Synthesis and reactions of the cationic seven-coordinate complexes, n = 1, 2 and 3; R = Et, n = 1). (see abstract)

Article abstract of DOI:10.1016/S0022-328X(02)01894-6

Equimolar quantities of [MoI₂(CO)₃{Ph₂P (CH₂)_nPPh₂}] (n = 1, 2 or 3) and Ag[BF₄] were reacted in acetonitrile at room temperature to give the cationic seven-coordinate complexes,

Full text of DOI:10.1016/S0022-328X(02)01894-6

Journal of Organometallic Chemistry 664 (2002) 45ꢂ58
/
www.elsevier.com/locate/jorganchem
Synthesis and reactions of the cationic seven-coordinate complexes,
[MoI(CO)3(NCR){Ph2P(CH2)nPPh2}][BF4] (RꢀMe, nꢀ1, 2 and 3;
RꢀEt, nꢀ1). Crystal structures of [MoI2(CO)2(PPh3)-
CH2Cl2,
/
/
/
/
{Ph2P(CH2)PPh2}], [MoI(CO)2{Ph2P(CH2)PPh2}2][BF4]×
/
[MoCl3O{Ph2PO(CH2)OPPh2}] and [Mo3(m3-I)2{m2-
Ph2P(CH2)PPh2}3]I
Paul K. Baker a,ꢁ, Michael G.B. Drew b, Deborah S. Moore a
a Department of Chemistry, University of Wales, Bangor, Gwynedd LL57 2UW, UK
b Department of Chemistry, University of Reading, Whiteknights, Reading RG6 6AD, UK
Received 30 July 2002; received in revised form 3 September 2002; accepted 3 September 2002
Abstract
Equimolar quantities of [MoI2(CO)3{Ph2P(CH2)nPPh2}] (nꢀ
temperature to give the cationic seven-coordinate complexes, [MoI(CO)3(NCMe){Ph2P(CH2)nPPh2}][BF4], (1ꢂ
Reactions of [MoI(CO)3(NCMe){Ph2P(CH2)PPh2}][BF4] (1) with one equivalent of L in CH2Cl2 at room temperature afford either
[MoI(CO)3L{Ph2P(CH2)PPh2}][BF4], {LꢀNCEt 4, P(OMe)3 5, P(OEt)3 6} or [MoI(CO)2(NCMe)L{Ph2P(CH2)nPPh2}][BF4] {Lꢀ
P(OPri)3 7, P(OPh)3 8, PPh3 9}. Complex 9 reacts with NaI to give the crystallographically characterised complex,
[MoI2(CO)2(PPh3){Ph2P(CH2)PPh2}] (10). Treatment of 1 with equimolar amounts of LfflL {where LfflLꢀ
1,10-phen, 4,7-Me2-
1,10-phen, 2,2?-bipy, Ph2P(CH2)nPPh2 (nꢀ
1, 2 and 3)} yielded the cationic complexes [MoI(CO)(LfflL){Ph2P(CH2)PPh2}][BF4]
(11ꢂ Ph2P(CH2)PPh2}, has been crystallographically characterised. Equimolar quantities of 2, 3 and
16). Complex 14, {LfflLꢀ
Ph2P(CH)2PPh2 give the complexes, [MoI(CO)2{Ph2P(CH2)PPh2}{Ph2P(CH2)nPPh2}][BF4] {nꢀ2, 17, nꢀ3, 18). Reaction of
equimolar amounts of 1 and [S2CX]ꢃ affords the neutral complexes [MoI(CO)2(S2CX){Ph2P(CH2)PPh2}], (where Xꢀ
NMe2 19,
NEt2 20, NC4H8 21). Reaction of 1 and NaX (XꢀF, Cl) or KSCN, in equimolar ratio, gave the neutral complexes
[MoXI(CO)3{Ph2P(CH2)PPh2}] (22ꢂ24) in good yield. Upon exposure to air of concentrated solutions of complex 1 in CDCl3,
/1, 2 or 3) and Ag[BF4] were reacted in acetonitrile at room
/3), in high yield.
/
/
/
/
/
/
/
/
/
/
/
the unusual crystallographically characterised species, [MoCl3O{Ph2PO(CH2)OPPh2}] and [Mo3(m3-I)2{m2-Ph2P(CH2)PPh2}3]I, are
obtained as decomposition products.
# 2002 Elsevier Science B.V. All rights reserved.
Keywords: Cationic; Seven-coordinate; Molybdenum(II); Iodide; Carbonyl; Phosphine; Nitrile; Crystal structure
1. Introduction
four geometries; capped octahedral, capped trigonal
prism, pentagonal bipyramidal or the 4:3 geometry [1ꢂ
5]. Both Bencze and co-workers [6,7] and, more recently,
/
Seven-coordination is not commonly observed in
transition metal chemistry. However, there are many
examples of seven-coordinate complexes of molybdenu-
m(II) and tungsten(II), which generally exhibit one of
Baker and co-workers [8], have shown that complexes of
the type [MX2(CO)3(L)2] (Mꢀ
/
Mo, W; Xꢀ
/
Cl, Br, I:
LꢀNCMe, PPh3, etc.) are active single component
/
alkene metathesis catalysts. Although there are a large
range of neutral, seven-coordinate halocarbonyl com-
plexes of molybdenum(II) and tungsten(II) known
ꢁ Corresponding author. Tel.: ꢄ
370-528
E-mail address: chs018@bangor.ac.uk (P.K. Baker).
