Reaction of 2 with 1 equiv. of XyNC (Xy = 2,6-
Me2C6H3) in toluene proceeded smoothly at room temper-
ature to give a mono(isocyanide) complex [MoCl2(-
XyNC)(j4-P4)] (7) in moderate yield (Scheme 2). The X-
ray analysis has disclosed the structure of 7 in detail, whose
ORTEP drawing is depicted in Fig. 1 and selected bond
distances and angles are listed in Table 1.
In contrast to the acylimido and alkyne complexes 3–6,
the isocyanide complex 7 is a seven-coordinate complex
having a distorted monocapped octahedral geometry with
P(3) as a capping atom on the P(2)–P(4)–C(47) face of
the octahedron. Alternatively, it might also be possible to
regard this structure as a monocapped trigonal–prism
C6H6 or C6H5Me
R = Ph, R' = H (4a)
R = Tol, R' = H (5a)
R = Me, R' = Ph (6a)
Cl
P1
C6D6
CDCl3, CD2Cl2
2
R'
P
C
CR
Cl
Ph
Ph
RC≡CR'
CH2Cl2
P
P
Mo
Cl
R = Ph, R' = H (4b)
R = Tol, R' = H (5b)
R = Me, R' = Ph (6b)
P
Scheme 1.

T. Ohnishi et al. / Journal of Organometallic Chemistry 693 (2008) 269–277
271
Table 1
Xy
N
˚
Selected bond distances (A) and angles (°) in 7
Ph
Ph
C
(a) Bond distance
Cl
Mo–Cl(1)
Mo–P(1)
Mo–P(3)
Mo–C(47)
N–C(48)
2.535(2)
2.556(2)
2.441(2)
2.036(9)
1.39(1)
Mo–Cl(2)
Mo–P(2)
Mo–P(4)
C(47)–N
2.558(2)
2.470(2)
2.511(2)
1.16(1)
P
P
P
P
Mo
Cl
C
XyNC
N
(b) Bond angle
P(1)–Mo–P(2)
P(1)–Mo–P(4)
P(1)–Mo–Cl(2)
P(2)–Mo–P(3)
P(2)–Mo–Cl(1)
P(2)–Mo–C(47)
P(3)–Mo–Cl(1)
P(3)–Mo–C(47)
P(4)–Mo–Cl(2)
Cl(1)–Mo–Cl(2)
Cl(2)–Mo–C(47)
C(47)–N–C(48)
Xy
75.07(8)
87.00(7)
82.97(8)
73.37(8)
149.31(8)
108.0(2)
137.30(8)
82.8(2)
P(1)–Mo–P(3)
P(1)–Mo–Cl(1)
P(1)–Mo–C(47)
P(2)–Mo–P(4)
P(2)–Mo–Cl(2)
P(3)–Mo–P(4)
P(3)–Mo–Cl(2)
P(4)–Mo–Cl(1)
P(4)–Mo–C(47)
Cl(1)–Mo–C(47)
Mo–C(47)–N
117.52(8)
87.05(7)
158.9(2)
129.34(8)
73.17(7)
74.13(7)
133.75(7)
72.95(7)
105.2(2)
80.4(2)
8
Xy
N
O
C
C
3
P
Cl
Ph
4
P
4
P
3
Cl
Cl
Mo
P
Ph
2
P
Xy
Mo
N
C
151.69(8)
80.13(7)
78.2(2)
2
1
CO
P
1
P
P
7
169.7(7)
XyNC
CO
Cl
171.4(8)
10b
2
consisting of the P(2)–P(1)–Cl(2) and P(3)–P(4)–C(47)
basal planes with the Cl(1) atom capping to the Cl(2)–
P(1)–P(4)–C(47) rectangle. The XyNC molecule is bound
to the Mo center in an linear end-on fashion with the
Mo–C(47)–N(1) and C(47)–N(1)–C(48) angles of 169.7(7)
and 171.4(8)°, respectively. The Mo–C(47) and C(47)–
O
C
O
C
Ph
Ph
Cl
P
P
P
P
XyNC
P
P
P
P
Ph
Ph
Mo
Cl
Mo
Cl
˚
N(1) bond lengths are 2.036(9) and 1.16(1) A, and the IR
C
Cl
spectrum of 7 shows the m(N„C) band at 2026 cmꢀ1
.
N
Xy
9
For comparison, the octahedral Mo(0) complex [Mo(X-
yNC)(j3-P4)(dppe)], having the averaged Mo–C and C–
N bond lengths in the Mo–C–N array at 2.00(1) and
10a
Scheme 2.
ꢀ1
˚
1.20(2) A, exhibits the m(N„C) band at 1848 cm
[2].
These data are consistent with the stronger electron-donat-
ing ability of the zero-valent Mo center to the XyNC ligand
in the latter complex than the Mo(II) center in 7. In the
31P{1H} NMR spectra of the CDCl3 and C6D6 solutions,
four signals with same intensities were observed, which is
in agreement with the solid state structure containing four
inequivalent P atoms. Based on the previous findings [1–5],
two signals in the lower field are assignable unambiguously
to the inner P atoms P2 and P3, while those in the higher
field to the outer P atoms P1 and P4. However, further
assignments of either P2 or P3 and either P1 or P4 were done
tentatively as shown in Section 3, where the P atoms P2 and
P1 having the longer Mo–P bonds in each pair were
assigned to the resonances observed in the higher field.
