2,2′:6′,2″-Terpyridine complexes of molybdenum(II) and tungsten(II). X-ray crystal structures of [MoI(CO)(terpy)(η2-PhC2Ph)]I and [WI(terpy)(η2-PhC2Ph)2]I·CDCl 3

Article abstract of DOI:10.1016/S0022-328X(00)00234-5

Equimolar quantities of [MI₂(CO)₃(NCMe)₂] (M = Mo or W) and terpy (terpy = 2,2′:6′,2″-terpyridine) react in CH₂Cl₂ at room temperature to give the cationic complexes [MI(CO)₃(terpy)]I (1 and 2) in high yield. Treatment of [MoCl(GeCl₃)(CO)₃(NCMe)(PPh₃)] with one equivalent of terpy affords [Mo(GeCl₃)(CO)₂(PPh₃)(terpy)]Cl (3) in good yield. Reaction of [MI₂(CO)(NCMe)(η²-RC₂R)₂](M = Mo, W; R = Ph; for M = W only, R = Me) with an equimolar quantity of terpy in CH₂Cl₂ at room temperature gives the cationic complexes [MI(CO)(terpy)(η²-RC₂R)]I (4 and 5) or the crystallographically characterised cationic complex [WI(terpy)(η²-PhC₂Ph)₂]I (6). Equimolar quantities of [WI(CO)(terpy)(η²-MeC₂Me)]I(5) and Na[BPh₄] react to give the anion-exchanged product, [WI(CO)(terpy)(η²-MeC₂Me)][BPh₄] (7). The X-ray crystal structure of [MoI(CO)(terpy)(η²-PhC₂Ph)]I shows the three nitrogen atoms of the terpy bonded in the equatorial plane of an octahedron together with the carbonyl group. The iodo and diphenylacetylene ligands are mutually trans- to each other in the axial positions. The structure of [WI(terpy)(η²-PhC₂Ph)₂]I·CDCl ₃ (6) has a distorted octahedral geometry, with the three nitrogen atoms of the terpy ligand in a mer-configuration, with two cis-and parallel diphenylacetylene ligands and an iodo group occupying the other three mer-sites.

Full text of DOI:10.1016/S0022-328X(00)00234-5

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 604 (2000) 191–196
2,2%:6%,2¦-Terpyridine complexes of molybdenum(II) and
tungsten(II). X-ray crystal structures of
[MoI(CO)(terpy)(h2-PhC2Ph)]I and
[WI(terpy)(h2-PhC2Ph)2]I·CDCl3
Nicholas Aimeloglou a, Paul K. Baker a,*, Michael G.B. Drew b, Bjoern Glaeser a,
Fiona Holland a, Margaret M. Meehan a
a Department of Chemistry, Uni6ersity of Wales, Bangor, Gwynedd LL57 2UW, UK
b Department of Chemistry, Uni6ersity of Reading, Whiteknights, Reading RG6 6AD, UK
Received 19 February 2000; accepted 16 April 2000
Abstract
Equimolar quantities of [MI2(CO)3(NCMe)2] (M=Mo or W) and terpy (terpy=2,2%:6%,2¦-terpyridine) react in CH2Cl2 at room
temperature to give the cationic complexes [MI(CO)3(terpy)]I (1 and 2) in high yield. Treatment of
[MoCl(GeCl3)(CO)3(NCMe)(PPh3)] with one equivalent of terpy affords [Mo(GeCl3)(CO)2(PPh3)(terpy)]Cl (3) in good yield.
Reaction of [MI2(CO)(NCMe)(h2-RC2R)2](M=Mo, W; R=Ph; for M=W only, R=Me) with an equimolar quantity of terpy
in CH2Cl2 at room temperature gives the cationic complexes [MI(CO)(terpy)(h2-RC2R)]I (4 and 5) or the crystallographically
characterised cationic complex [WI(terpy)(h2-PhC2Ph)2]I (6). Equimolar quantities of [WI(CO)(terpy)(h2-MeC2Me)]I(5) and
Na[BPh4] react to give the anion-exchanged product, [WI(CO)(terpy)(h2-MeC2Me)][BPh4] (7). The X-ray crystal structure of
[MoI(CO)(terpy)(h2-PhC2Ph)]I shows the three nitrogen atoms of the terpy bonded in the equatorial plane of an octahedron
together with the carbonyl group. The iodo and diphenylacetylene ligands are mutually trans- to each other in the axial positions.