/
44-1248-382-379; fax: ꢄ44-1248-
/
[4,5,9ꢂ
/
25], far fewer cationic complexes of this type
30].
have been reported [26ꢂ
/
0022-328X/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 3 2 8 X ( 0 2 ) 0 1 8 9 4 - 6

46
P.K. Baker et al. / Journal of Organometallic Chemistry 664 (2002) 45ꢂ58
/
Until the work described in this paper, the only report
including the crystallographically characterised com-
plexes [MoI2(CO)2(PPh3){Ph2P(CH2)PPh2}] and
of the use of silver salts to prepare cationic seven-
coordinate complexes of Mo(II) and W(II), by halide
abstraction, was by Beck and Rosendorfer in 1995 [31].
They treated [MoBr2(CO)2(PPh3)2] with Ag[CF3SO3] to
give [Mo(O3SCF3)2(CO)2(PPh3)2], which then gave the
seven-coordinate cation [Mo(CO)2(NCMe)3(PPh3)2]-
[CF3SO3]2 in acetonitrile solution. The tungsten analo-
gue, [W(CO)2(NCMe)3(PPh3)2][CF3SO3]2 was also de-
scribed [31]. Attempts by Beck and co-workers [32] to
[MoI(CO)2{Ph2P(CH2)PPh2}2][BF4] which are de-
scribed. Dissolving the cation, [MoI(CO)3(NC-
Me){Ph2P(CH2)PPh2}][BF4], to give a concentrated
CDCl3 solution to afford the novel, structurally char-
acterised complexes, [MoCl3O{Ph2PO(CH2)POPh2}]
and [Mo3(m3-I)2{m2-Ph2P(CH2)PPh2}3]I, as two separate
decomposition products is also reported.
react [MBr2(CO)2(PPh3)2] (MꢀMo, W) with Ag[BF4]
/
in CH2Cl2 gave the fluoro-bridged complexes,
[(Ph3P)2(CO)2M(m-F)3M(CO)2(PPh3)2], which has been
2. Results and discussion
structurally characterised for MꢀMo.
/
The molybdenum(II) complexes [MoI2(CO)3-
{Ph2P(CH2)nPPh2}] (nꢀ1, 2 or 3) were prepared by
the reaction of equimolar amounts of [MoI2(CO)3-
(NCMe)2] and Ph2P(CH2)nPPh2, as previously reported
[35]. Reaction of the neutral complexes [MoI2(CO)3-
{Ph2P(CH2)nPPh2}] (nꢀ1, 2 or 3) with one equivalent
of Ag[BF4] in acetonitrile at room temperature gave the
cationic complexes [MoI(CO)3(NCMe){Ph2P(CH2)n-
In 1986 [33,34], we described the synthesis and
characterisation of the highly versatile seven-coordinate
/
di-iodo complexes, [MI2(CO)3(NCMe)2] (MꢀMo, W),
/
and we have extensively investigated their chemistry
[4,5]. In 1987 [35], we reported the high yield synthesis of
the seven-coordinate complexes [MI2(CO)3{Ph2P-
/
(CH2)nPPh2}] (Mꢀ
the reactions of [Mo2(CO)3{Ph2P(CH2)nPPh2}] (nꢀ
3) with Ag[BF4] in NCMe to give the cationic complexes
[MoI(CO)3(NCMe){Ph2P(CH2)nPPh2}][BF4] (nꢀ1ꢂ3)
/
Mo, W; nꢀ
/
1ꢂ
/
6). In this paper,
/
1ꢂ
/
PPh2}][BF4] (nꢀ
/
1, 2 or 3) (1ꢂ3), in very good yields.
/
The three cationic complexes have been fully charac-
terised by elemental analysis (C, H, N), IR spectroscopy,
1H-NMR spectroscopy, 11B{1H} and 31P{1H} spectro-
/
/
are detailed. The reactions of the bis(diphenylphosphi-
no)methane (dppm) complex in particular, with a series
of neutral and anionic ligands gave a range of products,
scopy (Tables 1ꢂ
/
4) and 13C{1H}-NMR spectroscopy
{for (1) and (2) only} (Table 5).