Treatment of 2 with 3 equiv. of XyNC in toluene at
room temperature for 1 h resulted in the precipitation of
[MoCl(XyNC)2(j4-P4)]Cl (8) from the reaction mixture
as a red solid (Scheme 2). As expected, this cationic com-
plex is highly soluble in polar CH2Cl2 and was able to be
purified by crystallization from CH2Cl2-ether. This reac-
tion proceeded more smoothly when conducted directly
in CH2Cl2. The X-ray analysis was carried out to determine
the structure by using the single crystal of [MoCl-
(XyNC)2(j4-P4)][PF6] (80) obtained from 8 after the anion
metathesis, which has disclosed the distorted pentagonal–
C(48)
N(1)
C(47)
P(3)
Mo(1)
Cl(2)
Cl(1)
P(4)
P(2)
P(1)
Fig. 1. An ORTEP drawing for 7 at 30% probability level. All hydrogen
atoms are omitted for clarity.

272
T. Ohnishi et al. / Journal of Organometallic Chemistry 693 (2008) 269–277
to the inner P atoms of P4 ligand. In 80, the metrical
parameters associated with two axial XyNC ligands are
almost comparable except for the larger deviation of the
Mo–C(47)–N(1) angle at 170.6(4)° from the linearity than
the Mo–C(56)–N(2) angle at 178.9(4)°.
C(48)
On the other hand, the 31P{1H} NMR spectrum of 8 in
CDCl3 indicates the symmetrical structure containing the
mutually equivalent inner P2 and P3 atoms as well as the
equivalent outer P1 and P4 atoms. In solution, the two
inner P atoms as well as the two outer P atoms each
become equivalent by the fluxional motion of the chelating
rings. The 1H NMR and IR spectra are consistent with the
X-ray structure disclosed for 80.
N(1)
C(47)
P(3)
P(4)
Cl
Mo
P(1)
P(2)
As for the reaction of 2 with an excess amount of CO,
coordination of CO proceeded smoothly at room tempera-
ture in toluene or CH2Cl2, but only the mono(carbonyl)
complex [MoCl2(CO)(j4-P4)] (9) was obtained as the isola-
ble product presumably because of the relatively weak elec-
tron-donating ability of the Mo(II) center in 9 to the p-
acidic CO ligand (Scheme 2). This presents a contrast with
the reaction of the zero-valent Mo complex 1 with CO,
affording readily a bis(carbonyl) complex cis-[Mo(CO)2-
C(56)
N(2)
C(57)
(j4-P4)] in addition to
a
mono(carbonyl) species
Fig. 2. An ORTEP drawing for the cation of 80 at 30% probability level.
All hydrogen atoms are omitted for clarity.
[Mo(CO)(j3-P4)(dppe)] [2]. To determine the detailed
structure, the X-ray analysis has been carried out also for
9.
A single crystal of 9 contained three crystallographically
independent molecules having essentially identical struc-
tures. The ORTEP drawing of one molecule is shown in
Fig. 3, while the selected bond distances and angles are
listed in Table 3. Complex 9 is a neutral, seven-coordinate
complex with the distorted pentagonal–bipyramidal geom-
etry, where the equatorial positions are occupied by four P
atoms of P4 and one Cl ligand. The CO molecule binds to
one axial site opposite to the phenylene group of P4 with
Table 2
0
˚
Selected bond distances (A) and angles (°) in 8
(a) Bond distance
Mo–Cl
2.526(2)
2.461(2)
2.573(2)
2.071(5)
1.424(7)
1.400(7)
Mo–P(1)
Mo–P(3)
Mo–C(47)
C(47)–N(1)
C(56)–N(2)
2.615(2)
2.487(1)
2.097(5)
1.171(6)
1.176(7)
Mo–P(2)
Mo–P(4)
Mo–C(56)
N(1)–C(48)
N(2)–C(57)
(b) Bond angle
Cl–Mo–P(1)
Cl–Mo–P(3)
78.54(5)
141.92(5)
78.1(2)
71.77(5)
150.39(5)
91.5(2)
130.88(6)
78.8(2)
88.4(1)
102.5(2)
169.5(2)
170.9(5)
169.2(5)
Cl–Mo–P(2)
Cl–Mo–P(4)
148.47(5)
74.50(6)
91.8(2)
135.56(5)
83.5(2)
69.58(4)
108.1(2)
73.98(5)
101.6(1)
77.5(2)
Cl–Mo–C(47)
P(1)–Mo–P(2)
P(1)–Mo–P(4)
P(1)–Mo–C(56)
P(2)–Mo–P(4)
P(2)–Mo–C(56)
P(3)–Mo–C(47)
P(4)–Mo–C(47)
C(47)–Mo–C(56)
C(47)–N(1)–C(48)
C(56)–N(2)–C(57)
Cl–Mo–C(56)
P(1)–Mo–P(3)
P(1)–Mo–C(47)
P(2)–Mo–P(3)
P(2)–Mo–C(47)
P(3)–Mo–P(4)
P(3)–Mo–C(56)
P(4)–Mo–C(56)
Mo–C(47)–N(1)
Mo–C(56)–N(2)
O(1)
C(47)
170.6(4)
178.9(4)
P(2)
P(1)
Mo(1)
Cl(2)
P(3)
P(4)
bipyramidal structure of the cation as shown in Fig. 2 and
Table 2. In the cation, four P atoms as well as the Cl ligand
consist of the equatorial plane and two XyNC molecules
occupy the remaining axial positions. In a solid state, four
P atoms are all inequivalent by deviating upward and
downward alternately from the ideal equatorial plane.