The structure of [WI(terpy)(h2-PhC2Ph)2]I·CDCl3 (6) has a distorted octahedral geometry, with the three nitrogen atoms of the
terpy ligand in a mer-configuration, with two cis-and parallel diphenylacetylene ligands and an iodo group occupying the other
three mer-sites. © 2000 Elsevier Science S.A. All rights reserved.
Keywords: Molybdenum; Tungsten; Crystal structure; Terpyridine; Alkyne; Cationic complexes
1. Introduction
PF6, SbF6), which has been crystallographically charac-
terised for X=Br, X%=SbF6.
Although there are many complexes of molybdenum
and tungsten containing 2,2%-bipyridine ligands, very
few molybdenum and tungsten complexes are known
which contain 2,2%:6%,2¦-terpyridine [1–8]. Two exam-
ples include the terpy complexes [Mo(CO)4(terpy)] [9]
and [Mo(terpy)2] [10], with the terpy coordinated in
bidentate and tridentate modes, respectively. Very re-
cently, Daniel et al. [11] have described the synthesis of
the seven-coordinate molybdenum(II) complexes
[MoX(CO)(h4-C7H8)(terpy)]X% (X=Br, I; X%=Br, I,
In 1986 [12], we described the synthesis of the new
highly
versatile
seven-coordinate
complexes,
[MI2(CO)3(NCMe)2] (M=Mo and W). In 1988, we
described the reactions of [WI2(CO)3(NCMe)2] with
RC2R (R=Me, Ph) to give the crystallographically
characterised
tungsten
bis(alkyne)
complexes
[WI2(CO)(NCMe)(h2-RC2R)2] [13]. More recently, the
related molybdenum complexes [MoI2(CO)(NCMe)(h2-
RC2R%)2] (R=R%=Me or Ph; R=Me, R%=Ph) [14]
have been prepared.
The reactions of [MI2(CO)(NCMe)(h2-RC2R)2]
(M=Mo and W) with 2,2%-bipyridine (bipy) are very
different. For example, reaction of equimolar quantities
* Corresponding author. Fax: +44-1248-370528.
E-mail address: chs018@bangor.ac.uk (P.K. Baker).
0022-328X/00/$ - see front matter © 2000 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(00)00234-5

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N. Aimeloglou et al. / Journal of Organometallic Chemistry 604 (2000) 191–196
Table 1
Physical and analytical data for complexes 1–7
Complex
Colour
Yield (%)
Analytical data, found (Calc.) (%)
C
H
N
1 [MoI(CO)3(terpy)]I
2 [WI(CO)3(terpy)]I
Black
68
73
53
85
74
85
76
32.3(32.4)
29.2(28.6)
49.0(48.8)
43.8(43.2)
32.3(31.9)
49.7(50.2)
56.5(55.9)
2.0(1.7)
1.6(1.5)
3.6(3.0)
2.5(2.4)
2.3(2.3)
3.3(3.0)
3.9(3.8)
6.6(6.3)
5.8(5.6)
5.4(4.9)
5.5(5.6)
5.6(5.6)
4.1(4.1)
4.4(4.4)
Brown/Black
Purple/Black
Brown
Green
Brown/Orange
Green
3 [Mo(GeCl3)(CO)2(PPh3)(terpy)]Cl
4 [MoI(CO)(terpy)(h2-PhC2Ph)]I
5 [WI(CO)(terpy)(h2-MeC2Me)]I
6 [WI(terpy)(h2-PhC2Ph)2]I
7 [WI(CO)(terpy)(h2-MeC2Me)][BPh4]
of [WI2(CO)(NCMe)(h2-MeC2Me)2] and bipy in the
presence of Na[BPh4] gives the crystallographically
characterised complex [WI(CO)(bipy)(h2-MeC2Me)2]-
likely that the trinitrogen donor ligand, terpy displaces
two acetonitrile ligands and an iodide from
[MI2(CO)3(NCMe)2] to give the cationic seven-coordi-
nate complexes, [MI(CO)3(terpy)]I (1) and (2). This was
confirmed by the IR spectra (Table 2), which have three
carbonyl bands in their spectra. In the complex
[Mo(GeCl3)(CO)2(PPh3)(terpy)]Cl (3), the cationic for-
mulation is confirmed by there being two carbonyl
bands in its IR spectrum (Table 2) and elemental
analysis results. Several unsuccessful attempts to grow
suitable single crystals for X-ray analysis were made.