Table 1
a
Physical and analytical data for complexes 1ꢂ
/
24
Complex
Colour
Yield (%)
Analysis (%)
C
H
N
1
2
3
4
5
6
7
8
9
[MoI(CO)3(NCMe)(dppm)][BF4]
[MoI(CO)3(NCMe)(dppe)][BF4]
[MoI(CO)3(NCMe)(dpppr)][BF4]
[MoI(CO)3(NCEt)(dppm)][BF4]
Orangeꢂ
Orangeꢂ
Orangeꢂ
/
brown
brown
brown
brown
95
87
74
90
73
73
66
64
72
64
75
70
88
76
66
69
67
70
86
79
93
75
87
70
44.2 (44.0)
44.9 (44.7)
45.8 (45.4)
44.4 (44.7)
39.0 (39.0)
43.3 (43.2)
44.9 (44.9)
51.3 (51.3)
54.1 (53.6)
50.8 (51.4)
50.4 (50.2)
50.2 (49.8)
49.3 (49.0)
52.7 (52.2)
55.5 (55.4)
55.7 (55.8)
55.5 (55.4)
56.0 (55.8)
45.5 (46.0)
46.6 (47.4)
47.2 (47.5)
46.9 (47.3)
46.6 (46.3)
46.8 (46.5)
3.6 (3.1)
3.8 (3.3)
4.0 (3.5)
3.6 (3.3)
3.9 (3.4)
4.8 (4.0)
4.8 (4.6)
3.7 (3.7)
4.1 (3.8)
3.8 (3.5)
3.6 (3.5)
3.6 (3.5)
3.7 (3.3)
3.9 (3.8)
4.1 (4.0)
4.3 (4.2)
4.3 (4.0)
4.5 (4.2)
3.8 (3.6)
4.0 (4.0)
4.0 (3.7)
3.6 (3.1)
3.5 (3.1)
3.5 (3.0)
2.1 (1.7)
1.7 (1.7)
1.7 (1.7)
2.4 (1.7)
/
/
Orangeꢂ
Yellow
Yellow
/
[MoI(CO)3{P(OMe)3}(dppm)][BF4]×CH2Cl2
[MoI(CO)3{P(OEt)3}(dppm)][BF4]
[MoI(CO)2(NCMe){P(Oi Pr)3}(dppm)][BF4]×0.5CH2Cl2
[MoI(CO)2(NCMe){P(OPh)3}(dppm)][BF4]
[MoI(CO)2(NCMe)(PPh3)(dppm)][BF4]
ꢂ/
ꢂ/
Yellowꢂ
Yellowꢂ
Orange
/
brown
brown
1.0 (1.4)
1.2 (1.3)
1.6 (1.3)
/
10 [MoI2(CO)2(PPh3)(dppm)]
Bright orange
Dark brown
Dark brown
Dark brown
Yellow
ꢂ/
11 [MoI(CO)2(1,10-phen)(dppm)][BF4]
12 [MoI(CO)2(4,7-Me2-1,10-phen)(dppm)][BF4]×0.5CH2Cl2
13 [MoI(CO)2(2,2?-bipy)(dppm)][BF4]
14 [MoI(CO)2(dppm)2][BF4]×CH2Cl2
15 [MoI(CO)2(dppe)(dppm)][BF4]
16 [MoI(CO)2(dpppr)(dppm)][BF4]
17 [MoI(CO)2(dppm)(dppe)][BF4]
18 [MoI(CO)2(dppm)(dpppr)][BF4]
19 [MoI(CO)2(S2CNMe2)(dppm)]
20 [MoI(CO)2(S2CNEt2)(dppm)]
21 [MoI(CO)2(S2CNC4H8)(dppm)]
22 [MoFI(CO)3(dppm)]
3.0 (3.0)
3.0 (2.8)
3.7 (3.1)
ꢂ/
ꢂ/
ꢂ/
ꢂ/
Dark yellow
Dark yellow
Dark yellow
Dark yellow
Brown
ꢂ/
2.1 (1.8)
2.1 (1.7)
2.0 (1.7)
Brown
Brown
Brownꢂ/green
ꢂ/
ꢂ/
23 [MoClI(CO)3(dppm)]
24 [Mo(NCS)I(CO)3(dppm)]
Dark brown
Dark brown
1.9 (1.9)
a
Calculated values in parentheses; dppmꢀPh2P(CH2)PPh2; dppeꢀPh2P(CH2)2PPh2; dppprꢀPh2P(CH2)3PPh2.