Two axial positions are not equivalent because of the orien-
tation of two Ph groups and the phenylene group attached
Cl(1)
Fig. 3. An ORTEP drawing for the molecule 1 of 9 at 30% probability
level. All hydrogen atoms are omitted for clarity.

T. Ohnishi et al. / Journal of Organometallic Chemistry 693 (2008) 269–277
273
Table 3
Selected bond distances (A) and angles (°) in 9
˚
Molecule 1
Molecule 2
Molecule 3
(a) Bond distance
Mo–Cl(1)
Mo–Cl(2)
Mo–P(1)
Mo–P(2)
Mo–P(3)
Mo–P(4)
Mo–C(47)
C(47)–O(1)
2.640(1)
2.541(1)
2.5514(8)
2.492(1)
2.4859(9)
2.5902(9)
1.902(4)
1.162(6)
2.626(1)
2.5228(9)
2.567(1)
2.5133(8)
2.476(1)
2.590(1)
1.887(4)
1.191(4)
2.612(1)
2.517(1)
2.558(1)
2.500(2)
2.471(1)
2.579(2)
1.893(3)
1.178(4)
C(49)
N(1)
C(48)
(b) Bond angle
Cl(1)–Mo–Cl(2)
Cl(1)–Mo–P(1)
Cl(1)–Mo–P(2)
Cl(1)–Mo–P(3)
Cl(1)–Mo–P(4)
Cl(1)–Mo–C(47)
Cl(2)–Mo–P(1)
Cl(2)–Mo–P(2)
Cl(2)–Mo–P(3)
Cl(2)–Mo–P(4)
Cl(2)–Mo–C(47)
P(1)–Mo–P(2)
P(1)–Mo–P(3)
P(1)–Mo–P(4)
P(1)–Mo–C(47)
P(2)–Mo–P(3)
P(2)–Mo–P(4)
P(2)–Mo–C(47)
P(3)–Mo–P(4)
P(3)–Mo–C(47)
P(4)–Mo–C(47)
Mo–C(47)–O(1)
P(2)
P(4)
P(3)
96.23(4)
78.88(3)
91.00(4)
76.71(3)
93.39(4)
175.8(1)
72.77(2)
144.59(3)
143.95(3)
74.19(3)
86.9(1)
74.75(3)
137.46(3)
144.92(3)
99.4(1)
71.42(3)
140.06(3)
84.8(1)
89.97(3)
80.68(3)
91.12(3)
79.22(3)
94.73(3)
177.5(1)
72.95(3)
146.64(4)
143.15(3)
73.49(3)
91.4(1)
74.34(3)
137.82(3)
146.11(3)
97.7(1)
69.41(3)
139.53(4)
86.6(1)
88.94(3)
78.78(3)
93.67(4)
78.17(3)
93.75(4)
178.6(1)
72.95(4)
146.70(3)
143.47(4)
74.36(3)
90.7(2)
75.03(4)
135.42(5)
146.55(4)
99.9(1)
68.99(4)
138.34(3)
85.9(2)
Cl(1)
P(1)
Mo(1)
C(47)
O(1)
Fig. 4. An ORTEP drawing for the cation in the molecule 1 of 10a0 at 30%
probability level. All hydrogen atoms are omitted for clarity.
XyNC is occupying the axial site trans to the CO ligand
with the C–Mo–C angles of 175.0(2) and 172.6(2)° in two
molecules. The Mo–C–O angles of 178.6(4) and 178.7(5)°
as well as the Mo–C–N angles at 173.7(5) and 174.4(5)°
indicate the common linear end-on coordination of both
the CO and isocyanide molecules. Presumably due to the
strong trans effect exerted by CO, replacement of the Cl
ligand trans to CO in 9 proceeds selectively to give the
product having the axial XyNC and CO ligands. From
the 31P{1H} NMR data, the symmetrical structure in which
the inner P atoms as well as the outer P atoms are each
equivalent is indicated in a solution state. The m(N„C)
and m(C„O) bands appear at 2089 and 1872 cmꢀ1, respec-
tively, which are comparable to those at 2061 and
1861 cmꢀ1, observed for the X-ray analyzed, pentagonal–
bipyramidal complex [MoH(PhNC)(CO)(dppe)2][BF4] hav-
ing the PhNC and CO ligands at the axial positions [9].
In contrast, the reaction of the mono(isocyanide) com-
plex 7 with CO in CH2Cl2 gave a mixture of two products.
From the IR and NMR criteria, one product can be iden-
tified as 10a, while the other product 10b is presumed to be
the isomer of 10a, since these data for the other are well
comparable to those of 10a. The ratio of 10a and 10b in
the reaction mixture is estimated to be 4:5 from the
NMR spectra, which is unvariable after 24 h at room tem-
perature. However, when the ClCH2CH2Cl solution of this
mixture was heated to the refluxing temperature for 2 h, it
turned out that the resultant mixture contained only 10b.
By converting 10b obtained by this procedure to 10b0
through anion metathesis using KPF6, some single crystals
were available also for 10b0. Although the X-ray analysis
using these crystals did not complete satisfactorily because
71.07(3)
102.37(1)
90.2(1)
72.47(3)
100.9(1)
87.7(1)
72.60(4)
102.8(1)
87.4(2)
178.2(2)
178.6(4)
178.3(4)
the angle of the C(axial)–Mo–Cl(axial) array at 175.8(1)–
178.6(1)°.