The structures of halocarbonyl complexes of molybden-
[BPh4] [15]. Whereas,
a
similar reaction of
[MoI2(CO)(NCMe)(h2-MeC2Me)2] and bipy yields the
neutral mono(2-butyne) complex [MoI2(CO)(bipy)(h2-
MeC2Me)] [14]. In this paper, we describe the reactions
of [MI2(CO)3(NCMe)2] (M=Mo or W), [MoCl-
(GeCl3)(CO)3(NCMe)(PPh3)] and [MI2(CO)(NCMe)-
(h2-RC2R)2] (M=Mo, W; R=Me or Ph) with
2,2%:6%,2¦-terpyridine. The molecular structures of the
terpy complexes, [MoI(CO)(terpy)(h2-PhC2Ph)]I and
[WI(terpy)(h2-PhC2Ph)2]I·CDCl3 are also discussed.
Table 2
a
IR data (cm−1
)
for complexes 1–7
2. Results and discussion
Complex
w(CꢀO) (cm−1
)
w(CꢀC) (cm−1
)
2.1. Reactions of [MI2(CO)3(NCMe)2] (M=Mo or W)
and [MoCl(GeCl3)(CO)3(NCMe)(PPh3)] with
2,2%:6%,2¦-terpyridine
(1)
(2)
(3)
(4)
(5)
(6)
(7)
2010(s), 1937(s), 1849(s)
1958(s), 1925(s), 1902(m)
1944(s), 1870(s)
1967(s)
1922(s)
–
–
–
–
1602(w)
1602(w)
1600(w)
1602(w)
Equimolar quantities of [MI2(CO)3(NCMe)2] (M=
Mo or W) and terpy react in CH2Cl2 at room tempera-
ture to give the cationic complexes [MI(CO)3(terpy)]I
(1) and (2). A similar reaction of [MoCl(GeCl3)(CO)3-
(NCMe)(PPh3)] [16] with one equivalent of terpy gives
[Mo(GeCl3)(CO)2(PPh3)(terpy)]Cl (3) in good yield.
Complexes 1–3 were characterised by elemental analy-
1922(s)
a Spectra recorded in CHCl3 as thin films between NaCl plates;
m=medium, s=strong, w=weak.
Table 3
1H-NMR data a for complexes 1–7
1
sis (C, H and N) (Table 1), IR and H-NMR spec-
troscopy (Tables 2 and 3). Complexes 1–3 are only
moderately soluble in CH2Cl2 and CHCl3, and totally
insoluble in diethyl ether and hydrocarbon solvents.
The molybdenum (GeCl3) complex 3, is less soluble
than the iodo-complexes 1 and 2. Complexes 1–3 are
air-sensitive in solution, but can be stored under dini-
trogen in the solid state for several days without de-
composition. We have previously shown [17], that
reactions of [MI2(CO)3(NCMe)2] (M=Mo or W) with
equimolar amounts of PPh3 give [MI2(CO)3(NCMe)-
(PPh3)], which react in situ with one equivalent of
Complex
1H-NMR (l) ppm
1
2
3
4
7.5“9.2 (m, terpy-H)
7.5“9.0 (m, terpy-H)
7.5“9.0 (m, 11H, terpy-H); 7.2“7.4 (m, 15H, Ph)
8.8 (m,2H,terpy-N-CH); 8.0“8.2 (m,4H,terpy-H),
7.3“7.5(m,15H,terpy-H, +Ph)
9.0 (d, 2H, terpy N-CH); 7.9“8.1(m, 4H, terpy-H);
7.5 (m, 5H, terpy-H); 3.0(s, 6H, C2Me)
8.8 (m, 2H, terpy-N-CH), 8.0“8.2(m, 4H, terpy-H);
6.9“7.6(brm, 25H, terpy-H+Ph.)
5
6
7
7.5“9.1 (m,11H, terpy-H); 6.8“7.4 (m, 20H, BPh4);
3.0(s, 6H, C2Me)
/
/
N N (N N=2,2%-bipy or 1,10-phen) to give the cationic
complexes, [MI(CO)3(PPh3)(N N)]I. Hence, it is
a Spectra recorded in CDCl3 (+25°C) referenced to SiMe4.
/

N. Aimeloglou et al. / Journal of Organometallic Chemistry 604 (2000) 191–196
193
Suitable single crystals of [MoI(CO)(terpy)(h2-
PhC2Ph)]I (4) were grown from a concentrated CDCl3
solution of 4 at room temperature. The structure of 4 is
shown in Fig. 1, together with the atomic numbering
scheme.