P.K. Baker et al. / Journal of Organometallic Chemistry 664 (2002) 45ꢂ
/58
47
Table 2
Infrared data for complexes 1ꢂ
a
/
24
n(CÅN) cmꢃ1
n(CÅO) cmꢃ1
n(BÃF) cmꢃ1
1
2
2252, w
2254, w
2274, w
2250, w
2038, w, 1961, 1882 s, br
2046, w, 1957, 1890, s, br
1929, 1880, 1850, s, br
2041, w, 1960, 1888, s, br
1988, 1954, 1908, s, br
1982, 1953, 1901, s, br
1968, 1897, s, br
1069, 1028, s, br
1068, 1028, s, br
1067, 1028, s, br
1067, 1026, s, br
1068, 1029, s, br
1068, 1027, s, br
1062, 1024, s, br
1059, s, 1025, m
1066, 1027, s, br
3
4
5
ꢂ/
ꢂ/
6
7
2280, w
2278, w
2271, w
8
1978, 1911, s, br
1961, 1893, s
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
ꢂ
ꢂ/
ꢂ/
ꢂ/
ꢂ/
ꢂ/
ꢂ/
ꢂ/
ꢂ/
ꢂ/
ꢂ/
ꢂ/
ꢂ/
ꢂ/
/
1941, 1860, s, sh
1974, 1888, s, br
ꢂ
/
1064, 1026, s, br
1065, 1027, s, br
1065, 1028, s, br
1089, 1057, s, br
1065, 1028, s, br
1067, 1028, s, br
1066, 1027, s, br
1067, 1028, s, br
n(CS) 1786, m, br
n(CS) 1792, 1771, m, s br
n(CS) 1789, m, br
1972, 1889, s, br
1972, 1892, s, br
1934, 1862, s, sh
1950, s, sh, 1885, m, sh
1946, s, sh, 1879, m, sh
1950, s, sh, 1886, m, sh
1946, s, sh, 1879, m, sh
1946, m, 1882, s
1945, s, sh, 1880, s, br
1946, 1880, s, br
2043, m, 1972, s, br, 1885, m, br
2040, m, 1950, s, br, 1871, m
2071, 1955, 1880, s, br
ꢂ/
ꢂ/
ꢂ/
n(NCS) 2133, m
a
Spectra recorded as thin films in CHCl3, between NaCl plates; sꢀstrong, mꢀmedium, wꢀweak, shꢀsharp, brꢀbroad.
Complexes 1ꢂ
chloroform and dichloromethane, and are completely
insoluble in hexane and diethyl ether as expected for
/
3 are soluble in acetone, acetonitrile,
characteristic singlet due to [BF4]ꢃ in the 11B{1H}-
NMR spectra of 1 and 2 at ꢃ1.34 ppm and 3 at ꢃ1.20
ppm.
The H-NMR spectra of 1ꢂ
/
/
1
/
3 show the phenyl and
cationic complexes. All three complexes 1ꢂ3 show a
/
methylene protons of the parent bidentate phosphine
ligands (dppm, dppe or dpppr) in the expected regions,
upon comparison with both the 1H-NMR spectra of
marked increase in air sensitivity compared to their
neutral precursors [35], with deterioration of the com-
plexes apparent within 1 h at room temperature,
1
their neutral precursors [35], and the H-NMR spectra
accompanied by a change in colour from orangeꢂ
to dark brown. The cationic complexes can be stored
under N2 at ꢃ17 8C for up to 2 months with no signs of
/
brown
of the phosphine ligands themselves (CDCl3, 25 8C,
referenced to SiMe4). In addition, the methyl protons of
the acetonitrile ligand are observed as broad singlets
/
decomposition. Solution samples of complexes 1, 2 and
3 were considerably more sensitive to decomposition,
particularly upon exposure to air.
(Table 3). The 31P{1H}-NMR spectra of complexes 1ꢂ
3
/
have singlet resonances at ꢃ
/
0.63 ppm (1), ꢄ76.34 ppm
/
The IR spectra of 1ꢂ
stretching frequency at 2252, 2254 and 2274 cmꢃ1
respectively. Complexes 1ꢂ3 all have three carbonyl
n(CÅO) stretching bands; 1 and 2 have a weak band at
/
3 have a single weak n(NÅ
/
C)
(2) and ꢄ32.12 ppm (3), which differ markedly from
one another, but follow a similar pattern to that
/
,
/
observed for the free bis(diphenylphosphino)alkane
/
ligands [ꢃ
/
23.03 ppm (dppm), ꢃ13.23 ppm (dppe) and
/
2038 and 2046 cmꢃ1, respectively, and two strong
stretches at 1961, 1882 cmꢃ1 for 1 and 1957, 1890
cmꢃ1 for 2, whilst complex 3 has three strong, broad
carbonyl stretches at 1929, 1880 and 1850 cmꢃ1. The IR
spectra of all three cationic complexes are distinct from
their neutral precursors, which show three strong or
medium intensity carbonyl bands at 2035 cmꢃ1, be-
tween 1967 and 1940 cmꢃ1 and between 1920 and 1915
ꢃ
/
18.07 ppm (dpppr), in CDCl3, referenced to 85%
H3PO4]. The appearance of the two phosphorus atoms
as a singlet, rather than two individual resonances, is
indicative of the complex being fluxional at room
temperature. The room temperature 13C{1H}-NMR
spectra of complexes 1 and 2 both show a triplet
resonance due to the three carbonyl ligands, [223.06
ppm, JPÃC
ꢀ
/
22.6 Hz (1) and 229.98 ppm, JPÃC
ꢀ22.6
/
cmꢃ1 [35]. The cationic nature of complexes 1ꢂ
/
3 is
F)
Hz (2)], which also indicates that the complex is
fluxional at room temperature. Resonances attributable
to the dppm ligand in complex 1 were observed at
confirmed by the presence of two strong, broad n(BÃ
/
stretching frequencies at 1069, 1028 cmꢃ1 (1), 1068,
1028 cmꢃ1 (2) and 1067, 1028 cmꢃ1 (3), and by the
132.33ꢂ128.65 ppm (Ph2P(CH2)PPh2) and 37.66 ppm
/

48
P.K. Baker et al. / Journal of Organometallic Chemistry 664 (2002) 45ꢂ58
/
Table 3
a
Proton NMR data for complexes 1ꢂ
/
24
1H (d) ppm
1
2
3
4
7.65ꢂ
7.70ꢂ
7.55ꢂ
7.53ꢂ
CH3CH2CN, Jꢀ7.5 Hz).