The 31P{1H} NMR spectrum of 9 shows two signals
with the same intensities, indicating that two inner P atoms
and two outer P atoms of P4 are each equivalent as
observed for 8. The IR spectrum exhibits the characteristic
m(C„O) band at 1793 cmꢀ1. It is to be noted that the spec-
troscopic data indicate the formation of only one isomer
for 9, although coordination of CO to one equatorial posi-
tion or the other axial site also seems possible.
The reaction of 9 with CO did not proceed further.
However, treatment of 9 with XyNC in CH2Cl2 at room
temperature afforded cleanly a carbonyl-isocyanide com-
plex [MoCl(CO)(XyNC)(j4-P4)]Cl (10a) (Scheme 2). To
determine the structure of 10a, the X-ray diffraction has
been carried out by using the single crystal of [MoCl-
(CO)(XyNC)(j4-P4)][PF6] (10a0) obtained from 10a after
anion metathesis with KPF6.
The single crystal of 10a0 contained two crystallograph-
ically independent molecules with essentially identical
structures, and the view of the cation of one molecule is
depicted in Fig. 4, while the selected bond distances and
angles are summarized in Table 4. The cation has a dis-
torted pentagonal–bipyramidal geometry with four P and
one Cl atoms at the equatorial sites. The incorporated

274
T. Ohnishi et al. / Journal of Organometallic Chemistry 693 (2008) 269–277
Table 4
[MoCl(CO)2{(i-Pr)2PCH2CH2P(i-Pr)2}2]Cl was presumed
to be monocapped octahedral [13].
0
˚
Selected bond distances (A) and angles (°) in 10a
Molecule 1
Molecule 2
(a) Bond distance
Mo–Cl(1)
Mo–P(1)
Mo–P(2)
Mo–P(3)
2.529(2)
2.576(1)
2.502(1)
2.507(2)
2.566(1)
1.972(6)
2.115(6)
1.166(7)
1.169(8)
1.404(8)
2.527(2)
2.591(1)
2.467(2)
2..504(2)
2.558(1)
1.964(6)
2.108(5)
1.169(7)
1.163(7)
1.410(8)
3. Experimental
3.1. General
Mo–P(4)
All manipulations were carried out under N2 using stan-
dard Schlenk techniques. Solvents were dried by common
methods and distilled under N2 before use. Complex 2
was prepared according to the method described previously
[4], while other chemicals were obtained commercially and
used as received.
NMR spectra were recorded on a JEOL alpha-400 spec-
trometer, while IR spectra were obtained by a JASCO FT/
IR-420 spectrometer. For the H NMR data below, those
due to the P4 ligand, aryl protons, and the solvating
CH2Cl2 molecules are omitted. Numbering schemes for
the P atoms are shown in Schemes 1 and 2. Elemental anal-
yses were done with a Perkin–Elmer 2400 series II CHN
analyzer.
Mo–C(47)
Mo–C(48)
C(47)–O(1)
C(48)–N(1)
N(1)–C(49)
(b) Bond angle
Cl(1)–Mo–P(1)
Cl(1)–Mo–P(2)
Cl(1)–Mo–P(3)
Cl(1)–Mo–P(4)
Cl(1)–Mo–C(47)
Cl(1)–Mo–C(48)
P(1)–Mo–P(2)
P(1)–Mo–P(3)
P(1)–Mo–P(4)
P(1)–Mo–C(47)
P(1)–Mo–C(48)
P(2)–Mo–P(3)
P(2)–Mo–P(4)
P(2)–Mo–C(47)
P(2)–Mo–C(48)
P(3)–Mo–P(4)
P(3)–Mo–C(47)
P(3)–Mo–C(48)
P(4)–Mo–C(47)
P(4)–Mo–C(48)
C(47)–Mo–C(48)
Mo–C(47)–O(1)
Mo–C(48)–N(1)
C(48)–N(1)–C(49)
73.62(4)
143.95(4)
145.91(3)
70.82(4)
92.1(2)
75.86(4)
146.89(4)
143.76(3)
72.16(4)
88.0(2)
1
83.0(2)
85.4(2)
73.07(4)
140.33(4)
144.44(5)
87.5(2)
72.98(4)
138.93(4)
146.13(5)
87.9(2)
90.3(2)
87.4(2)
69.06(4)
140.95(5)
99.8(2)
83.8(2)
75.18(4)
87.7(2)
96.9(2)
93.8(1)
85.5(1)
175.0(2)
178.6(4)
173.7(5)
177.0(5)
69.23(4)
134.43(5)
101.7(2)
82.3(2)
74.77(5)
84.5(2)
102.7(2)
101.7(1)
79.3(1)
172.6(2)
178.7(5)
174.4(5)
170.9(5)
3.2. Preparation of 4
(1) A mixture of 2 (86 mg, 0.097 mmol) and PhC„CH
(22 lL, 0.20 mmol) in benzene (10 cm3) was stirred
at room temperature for 72 h. The resulting green
solution was filtered and concentrated in vacuo.
Addition of hexane afforded 4a as green powder
1
(45 mg, 47% yield). H NMR (C6D6): d 11.38 (dt,
J(H–P) = 16.4, 4.0 Hz, 1H, HC„). 31P{1 H} NMR
(C6D6): ꢀ10.4 (d, 1P, P1), 41.0 (d, 1P, P4), 56.3 (dd,
1P, P2), 95.1 (s, 1P, P3); J(P1–P2) = 38, J(P2–
P4) = 161 Hz. Anal. Calc. for C54H48Cl2MoP4: C,
65.67; H, 4.90. Found: C, 65.24; H, 5.07%.