The
structure
contains
discrete
[MoI(CO)(terpy)(h2-PhC2Ph)]I cations and iodide an-
ions. The cation is shown in Fig. 1 and selected bond
,
lengths (A) and angles (°) are presented in Table 4. The
metal environment can best be considered as a distorted
octahedron with the diphenylacetylene in an axial posi-
tion occupying one site trans to the iodide. The terpy
ligand is tridentate occupying the equatorial plane to-
gether with a carbonyl group. The dimensions from the
metal atom are as expected; the bond to the central
,
nitrogen, N(21) atom is at 2.10 (2) A, shorter than the
bonds to the two outer nitrogen atoms N(11) and
,
N(31){2.23(2), 2.17(2) A}, respectively. These distances
are comparable with the values of 2.230 (4), 2.158(4)
4
+
,
and 2.208 (5) A found in [MoBr(CO)(terpy)(h -C7H8)] ,
[11]. Suitable single crystals of 6 were grown from a
concentrated CDCl3 solution of 6 in a NMR tube. The
asymmetric unit of 6 consists of a discrete cation and
anion together with a solvent deuterated chloroform
molecule. The structure of the [WI(terpy)(h2-
PhC2Ph)2]+ cation is shown in Fig. 2, together with the
atomic numbering scheme, and the dimensions in the
coordination sphere are given in Table 4. The environ-
ment of the metal coordination sphere can also be
considered to be a distorted octahedron with the two
PhC2Ph ligands occupying single octahedral sites. The
Wꢁterpy distances are WꢁN(11){2.24(2)},WꢁN(21)-
Fig. 1. The structure of the cation in (4), together with ellipsoids
shown at 30% probability.
um(II) and tungsten(II) most commonly have capped
octahedral geometry [18–22], which may be the geo-
metry of complexes 1–3.
2.2. Reactions of [MI2(CO)(NCMe)(p2-RC2R%)2] with
2,2%:6%,2¦-terpyridine
Equimolar quantities of [MI2(CO)(NCMe)(h2-
RC2R)2] (M=Mo, W; R=Ph; M=W only, R=Me)
[13,14] and terpy react in CH2Cl2 at room temperature
to give the cationic complexes [MI(CO)(terpy)(h2-
RC2R)]I (4 and 5), and the bis(alkyne) complex
[WI(terpy)(h2-PhC2Ph)2]I(6) in good yield. Complexes
4–6 have been characterised by elemental analysis (C,
,
{2.21(3)}, WꢁN(31){2.37(3)} A, with the central nitro-
gen trans to a PhC2Ph ligand. The plane of the three-
membered WCC ring makes an angle of 25.9° with the
terpy ligand plane. The other PhC2Ph ligand is trans to
the iodide. There are very few examples of structures in
the Cambridge Crystallographic Database containing
the Mo(terpy) moiety, and indeed none containing the
W(terpy) moiety. Of the structures containing the
Mo(terpy) moiety, the only one related to the present
structure is the aforementioned [MoBr(CO)(terpy)(h4-
norbornadiene)][SbF6] [11], where the carbonyl group is
also trans-to the central nitrogen of the terpy in the
equatorial plane and the bromide is trans- to the nor-
bornadiene. There are related structures containing the
bipyridyl ligand viz [WI(CO)(bipy)(h2-MeC2Me)2]-
[BPh4] [15], [WCl(CO)(bipy)(h2-MeC2Me)2]I [23], and
where in both cations the equatorial plane is occupied
by two mutually cis 2-butyne ligands, and the bipy
ligand. Again the halides are trans- to the carbonyl
groups.
1
H and N) (Table 1), IR (Table 2) and H-NMR spec-
troscopy (Table 3), and complexes 4 and 6 by X-ray
crystallography. The cationic complexes 4–5 are solu-
ble in polar chlorinated solvents such as CH2Cl2 and
CHCl3, but totally insoluble in diethyl ether, whereas
the non-carbonyl containing cationic complex 6 is also
soluble in CH2Cl2 and CHCl3, but also slightly soluble
in diethyl ether. Complexes 4–6 are all air-sensitive in
solution, however they can all be stored under nitrogen
in the solid state for several days without significant
decomposition. The cationic nature of [WI(CO)(terpy)-
(h2-MeC2Me)]I (5), was confirmed by the reaction of 5
with an equimolar amount of Na[BPh4] in acetonitrile
to give the anion exchanged product, [WI(CO)(terpy)-
(h2-MeC2Me)][BPh4] (7), which has been fully charac-
terised (see Tables 1–3). The cationic nature of these
complexes was also confirmed by the X-ray crystal
structure determinations of [MoI(CO)(terpy)(h2-
PhC2Ph)]I (4) and [WI(terpy)(h2-PhC2Ph)2]I·CDCl3(6).