7.59ꢂ7.20 (m, 20H, Ph2P(CH2)PPh2); 5.33 (s, 2H, CH2Cl2); 5.29ꢂ
7.60ꢂ7.10 (br m, 20H, Ph2P(CH2)PPh2); 5.35ꢂ5.25 (t, 2H, P(CH2)P, JPÃHꢀ10.3 Hz); 4.25ꢂ
P(OCH2CH3)3).
7.75ꢂ7.00 (br m, 20H, Ph2P(CH2)PPh2); 5.45 (s, 1H, 0.5CH2Cl2); 4.95ꢂ
1H, P(CH2)P); 1.95ꢂ1.85 (s, 3H, CH3CN); 1.40ꢂ1.25 (m, 18H, P{OCH(CH3)2}3).
8.25ꢂ6.80 (br m, 35H, Ph2P(CH2)PPh2/P(OPh)3); 5.10ꢂ4.90 (m, 1H, P(CH2)P); 4.55ꢂ
8.00ꢂ7.10 (br m, 35H, Ph2P(CH2)PPh2/PPh3); 5.60ꢂ5.40 (m, 1H, P(CH2)P); 4.80ꢂ4.60 (m, 1H, P(CH2)P); 2.05 (s, 3H, CH3CN).
7.10 (br m, 35H, Ph2P(CH2)PPh2/PPh3); 4.55 (br s, 2H, P(CH2)P).
11 8.74 (d, 2H, Jꢀ4.3 Hz); 8.56 (d, 2H, Jꢀ7.9 Hz); 7.77 (d, 2H, Jꢀ5.2 Hz); 7.57 (d, 2H, Jꢀ5.2 Hz)ꢂ
Ph2P(CH2)PPh2); 4.72 (t, 2H, P(CH2)P, JPÃHꢀ10.4 Hz).
/
7.10 (br s, 20H, Ph2P(CH2)PPh2); 4.50ꢂ
7.30 (s, 20H, Ph2P(CH2)2PPh2); 2.70ꢂ2.50 (d, 4H, P(CH2)2P, JPÃHꢀ18.8 Hz); 2.10ꢂ
7.06 (m, 20H, Ph2P(CH2)3PPh2); 2.78ꢂ2.15 (br m, 6H, P(CH2)3P); 2.05ꢂ2.00 (s, 3H, CH3CN).
7.25 (m, 20H, Ph2P(CH2)PPh2); 4.49ꢂ4.40 (t, 2H, P(CH2)P, JPÃHꢀ11.2 Hz); 2.60ꢂ2.40 (m, 2H, CH3CH2CN); 1.01ꢂ0.95 (t, 3H,
/
4.35 (t, 2H, P(CH2)P, JPÃHꢀ11.1 Hz); 2.10ꢂ
/
1.95 (s, 3H, CH3CN).
/
/
/1.90 (s, 3H, CH3CN).
/
/
/
/
/
/
/
5
6
/
/
5.21 (t, 2H, P(CH2)P, JPÃHꢀ10.2 Hz); 3.77ꢂ/3.68 (m, 9H, P(OCH3)3).
/
/
/
4.15 (m, 6H, P(OCH2CH3)3); 1.40ꢂ/1.25 (m, 9H,
7
/
/
4.85 (m, 1H, P(CH2)P); 4.80ꢂ
/
4.60 (m, 3H, P(OCHMe2)3); 4.10ꢂ4.00 (m,
/
/
/
8
9
/
/
/
4.40 (m, 1H, P(CH2)P); 2.05 (s, 3H, CH3CN).
/
/
/
10 7.80ꢂ
/
/
1,10-phen; 7.34ꢂ7.27 (m, 20H,
/
12 8.62 (d, 2H, Jꢀ5.1 Hz); 8.12 (s, 2H); 7.27 (s, 2H, 4,7-Me2-1,10-phen); 7.62ꢂ/7.31 (m, 20H, Ph2P(CH2)PPh2); 5.30 (s, 1H, 0.5CH2Cl2); 4.66 (t, 2H,
P(CH2)P, JPÃHꢀ10.3 Hz); 2.85 (s, 6H, 4,7-Me2-1,10-phen).