(2) Similar reaction carried out in CH2Cl2 (7 cm3) affor-
ded 4b ꢁ 0.5CH2Cl2 as a green solid (56 mg, 59%
yield) after deposition from CH2Cl2-hexane. 1H
NMR (CDCl3): d 12.37 (tt, J(H–P) = 10.0, 1.6 Hz,
1H, HC„). 31P{1H} NMR (CDCl3): 55.1 (m, 2P,
P1 and P4), 93.4 (m, 2P, P2 and P3). Anal. Calc. for
of their poor quality, atom connecting scheme in 10b0 has
been disclosed unequivocally as shown in Scheme 2. Thus,
10b has a distorted pentagonal–bipyramidal structure with
CO and Cl ligands at the axial positions and XyNC at one
equatorial site. Probably because of the steric crowding of
the pentagonal equatorial plane, one outer P atom P4 is
much deviated from the plane defined by other three P
atoms and Mo, while the Xy ring is oriented almost per-
pendicularly to the equatorial plane. Replacement of the
XyNC ligand at the trans site by the Cl anion, the
m(C„O) band at 1872 cmꢀ1 for 10a shifts significantly to
the lower frequency region (10b: 1844 cmꢀ1).
C
54.5H49Cl3MoP4: C, 63.54; H, 4.79. Found: C,
63.74; H, 4.89%. The NMR specra of 4a and 4b
change reversibly upon replacement of the solvent
from C6D6 to CDCl3 and vice versa.
3.3. Preparation of 5
Among the related seven-coordinate Mo(II) complexes
with four P ligands [10], a dicarbonyl complex with diphos-
phine ligands [MoCl(CO)2(Me2PCH2CH2PMe2)2][PF6]
was fully characterized previously, which, by contrast,
has a monocapped trigonal–prismatic geometry with two
P–P–C basal planes together with the Cl ligand capping a
P4 face [11]. The structure of [MoCl(CO)2{o-C6H4(As-
Me2)2}2][I3] [12] was also crystallographically determined
to be monocapped trigonal–prismatic, while that of
(1) A mixture of 2 (96 mg, 0.11 mmol) and TolC„CH
(28 lL, 0.22 mmol) in toluene (10 cm3) was stirred
at 60 °C for 3 h. After cooling, the mixture was fil-
tered and hexane was added to the concentrated fil-
trate, affording 5a as green–brown solid (58 mg,
53% yield). 1H NMR (C6D6): d 11.37 (dt, J(H–
P) = 14.0, 5.2 Hz, 1H, HC„), 1.93 (s, 3H, Me).

T. Ohnishi et al. / Journal of Organometallic Chemistry 693 (2008) 269–277
275
31P{1H} NMR (C6D6): ꢀ10.2 (d, 1P, P1), 42.9 (d, 1P,
3.6. Preparation of 8
P4), 55.6 (dd, 1P, P2), 97.2 (s, 1P, P3); J(P1–P2) = 40,
J(P2–P4) = 162 Hz. Anal. Calc. for C55H50Cl2MoP4:
C, 65.95; H, 5.03. Found: C, 65.53; H, 5.11%.
(1) A mixture of 2 (93 mg, 0.10 mmol) and XyNC
(41 mg, 0.31 mmol) in toluene (15 cm3) was stirred
at room temperature for 1 h to give an orange sus-
pension. The reaction mixture was filtered off, and
the remaining solid was washed with ether and then
crystallized from CH2Cl2-hexane, yielding 8 as a red
crystalline solid (67 mg, 56% yield).
(2) Reaction of 2 (102 mg, 0.115 mmol) and TolC„CH
(15 lL, 0.121 mmol) in CH2Cl2 (5 cm3) at room tem-
perature for 24 h afforded 5b ꢁ 0.5CH2Cl2 as green
crystals after crystallization of the product from
CH2Cl2-hexane (63 mg, 52% yield). 1H NMR
(CDCl3): d 12.14 (m, 1H, HC„), 2.06 (s, 3H, Me).
31P{1H} NMR (CDCl3): 55.7 (m, 2P, P1 and P4),
94.0 (m, 2P, P2 and P3). Anal. Calc. for
(2) Reaction of 2 (93 mg, 0.10 mmol) and XyNC (41 mg,
0.31 mmol) in CH2Cl2 (6 cm3) afforded rapidly an
orange solution. After 15 min, ether was added to a
concentrated product solution, giving 8 as a red crys-
talline solid (70 mg, 61% yield). IR (KBr): 2057sh,
C55.5H51Cl3MoP4: C, 63.84; H, 4.92. Found: C,
64.12; H, 4.99%.
1989 (mN„C) cmꢀ1. H NMR (CDCl3): d 1.06, 1.65
1
(s, 6H each, Me). 31P{1H} NMR (CDCl3): 61.8 (m,
2P, P1 and P4), 93.6 (m, 2P, P2 and P3). Anal. Calc.
for C64H60Cl2MoN2P4 requires C, 66.96; H, 5.27;
N, 2.44. Found: C, 67.30; H, 5.52; N, 2.14%.
3.4. Preparation of 6
(1) Reaction of 2 (68 mg, 0.071 mmol) and MeC„CPh
(29 lL, 0.23 mmol) in toluene (7 cm3) at 60 °C for
12 h afforded a red–orange product solution. Crys-
tallization of the product from toluene–hexane gave
6a as yellow–brown crystalline solid (38 mg, 53%
yield). 1H NMR (C6D6): d 1.60 (s, 3H, Me).