In order to see if the complex, [MoI(CO)(terpy-
N,N%)(h2-PhC2Ph)2]I, is initially formed which has terpy
attached in a bidentate manner, the reaction of
[MoI2(CO)(NCMe)(h2-PhC2Ph)2] with one equivalent

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N. Aimeloglou et al. / Journal of Organometallic Chemistry 604 (2000) 191–196
Table 4
of terpy was followed by IR spectroscopy. Equimolar
quantities of the complex, [MoI2(CO)(NCMe)(h2-
PhC2Ph)2] and terpy in CHCl3 gave after 30 s an IR
spectrum which showed all the [MoI2(CO)(NCMe)(h2-
PhC2Ph)2] {w(CO)=2080 cm−1} had disappeared, and
only a carbonyl band at 1967 cm−1, due to the crystal-
lographically characterised product, [MoI(CO)(terpy)-
(h2-PhC2Ph)]I (4) was observed. Refluxing a CHCl3
solution of 4 in the presence of dissolved PhC2Ph for 12
h surprisingly did not give the carbonyl displaced
product, [MoI(terpy)(h2-PhC2Ph)2]I, related to the crys-
tallographically characterised tungsten product,
[WI(terpy)(h2-PhC2Ph)2]I (6), which was the only
product observed from the reaction of equimolar
amounts of [WI2(CO)(NCMe)(h2-PhC2Ph)2] and terpy
in CH2Cl2.
,
Selected bond lengths (A) and angles (°) for 4
Mo(1)ꢁC(20)
Mo(1)ꢁC(71)
Mo(1)ꢁC(81)
Mo(1)ꢁN(21)
Mo(1)ꢁN(31)
Mo(1)ꢁN(11)
Mo(1)ꢁI(2)
1.98(2)
1.99(2)
2.04(2)
2.10(2)
2.17(2)
2.23(2)
2.873(3)
C(20)ꢁMo(1)ꢁC(71)
C(20)ꢁMo(1)ꢁC(81)
C(71)ꢁMo(1)ꢁC(81)
C(20)ꢁMo(1)ꢁN(21)
C(71)ꢁMo(1)ꢁN(21)
C(81)ꢁMo(1)ꢁN(21)
C(20)ꢁMo(1)ꢁN(31)
C(71)ꢁMo(1)ꢁN(31)
C(81)ꢁMo(1)ꢁN(31)
N(21)ꢁMo(1)ꢁN(31)
C(20)ꢁMo(1)ꢁN(11)
C(71)ꢁMo(1)ꢁN(11)
C(81)ꢁMo(1)ꢁN(11)
N(21)ꢁMo(1)ꢁN(11)
N(31)ꢁMo(1)ꢁN(11)
C(20)ꢁMo(1)ꢁI(2)
C(71)ꢁMo(1)ꢁI(2)
C(81)ꢁMo(1)ꢁI(2)
N(21)ꢁMo(1)ꢁI(2)
N(31)ꢁMo(1)ꢁI(2)
N(11)ꢁMo(1)ꢁI(2)
115.2(8)
77.7(8)
37.6(7)
160.7(7)
83.8(7)
121.3(7)
102.2(7)
88.4(6)
97.7(7)
73.8(6)
104.5(7)
97.9(6)
107.2(8)
74.4(6)
146.6(6)
78.2(6)
165.6(5)
155.6(6)
82.6(4)
83.4(4)
82.8(4)
3. Conclusions
2,2%;6%,2¦-Terpyridine(terpy) reacts with [MI2(CO)3-
(NCMe)2], [MoCl(GeCl3)(CO)3(NCMe)(PPh3)] and
[MI2(CO)(NCMe)(h2-RC2R)2] to give a range of prod-
ucts, all of which have terpy coordinated in a tridentate
manner. It is interesting to note that two different
crystallographically characterised products, namely
[MoI(CO)(terpy)(h2-PhC2Ph)]I (4) and [WI(terpy)(h2-
PhC2Ph)2]I (6) are obtained from reactions of equimo-
lar amounts of [MI2(CO)(NCMe)(h2-PhC2Ph)2] and
terpy in CH2Cl2 at room temperature.