13 8.49 (d, 2H, Jꢀ8.1 Hz); 8.26 (s, 2H); 8.05 (d, 2H, Jꢀ7.7 Hz)ꢂ
Hz).
14 7.50ꢂ
15 7.60ꢂ
P(CH2)2P); 2.80ꢂ
16 7.70ꢂ7.15 (m, 40H, Ph2P(CH2)PPh2/Ph2P(CH2)3PPh2); 6.45ꢂ
PCH2(CH2)CH2P); 3.15ꢂ2.85 (m, 2H, PCH2(CH2)CH2P).
17 7.67ꢂ7.03 (m, 40H, Ph2P(CH2)PPh2/Ph2P(CH2)2PPh2); 6.05ꢂ
P(CH2)2P); 2.80ꢂ2.60 (br m, 2H, P(CH2)2P).
18 7.72ꢂ6.92 (m, 40H, Ph2P(CH2)PPh2/Ph2P(CH2)3PPh2); 6.00ꢂ
PCH2(CH2)CH2P); 2.70ꢂ2.50 (m, 2H, PCH2(CH2)CH2P).
19 7.60ꢂ6.95 (m, 20H, Ph2P(CH2)PPh2); 4.45ꢂ4.30 (t, 2H, P(CH2)P, JPÃHꢀ11.1 Hz); 3.55ꢂ
20 7.73ꢂ7.01 (m, 20H, Ph2P(CH2)PPh2); 4.43ꢂ4.36 (t, 2H, P(CH2)P, JPÃHꢀ10.1 Hz); 3.98ꢂ
(CH3CH2)2NCS2).
21 7.70ꢂ6.90 (m, 20H, Ph2P(CH2)PPh2); 4.40ꢂ
22 7.54ꢂ7.08 (m, 20H, Ph2P(CH2)PPh2); 5.05ꢂ
23 7.80ꢂ7.10 (br m, 20H, Ph2P(CH2)PPh2); 5.10ꢂ
24 7.80ꢂ7.00 (br m, 20H, Ph2P(CH2)PPh2); 5.05ꢂ
/
2,2?-bipy; 7.47ꢂ
/
7.26 (m, 20H, Ph2P(CH2)PPh2); 4.68 (t, 2H, P(CH2)P, JPÃHꢀ10.5
/
7.00 (m, 40H, 2ꢅPh2P(CH2)PPh2); 5.25 (s, 2H, CH2Cl2); 4.45ꢂ
7.00 (m, 40H, Ph2P(CH2)PPh2/Ph2P(CH2)2PPh2); 6.10ꢂ5.90 (br s, 1H, P(CH2)P); 5.00ꢂ
2.60 (br m, 2H, P(CH2)2P).
/4.30 (m, 4H, P(CH2)P).
/
/
/
4.80 (br s, 1H, P(CH2)P); 3.45ꢂ3.25 (br m, 2H,
/
/
/
/
6.25 (m, 1H, P(CH2)P); 5.20ꢂ
5.85 (br s, 1H, P(CH2)P); 5.00ꢂ
5.80 (m, 1H, P(CH2)P); 4.80ꢂ4.55 (m, 1H, P(CH2)P); 4.00ꢂ
/
5.00 (m, 1H, P(CH2)P); 4.38ꢂ4.12 (m, 4H,
/
/
/
/
/
4.75 (br s, 1H, P(CH2)P); 3.50ꢂ/3.30 (br m, 2H,
/
/
/
/
/3.80 (m, 4H,
/
/
/
/3.45 (m, 6H, (CH3)2NCS2).
/
/
/
3.86 (m, 4H, (CH3CH2)2NCS2); 1.41ꢂ1.20 (m, 6H,
/
/
/
4.30 (t, 2H, P(CH2)P, JPÃHꢀ11.0 Hz); 4.00ꢂ
4.90 (br s, 2H, P(CH2)P).
/3.20 (br m, 8H, C4H8NCS2).
/
/
/
/
4.90 (br s, 2H, P(CH2)P).
/
/
4.90 (br s, 2H, P(CH2)P).
a
Spectra recorded in CDCl3 at ꢄ25 8C, referenced to SiMe4; sꢀsinglet, dꢀdoublet, ddꢀdoublet of doublets, tꢀtriplet, qꢀquartet,
mꢀmultiplet, brꢀbroad.
(Ph2P(CH2)PPh2). The acetonitrile resonances for com-
plex 1 were observed at 130.96 ppm (CH3CN) and 4.14
ppm (CH3CN).