31P{1H} NMR (C6D6): ꢀ10.1 (m, 1P, P1), 46.7–
47.0 (m, 2P, P4 and P2), 93.8 (s, 1P, P3). Anal. Calc.
for C55H50Cl2MoP4: C, 65.95; H, 5.03. Found: C,
65.97; H, 5.25%.
(2) From the reaction of 2 (98 mg, 0.11 mmol) and
MeC„CPh (28 lL, 0.22 mmol) in CH2Cl2
(5 cm3) at room temperature for 20 h, followed
by crystallization from CH2Cl2-hexane, 6b ꢁ
0.5CH2Cl2 was obtained as a dark green solid
(53 mg, 46% yield). 1H NMR (CDCl3): d 1.79
(s, 3H, Me). 31P{1H} NMR (CDCl3): 53.5 (m,
2P, P1 and P4), 93.1 (m, 2P, P2 and P3). Anal.
Calc. for C55.5H51Cl3MoP4: C, 63.84; H, 4.92.
Found: C, 63.26; H, 4.88%.
3.7. Preparation of 80
A mixture of 8 (34 mg, 0.030 mmol) and KPF6 (17 mg,
0.092 mmol) in CH2Cl2 (7 cm3) was stirred at room temper-
ature for 24 h and then filtered. Addition of ether to the
concentrated filtrate afforded 80 ꢁ 0.5CH2Cl2 (23 mg, 60%
yield). Anal. Calc. for C64.5H61Cl2F6MoN2P5: C, 59.60;
H, 4.73; N, 2.16. Found: C, 60.38; H, 4.72; N, 2.06%. Sin-
gle crystals for X-ray diffraction were grown from
ClCH2CH2Cl-ether.
3.8. Preparation of 9
A solution of 2 (115 mg, 0.130 mmol) in CH2Cl2
(10 cm3) was stirred under a CO atmosphere for 1 h at
room temperature. Addition of hexane to the concentrated
product solution afforded 9 ꢁ 0.5CH2Cl2 as a red–brown
solid (72 mg, 58% yield). The reaction conducted in toluene
also afforded 9 in comparable isolated yield. IR (KBr):
1793 (mC„O) cmꢀ1 31P{1H} NMR (CDCl3): d 59.9 (m,
.
3.5. Preparation of 7
2P, P1 and P4), 96.0 (m, 2P, P2 and P3). Complex 9 dis-
solved in C6D6 showed the analogous NMR spectra. Anal.
Calc. for C47.5H43Cl3MoOP4: C, 59.67; H, 4.53. Found: C,
59.74; H, 4.74%. Single crystals for X-ray diffraction were
grown from CH2Cl2–C6H6–hexane.
A mixture of 2 (92 mg, 0.10 mmol) and XyNC (14 mg,
0.11 mmol) in toluene (15 cm3) was stirred at room temper-
ature for 10 min. Addition of hexane to the resultant red–
brown solution deposited an orange solid, which was fil-
tered off, washed with ether, and then crystallized from
CH2Cl2-hexane, yielding 7 as red crystals (53 mg, 50%
3.9. Preparation of 10
1
yield). IR (KBr): 2026 (mN„C) cmꢀ1. H NMR (CDCl3):
d 1.89 (s, 6H, Me). 31P{1H} NMR (CDCl3): 55.6 (ddd,
1P, P1), 79.8 (ddd, 1P, P4), 103.7 (ddd, 1P, P2), 127.7
(ddd, 1P, P3); J(P1–P2) = 64, J(P1–P3) = 27, J(P1–
P4) = 29, J(P2–P3) = 72, J(P2–P4) = 9, J(P3–P4) = 3 Hz.
Complex 7 dissolved in C6D6 showed the analogous
NMR spectra. Anal. Calc. for C55H51Cl2MoNP4: C,
64.97; H, 5.06; N, 1.38. Found: C, 65.11; H, 5.18; N,
1.27%.
(1) A mixture of 9 (51 mg, 0.056 mmol) and XyNC
(15 mg, 0.11 mmol) in CH2Cl2 (10 cm3) was stirred
at room temperature for 20 h. Addition of ether to
a
concentrated product solution afforded 10a ꢁ
0.5CH2Cl2 as an yellow–brown solid (34 mg, 55%
yield). IR (KBr): 2089 (mN„C), 1872 (mC„O) cmꢀ1
.
1H NMR (CDCl3): d 0.86 (s, 6H, Me). 31P{1H}
NMR (CDCl3): 61.1 (m, 2P, P1 and P4), 90.7 (m,

276
T. Ohnishi et al. / Journal of Organometallic Chemistry 693 (2008) 269–277
2P, P2 and P3). Anal. Calc. for C56.5H52Cl3MoNOP4:
C, 62.42; H, 4.82; N, 1.29. Found: C, 63.02; H, 4.67;
N, 1.31%.
C56.8H52.6Cl2.6F6MoNOP5: C, 55.82; H, 4.34; N,
1.15. Found: C, 55.69; H, 4.47; N, 1.08%. Preliminary
X-ray analysis was conducted by using the crystal
10b0 ꢁ 3CH2Cl2 deposited from the reaction mixture,
which was mounted without separation from the
mother liquor.