,
Selected bonds lengths (A) and angles (°) for 6
W(1)ꢁC(61)
W(1)ꢁC(71)
W(1)ꢁC(91)
W(1)ꢁC(81)
W(1)ꢁN(21)
W(1)ꢁN(11)
W(1)ꢁN(31)
W(1)ꢁI(2)
1.94(5)
2.08(5)
2.09(4)
2.09(3)
2.21(3)
2.24(2)
2.37(3)
2.888(4)
C(61)ꢁW(1)ꢁC(71)
C(61)ꢁW(1)ꢁC(91)
C(71)ꢁW(1)ꢁC(91)
C(61)ꢁW(1)ꢁC(81)
C(71)ꢁW(1)ꢁC(81)
C(91)ꢁW(1)ꢁC(81)
C(61)ꢁW(1)ꢁN(21)
C(71)ꢁW(1)ꢁN(21)
C(91)ꢁW(1)ꢁN(21)
C(81)ꢁW(1)ꢁN(21)
C(61)ꢁW(1)ꢁN(11)
C(71)ꢁW(1)ꢁN(11)
C(91)ꢁW(1)ꢁN(11)
C(81)ꢁW(1)ꢁN(11)
N(21)ꢁW(1)ꢁN(11)
C(61)ꢁW(1)ꢁN(31)
C(71)ꢁW(1)ꢁN(31)
C(91)ꢁW(1)ꢁN(31)
C(81)ꢁW(1)ꢁN(31)
N(21)ꢁW(1)ꢁN(31)
N(11)ꢁW(1)ꢁN(31)
C(61)ꢁW(1)ꢁI(2)
C(71)ꢁW(1)ꢁI(2)
C(91)ꢁW(1)ꢁI(2)
C(81)ꢁW(1)ꢁI(2)
N(21)ꢁW(1)ꢁI(2)
N(11)ꢁW(1)ꢁI(2)
N(31)ꢁW(1)ꢁI(2)
32.3(16)
87.6(18)
106.4(17)
95.1(15)
95.4(13)
35.1(12)
164.8(15)
162.1(15)
86.4(13)
88.0(9)
93.3(15)
119.9(14)
86.4(12)
120.1(9)
72.4(9)
4. Experimental
All reactions were carried out under an atmosphere
of dry nitrogen using standard Schlenk line techniques.
All chemicals were purchased from commercial sources
except for [MI2(CO)3(NCMe)2] (M=Mo or W) [12],
[MoCl(GeCl3)(CO)3(NCMe)(PPh3)] [16], [MI2(CO)-
(NCMe)(h2-RC2R)2] (M=Mo, W; R=Me, Ph)
[13,14], which were prepared by the published methods.
Elemental analyses were determined using a Carlo
Erba Elemental Analyser MOD 1108 (using helium as a
carrier gas). IR spectra were recorded on a Perkin–
Elmer 1600 FTIR spectrophotometer. The 1H-NMR
spectra were recorded on a Bruker AC 250 MHz NMR
spectrometer, and referenced to SiMe4.
122.2(16)
90.4(15)
111.4(13)
78.5(9)
73.0(9)
139.7(9)
99.1(14)
87.2(12)
162.7(10)
156.8(7)
83.0(7)
4.1. Preparation of [MoI(CO)3(terpy)]I (1)
The complex [MoI2(CO)3(NCMe)2] (0.305 g, 0.592
mmol) was dissolved in dry and degassed CH2Cl2 (30
cm3) with continuous stirring under a stream of dry
nitrogen and (0.138 g, 0.592 mmol) of terpy was added.
77.4(7)
78.5(6)

N. Aimeloglou et al. / Journal of Organometallic Chemistry 604 (2000) 191–196
195
g, 1.15 mmol). After stirring at r.t., under an atmo-
sphere of dry nitrogen for 24 h, followed by filtration
and removal of the solvent in vacuo gave the brown–
orange solid [WI(terpy)(h2-PhC2Ph)2]I (6). The complex
was recrystallised from CH2Cl2–Et2O at −17°C
(yield=1.02 g, 85%). Suitable single crystals for X-ray
crystallography of 6 were grown from a concentrated
CDCl3 solution of 6 in a NMR tube.
4.4. Preparation of [WI(CO)(terpy)(p2-MeC2Me)]
[BPh4] (7)
To a solution of [WI(CO)(terpy)(h2-MeC2Me)]I (0.57
g,0.76 mmol) in NCMe (25 cm3), Na[BPh4](0.26 g, 0.76
mmol) was added. After stirring for 24 h followed by
filtration and removal of the solvent in vacuo, the dark
green powder was redissolved in CH2Cl2 (30 cm3) and
filtered, and the solvent removed in vacuo to give a
dark green powder [WI(CO)(terpy)(h2-MeC2Me)]
[BPh4] (7) which was recrystallised twice from CH2Cl2
(yield=0.54 g, 76%).