Equimolar quantities of [MoI(CO)3(NCMe){Ph2P-
(CH2)PPh2}][BF4] (1) and L react at room temperature
in CH2Cl2 to give either the acetonitrile displaced
The majority of seven-coordinate complexes of mo-
lybdenum(II) and tungsten(II) have capped octahedral
geometry [1,5], therefore it may be that the complexes
complexes [MoI(CO)3L{Ph2P(CH2)PPh2}][BF4], {Lꢀ
/
NCEt (4); P(OMe)3 (5); P(OEt)3 (6)} or the carbonyl
displaced products, [MoI(CO)2(NCMe)L{Ph2P(CH2)-
1ꢂ
/
3 also have this geometry. Two possible structures for
PPh2}][BF4], {Lꢀ
/
P(OiPr)3 (7); P(OPh)3 (8); PPh3 (9)}
1ꢂ/3 are shown in Fig. 1(a) and (b). The proposed
in good yields. Complexes 4ꢂ9 have all been charac-
/
structure (Fig. 1(a)) is the most likely structure for 1ꢂ
/
3,
terised by elemental analysis (C, H and N) (Table 1), IR
1
as the acetonitrile ligand is arranged distally to the bulky
phenyl groups of the bidentate phosphine ligand. The
structure shown in (Fig. 1(b)), however, is least favoured
as there would be considerable steric hindrance about
the acetonitrile coordination site due to the phenyl
groups of the bis(diphenylphosphino)alkane ligands. A
number of unsuccessful attempts were made to grow
spectroscopy (Table 2) and H-, 11B{1H}- and 31P{1H}-
NMR spectroscopy (Tables 3 and 4). Complex 4 has
comparable air-sensitivity to complex 1, is soluble in
acetone, acetonitrile, chloroform and dichloromethane,
and insoluble in diethyl ether and hexane. Complexes 5
and 6 are slightly more stable than complex 1, but
decompose within 2 h upon exposure to air at room
temperature. Complexes 5 and 6 are very air-sensitive in
solution and are very soluble in acetone, acetonitrile,
dichloromethane and chloroform, but were completely
suitable single crystals of 1ꢂ3 using a range of mixed
/
solvents and temperatures to obtain crystals suitable for
a single crystal X-ray diffraction study.

P.K. Baker et al. / Journal of Organometallic Chemistry 664 (2002) 45ꢂ
/58
49
Table 4
Boron and phosphorus NMR data for complexes 1ꢂ
a
/
24
b
11B{1H} (d)
ppm
31P{1H} (d) ppm
1
2
3
4
5
6
7
ꢃ1.34, s
ꢃ1.34, s
ꢃ1.20, s
ꢃ1.27, s
ꢃ1.34, s
ꢃ1.34, s
ꢃ1.27, s
ꢃ0.63 (s, dppm)
ꢄ76.34 (s, dppm)
ꢄ32.12 (s, dppm)
ꢃ0.87 (s, dppm)
ꢄ152.14 (s, 1P, P(OMe)3); ꢃ21.06 (s, 2P, dppm)
ꢄ149.18 (s, 1P, P(OEt)3); ꢃ21.38 (s, 2P, dppm)
ꢄ128.23 (dd, 1P, P(Oi Pr)3, JP1ÃP2ꢀ28.7 Hz, JP1ÃP3ꢀ217.8 Hz); ꢃ7.51 (dd, 1P, dppm, JP2ÃP1ꢀ28.7 Hz, JP2ÃP3ꢀ77.7 Hz);
ꢃ43.39 (dd, 1P, dppm, JP3ÃP2ꢀ77.7 Hz, JP3ÃP1ꢀ217.8 Hz)
ꢄ130.25 (dd, 1P, P(OPh)3, JP1ÃP2ꢀ25.7 Hz, JP1ÃP3ꢀ231.7 Hz); ꢄ5.51 (dd, 1P, dppm, JP2ÃP1ꢀ25.7 Hz, JP2ÃP3ꢀ84.0 Hz);
40.59 (dd, 1P, dppm, JP3ÃP2ꢀ84.0 Hz, JP3ÃP1ꢀ231.7 Hz)
ꢄ29.29 (d, 1P, PPh3, JP1ÃP2ꢀN/O, JP1ÃP3ꢀ132.93 Hz); ꢄ8.30 (d, 1P, dppm, JP2ÃP1ꢀ29.8 Hz, JP2ÃP3ꢀN/O); ꢃ34.81 (m,
1P, dppm)
8
9
ꢃ1.19, s
ꢃ1.19, s
b
10
11
12
13
14
15
16
17
18
19
20
21
23
24
ꢂ/
ꢄ21.35 (s, 1P, PPh3); ꢃ4.06 (s, 1P, dppm); ꢃ9.72 (s, 1P, dppm)
ꢃ4.18 (s, dppm)
ꢃ3.30 (s, dppm)
ꢃ4.76 (s, dppm)
ꢃ10.04 (s, 4P, dppm)
ꢄ53.74 (d, 2P, dppe, JPÃPꢀ89.6 Hz); ꢃ14.73 (d, 2P, dppm, JPÃPꢀ89.6 Hz)
ꢄ2.89 (d, 2P, dpppr, JPÃPꢀ93.3 Hz); ꢃ14.35 (d, 2P, dppm, JPÃPꢀ93.3 Hz)
ꢄ53.70 (d, 2P, dppe, JPÃPꢀ87.6 Hz); ꢃ14.77 (d, 2P, dppm, JPÃPꢀ87.6 Hz)
ꢄ2.92 (d, 2P, dpppr, JPÃPꢀ95.0 Hz); ꢃ14.32 (d, 2P, dppm, JPÃPꢀ95.0 Hz)
ꢄ0.40 (d, 1P, dppm, JPÃPꢀ86.0 Hz); ꢃ17.38 (d, 1P, dppm, JPÃPꢀ86.0 Hz)
ꢄ0.17 (d, 1P, dppm, JPÃPꢀ86.0 Hz); ꢃ17.34 (d, 1P, dppm, JPÃPꢀ86.0 Hz)
ꢄ0.35 (d, 1P, dppm, JPÃPꢀ87.3 Hz); ꢃ17.05 (d, 1P, dppm, JPÃPꢀ87.3 Hz)
ꢃ1.59 (s, dppm)
ꢃ1.13, s
ꢃ1.20, s
ꢃ1.19, s
ꢃ0.46, s
ꢃ1.28, s
ꢃ1.33, s
ꢃ1.33, s
ꢃ1.33, s
ꢂ/
ꢂ/
ꢂ/
ꢂ/
ꢂ/
ꢃ10.98 (s, dppm)
a
Spectra recorded in CDCl3 at ꢄ25 8C, referenced to BF3×OEt2.