(2) A mixture of 7 (36 mg, 0.035 mmol) in CH2Cl2
(5 cm3) was stirred under CO for 90 min. Addition
of ether to a concentrated product solution gave a
mixture of 10a ꢁ 0.5CH2Cl2 and 10b ꢁ 0.5CH2Cl2 as
an yellow–brown solid (21 mg, 54% yield). The ratio
of 10a and 10b in the reaction mixture was 4:5 from
the NMR criteria. 10b ꢁ 0.5CH2Cl2: IR (KBr): 2050
3.10. X-ray crystallography
(mN„C), 1844 (mC„O) cmꢀ1
.
1H NMR (CDCl3): d
A single crystal of 7 was sealed in a glass capillary under
argon, while those of 80 ꢁ 1.7 C2H4Cl2 ꢁ 0.3(C2H5)2O and
9 ꢁ 1.15C6H6 ꢁ 0.3C6H14 ꢁ 0.12CH2Cl2 were sealed in glass
capillaries together with the mother liquor of crystalliza-
tion. On the other hand, the crystals of 10a0 ꢁ 1.5CH2Cl2
and 10b0 ꢁ 3CH2Cl2 were mounted on cryoloops with
mother liquor mixed with Paratone oil. Diffraction studies
were done by a Rigaku AFC7R four-circle diffractometer
for 7 or a Mercury-CCD diffractometer for others,
equipped with a graphite-monochromatized Mo Ka source
at 20 °C for 7, 80 and 9 or ꢀ160 °C for 10a0 and 10b0.
Details are listed in Table 5 except for those of 10b0, for
which only the preliminary results were available due to
the poor quality of the crystals. For 10b0 ꢁ 3CH2Cl2, for-
mula: C59H57Cl7F6MoNOP5, fw: 1409.08, space group:
1.58 (s, 6H, Me). 31P{1H} NMR (CDCl3): 75.6 (m,
2P, P1 and P4), 92.7 (m, 2P, P2 and P3). For a mixture
of 10a ꢁ 0.5CH2Cl2 and 10b ꢁ 0.5CH2Cl2: Anal. Calc.
for C56.5H52Cl3MoNOP4: C, 62.42; H, 4.82; N,
1.29. Found: C, 62.26; H, 4.94; N, 1.10%.
(3) A mixture of 10a (30 mg, 0.029 mmol) and KPF6
(17 mg, 0.092 mmol) in CH2Cl2 (6 cm3) was stirred
at room temperature for 24 h and then filtered. Addi-
tion of ether to the concentrated filtrate afforded 10a0
(23 mg, 69% yield). The X-ray analysis was carried
out by using the crystals 10a0 ꢁ 1.5CH2Cl2 present in
this mixture without separation from the mother
liquor.
(4) A solution of 10a0 (15 mg) in ClCH2CH2Cl (6 cm3)
was heated to reflux for 2 h and the resultant mixture
was dried up. Crystallization of the residue from
CH2Cl2-hexane gave crystals of 10b0 (10 mg). The
1H NMR spectrum of this crystals after drying in
vacuo suggested the presence of 0.8 equiv of solvating
CH2Cl2 molecule. 10b0 ꢁ 0.8CH2Cl2: Anal. Calc. for
˚
P21/n (no. 14), a: 20.45(1), b: 11.455(6), c: 25.88(1) A, b:
3
˚
93.530(3)°, V: 6052(5) A , Z: 4, R1 = 0.0805 for 4531 reflec-
tions of I > 2r(I); wR2 = 0.246 for 13811 observed
reflections.
Data collection were performed by using the WinAFC
(for 7) or CrystalClear (for others) program package [14].
Table 5
Crystal data for 7, 80, 9, and 10a0
7
80 ꢁ 1.7C2H4Cl2 ꢁ 0.3(C2H5)2O 9 ꢁ 1.15C6H6 ꢁ 0.3C6H14 ꢁ 0.12CH2Cl2 10a0 ꢁ 1.5CH2Cl2
Formula
Fw
C55H51Cl2MoNP4 C68.6H69.8Cl4.4F6MoN2O0.3P5 C55.8H53.32Cl2.24MoOP4
C57.5H54Cl4F6MoNOP5
1281.68
1016.74
P21/c (No. 14)
16.351(4)
11.152(6)
27.658(4)
90
105.05(1)
90
4870(3)
4
1447.91
P212121 (No. 19)
11.724(1)
22.116(2)
26.634(3)
90
90
90
6906(1)
4
1039.20
ꢀ
Space group
P1 (No. 2)
P21/n (No. 14)
20.878(5)
25.347(6)
23.361(6)
90
110.819(1)
90
11555(5)
8
˚
a (A)
18.941(2)
22.005(1)
22.280(2)
61.509(3)
80.630(4)
76.313(4)
7916(1)
6
˚
b (A)
˚
c (A)
a (°)
b (°)
c (°)
3
˚
V (A )
Z
qcalc (g cmꢀ3
)
1.387
1.393
1.308
1.473
Crystal size (mm3)
0.40 ꢂ 0.15 ꢂ 0.10 0.40 ꢂ 0.15 ꢂ 0.05
0.40 ꢂ 0.35 ꢂ 0.15
0.40 ꢂ 0.30 ꢂ 0.05
Number of unique reflections
Number of data with I > 2r(I) 4807
11173
15778
8018
36102
26381
22442
11233
Number of variables
Transmission factor
R1a
619
841
1766
1553
0.841–0.947
0.0610
0.0686b
1.048d
0.730–0.974
0.0558
0.154c
1.008e
0.751–0.925
0.0529
0.150c
1.034e
0.824–0.970
0.0624
0.185c
1.004e
wRb or wRc2
GOFd,e
P
P
a
R1 = kFo| ꢀ |Fck/ |Fo| (I > 2r(I)).