Fig. 2. X-ray crystal structure of the cation in (6), together with the
atomic numbering scheme. Ellipsoids shown at 30% probability.
4.5. Crystal structure and analysis of 4 and 6
After stirring for 2 h, the mixture was filtered and the
solvent was removed in vacuo to give the black crys-
talline ionic solid, [MoI(CO)3(terpy)]I (1), which was
recrystallised from CH2Cl2 (yield=0.268 g, 68%).
In similar reactions of equimolar quantities of
Crystal data for 4 and 6 are given in Table 5.
Intensity data were collected with Mo–Ka radiation
using the MARresearch Image Plate system. The crys-
tals were positioned at 70 mm from the Image Plate. 95
frames were measured at 2° intervals with a counting
time of 2 min. Data analysis was carried out with the
XDS program [24].
The structures were solved using direct methods with
the SHELX86 program [25]. In 4 all non-hydrogen atoms
were refined with anisotropic thermal parameters. In 6
only the tungsten and iodine atoms were refined an-
isotropically. In both structures the hydrogen atoms
were included in geometric positions and given thermal
parameters equivalent at 1.2 times those of the atom to
which they were attached. The data for 6 was of poor
quality and constraints on thermal parameters for
atoms in rings proved necessary. Empirical absorption
corrections were carried out for both structures using
the DIFABS program [26]. The structures were refined
on F2 using the SHELX program [27].
[WI2(CO)3(NCMe)2],
[MoCl(GeCl3)(CO)3(NCMe)-
(PPh3)] and terpy gave the cationic complexes
[WI(CO)3(terpy)]I (2) and [Mo(GeCl3)(CO)2(PPh3)-
(terpy)]Cl (3), respectively. For physical and analytical
data see Table 1.
4.2. Preparation of [MoI(CO)(terpy)(p2-PhC2Ph)]I (4)
To a solution of [MoI2(CO)(NCMe)(h2-PhC2Ph)2]
(0.5 g, 0.06 mmol) in CH2Cl2 (30 cm3), terpy (0.15g,
0.06 mmol) was added. After stirring for 17 h a green
precipitate was allowed to settle, and the brown solu-
tion was removed by syringe and the solvent removed
in vacuo to give the brown solid, [MoI(CO)(terpy)(h2-
PhC2Ph)]I (4) which was recrystallised from CHCl3 at
−17°C to give single crystals suitable for X-ray crystal-
lography (yield=0.41 g 85%).
In a similar reaction of equimolar quantities of
[WI2(CO)(NCMe)(h2-MeC2Me)2] and terpy in CH2Cl2
at room temperature (r.t.) gave [WI(CO)(terpy)(h2-
MeC2Me)]I (5). For physical and analytical data see
Table 1.
5. Supplementary material
For complexes 4 and 6, tables of remaining molecu-
lar dimensions not included in this paper, anisotropic
and isotropic thermal parameters, and hydrogen coor-
dinates are available. Ordering information is given on
any current masthead page. The data have been lodged
with the Cambridge Crystallographic Database; CCDC
nos. 142074 and 142075 for 4 and 6, respectively.
Copies of this information can be obtained free of
4.3. Preparation of [WI(terpy)(p2-PhC2Ph)2]I (6)
To a solution of [WI2(CO)(NCMe)(h2-PhC2Ph)2] (1.0
g, 1.15 mmol) in CH2Cl2 (30 cm3) was added terpy (0.27

196
N. Aimeloglou et al. / Journal of Organometallic Chemistry 604 (2000) 191–196
Table 5
Crystal data for 4 and 6
EPSRC and the University of Reading for the purchase
of the Image Plate System. We also thank A.W. Johans
for help with the crystallographic work.
Compound
4
6
Empirical formula
C
30H20I2MoN3O C44H32C13I2N3W
Molecular weight
Temperature (K)
788.23
293(2)
1146.72
293(2)
References
,
Wavelength (A)
Crystal system
0.71073
Monoclinic
P21/n, 4
0.71073
Triclinic
[1] P. Legzdins, J.C. Oxley, Inorg. Chem. 23 (1984) 1053.
[2] J.A. Connor, E.J. James, J. Organomet. Chem. 325 (1987) 181.
[3] J. Granifo, M.E. Vargas, J. Organomet. Chem. 408 (1991) 357.
[4] S. Sto¨tzel, K. Wieghardt, B. Nuber, Inorg. Chem. 32 (1993)
2128.
[5] C.-H. Lai, C.-H. Cheng, W.-C. Chou, S.-L. Wang, Organometal-
lics 12 (1993) 1105.