P
P
b
c
wR = |w(|Fo| ꢀ |Fck)/ w|Fo|.
P
P
2
2 1=2
wR2 ¼ ½ ðwðF 2o ꢀ F 2c Þ Þ= wðF 2oÞ ꢃ ðI > 2rðIÞÞ.
P
d
e
GOF = |w(|Fo| ꢀ |Fck)/{(no. observed) ꢀ (no. variables)}.
P
GOF = [ w(|Fo| ꢀ |Fc|)2/{(no. observed) ꢀ (no. variables)}]1/2
.

T. Ohnishi et al. / Journal of Organometallic Chemistry 693 (2008) 269–277
277
[2] H. Seino, C. Arita, M. Hidai, Y. Mizobe, J. Organomet. Chem. 658
(2002) 106.
[3] T. Ohnishi, H. Seino, M. Hidai, Y. Mizobe, J. Organomet. Chem.
690 (2005) 1140.
All data were corrected for Lorentz and polarization effects
as well as absorption (w-scans for 7 and multi-scans for
others).
Structure solution and refinements were conducted by
using the Crystal Structure program package [15]. The
positions of non-hydrogen atoms were determined by Patt-
erson methods (PATTY) [16] and subsequent Fourier syn-
thesis (DIRDIF99) [17], which were refined with anisotropic
thermal parameters by full-matrix least-squares techniques.
Hydrogen atoms were placed at the calculated positions
and included at the final stages of the refinements with
fixed parameters.
[4] H. Seino, D. Watanabe, T. Ohnishi, C. Arita, Y. Mizobe, Inorg.
Chem. 46 (2007) 4784.
[5] D. Watanabe, S. Gondo, H. Seino, Y. Mizobe, Organometallics 26
(2007) 4909.
[6] F. Niikura, H. Seino, Y. Mizobe, unpublished results.
[7] R. Ellis, R.A. Henderson, A. Hills, D.L. Hughes, J. Organomet.
Chem. 333 (1987) C6.
[8] Y. Wang, J.J.R. Frau´sto Da Silva, A.J.L. Pombeiro, M.A. Pellingh-
elli, A. Tiripicchio, R.A. Henderson, R.L. Richards, J. Chem. Soc.,
Dalton Trans. 1183 (1995).
[9] H. Seino, D. Nonokawa, G. Nakamura, Y. Mizobe, M. Hidai,
Organometallics 19 (2000) 2002.
[10] (a) M.G.B. Drew, Prog. Inorg. Chem. 23 (1977) 67;
(b) M. Melnik, P. Sharrock, Coord. Chem. Rev. 65 (1985)
49.
[11] L.K. Fong, J.R. Fox, B.M. Foxman, N.J. Cooper, Inorg. Chem. 25
(1986) 1880.
[12] M.G.B. Drew, J.D. Wilkins, J. Chem. Soc., Dalton Trans. 2664
(1973).
Supplementary material
CCDC 659213, 659214, 659215 and 659216 contain the
supplementary crystallographic data for 7, 80, 9 and 10a0.
These data can be obtained free of charge from The Cam-
bridge Crystallographic Data Centre via www.ccdc.cam.a-
c.uk/data_request/cif.
´
[13] M. Jimenez-Tenorio, M.C. Puerta, P. Valerga, D.L. Hughes, J.
Chem. Soc., Dalton Trans. 2431 (1994).
[14] CrystalClear 1.3.5: Rigaku Corporation, 1999. CrystalClear Software
User’s Guide, Molecular Structure Corporation, 2000: J.W. Pflug-
rath, Acta Crystallogr. D 55 (1999) 1718.
[15] CrystalStructure 3.8: Crystal Structure Analysis Package, Rigaku and
Rigaku/MSC, 2000–2002. CRYSTALS Issue 10: D.J. Watkin, C.K.
Prout, J.R. Carruthers, P.W. Betteridge, Chemical Crystallography
Laboratory: Oxford, UK.
[16] PATTY: P.T. Beurskens, G. Admiraal, G. Beurskens, W.P. Bosman,
S. Garcia-Granda, R.O. Gould, J.M.M. Smits, C. Smykall, The
DIRDIF program system; Technical Report of the Crystallography
Laboratory: University of Nijmegen, Nijmegen, The Netherlands,
1992.
Acknowledgements
This work was supported by Grant-in-Aid for Scientific
Research on Priority Areas (No. 18065005, ‘‘Chemistry of
Concerto Catalysis”) from the Ministry of Education, Cul-
ture, Sports, Science and Technology, Japan and by
CREST of JST (Japan Science and Technology Agency).
References
[17] DIRDIF99: P.T. Beurskens, G. Admiraal, G. Beurskens, W.P. Bosman,
R. de Gelder, R. Israel, J.M.M. Smits, The DIRDIF99 program system;
Technical Report of the Crystallography Laboratory: University of
Nijmegen, Nijmegen, The Netherlands, 1999.
[1] (a) C. Arita, H. Seino, Y. Mizobe, M. Hidai, Chem. Lett. 28 (1999)
611;
(b) C. Arita, H. Seino, Y. Mizobe, M. Hidai, Bull. Chem. Soc. Jpn.
74 (2001) 561.