[6] M. Handa, M. Mikuriya, R. Nukada, H. Matsumoto, K.
Kasuga, Bull. Chem. Soc. Jpn. 67 (1994) 3125.
[7] E.S. Dodsworth, A.A. Vlcˇek, A.B.P. Lever, Inorg. Chem. 33
(1994) 1045.
(
Space group, Z
Unit cell dimensions
P1, 2
,
a (A)
14.356(12)
11.684(12)
17.149(17)
(90)
97.53(1)
(90)
2852
1.836
2.652
12.341(15)
13.013(15)
15.506(17)
101.62(1)
111.86(1)
97.97(1)
2200
,
b (A)
,
c (A)
h (°)
i (°)
k (°)
3
,
V (A )
Dcalc (Mg m−3
Absorption coefficient
)
1.731
4.243
[8] K. Shinozaki, Y. Kaizu, Bull. Chem. Soc. Jpn. 67 (1994) 2314.
ˇ
[9] E.W. Abel, K.G. Orrell, A.G. Osborne, H.M. Pain, V. Sik, J.
(mm−1
)
Chem. Soc. Dalton Trans. (1994) 111.
[10] H. Behrens, U. Anders, Z. Naturforsch. Teil B 19 (1964) 767.
[11] T. Daniel, H. Nagao, H. Nakajima, K. Tanaka, A. Nakamura,
J. Organomet. Chem. 509 (1996) 225.
F (000)
1508
0.35×0.25
1096
0.25×0.10×0.10
Crystal size (mm3)
.
×0.20
q range for data collection
(°)
2.40 to 25.03
2.46 to 25.93
[12] P.K. Baker, S.G. Fraser, E.M. Keys, J. Organomet. Chem. 309
(1986) 319.
Index ranges
−175h517
05k513
−2051520
8035
4663/0.0733
4663/0/335
0.1078
05h515
−165k515
−1851516
7559
7559
7559/48/228
0.1215
[13] E.M. Armstrong, P.K. Baker, M.G.B. Drew, Organometallics 7
(1988) 319.
[14] N. Aimeloglou, P.K. Baker, M.M. Meehan, M.G.B. Drew,
Polyhedron 17 (1998) 3455.
[15] P.K. Baker, E.M. Armstrong, M.G.B. Drew, Inorg. Chem. 27
(1988) 2287.
[16] P.K. Baker, D. ap Kendrick, J. Organomet. Chem. 466 (1994)
139.
Reflections measured
Independent reflections [Rint
Data/restraints/parameters
R indices ([I\2|(I) R1
wR2
]
0.2358
0.2205
R indices (all data) R1
wR2
0.2206
0.2882
0.2643
0.2915
[17] P.K. Baker, M. Bamber, G.W. Rogers, J. Organomet. Chem.
367 (1989) 101.
Largest difference peak and 2.387, −0.770
1.594, −0.769
[18] M.G.B. Drew, Prog. Inorg. Chem. 23 (1977) 67, and refs. cited
therein.
−3
,
hole (e A
)
[19] M. Meln´ık, P. Sharrock, Coord. Chem. Rev. 65 (1985) 49, and
refs. cited therein.
[20] C.W. Haigh, P.K. Baker, Polyhedron 13 (1994) 417.
[21] P.K. Baker, Adv. Organomet. Chem. 40 (1996) 45, and refs.
cited therein.
[22] P.K. Baker, Chem. Soc. Rev. 27 (1998) 125, and refs. cited
therein.
[23] P.K. Baker, M.G.B. Drew, M.M. Meehan, H.K. Patel, A.
White, J. Chem. Res. (S) (1998) 379; J. Chem. Res. (M) (1998)
1461.
charge from The Director, CCDC, 12 Union Road,
Cambridge CB2 1EZ, UK (Fax: +44-1223-336033;
e-mail: deposit@ccdc.cam.ac.uk or www: http://
www.ccdc.cam.ac.uk).
Acknowledgements
[24] W. Kabsch, J. Appl. Cryst. 21 (1988) 916.
[25] SHELX 86, G.M. Sheldrick, Acta Crystallogr. Sect. A 46 (1990)
467
[26] DIFABS, N. Walker, D. Stuart, Acta Crystallogr. Sect. A 39
(1983) 158.
We thank the EPSRC for support, and M.M.M.
thanks the EPSRC for a studentship. N.A. also thanks
the Training for Work Scheme for support. B.J. thanks
the ERASMUS Scheme for support. We also thank the
[27] SHELXL, G.M. Sheldrick, Program for crystal structure refine-
ment. University of Go¨ttingen, 1993.