Spectrum recorded in CDCl3 or in CD2Cl2 at ꢄ25 8C, referenced to 85% H3PO4; at ꢄ25 8C; sꢀsinglet, dꢀdoublet, mꢀmultiplet; N/Oꢀnot
b
observed.
plexes 7 and 8 have similar solubility and stability to
complexes 5 and 6, with the triphenylphosphine complex
9 being the least soluble complex so far described.
Table 5
Carbon NMR data for complexes 1 and 2
a
13C{1H} (d) ppm
The IR spectra (Table 2) of complexes 4ꢂ
carbonyl stretching bands, whereas the acetonitrile
complexes 7ꢂ9 have two carbonyl stretching bands
and weak acetonitrile bands, as expected. All six
complexes, 4ꢂ9, have n(BÃF) stretching bands at
approximately 1060 and 1030 cmꢃ1. The 1H-NMR
spectra of 4ꢂ9 all have the expected resonances shifted
/6 have three
1
2
223.06 (t, 3ꢅCÅO, JPÃCꢀ22.6 Hz); 132.33ꢂ128.65 (m, CÄC,
Ph2P(CH2)Ph2); 130.96 (s, CH3CN); 37.66 (t, Ph2P(CH2)Ph2,
JPÃCꢀ26.4 Hz); 4.14, (s, CH3CN).
/
/
229.98 (t, 3ꢅCÅO, JPÃCꢀ22.6 Hz); 132.44ꢂ129.69 (m, CÄC,
/
/
/
Ph2P(CH2)2Ph2); 130.91 (s, CH3CN); 27.46 (d, Ph2P(CH2)2Ph2,
JPÃCꢀ23.6 Hz); 4.11 (s, CH3CN).
/
a
Spectra recorded in CDCl3 at ꢄ25 8C, referenced to SiMe4;
sꢀsinglet, dꢀdoublet, tꢀtriplet, mꢀmultiplet.
slightly downfield from the free ligands. It is interesting
to note that the room temperature 31P{1H}-NMR
spectra of [MoI(CO)3{P(OR)3}{Ph2P(CH2)PPh2}][BF4]
(5 and 6) both show two phosphorus resonances at
152.14 and ꢃ
/
21.06 ppm (5) and 149.18 and ꢃ
/
21.38ppm
Fig.
1. Proposed
structures
of
[MoI(CO)2(NC-
Me){Ph2P(CH2)n PPh2}][BF4] {nꢀ
/
1 (1), 2 (2) and 3 (3)}.
insoluble in diethyl ether and hexane. They are much
more soluble than their nitrile counterparts, 1ꢂ3. Com-
Fig.
2. Proposed
structure
of
the
cations,
/
[MoI(CO)2(NCMe)(PR3)(dppm)]ꢄ, (7ꢂ
/
9), {Rꢀ
/
(Oi Pr), (OPh) or Ph}.

50
P.K. Baker et al. / Journal of Organometallic Chemistry 664 (2002) 45ꢂ58
/
(6), respectively, with no apparent phosphorusꢂ
/
phos-
[MI2(CO)2{P(OR)3}{Ph2P(CH2)nPPh2}]
RꢀMe, Et, nꢀ1; Rꢀ
Et, iPr, Ph, nꢀ
RꢀPh, nꢀ1; RꢀMe, Et, Pr, nꢀ
(Mꢀ
2; Mꢀ
2) [36]. The mixed
/
Mo,
phorus coupling which could result from poorly re-
solved spectra, or a fluxional process. The two singlets
could result from phosphine dissociation (one for the
phosphite’s and also one resonance for the bidentate
phosphine either in a symmetrical environment or
rapidly equilibrating), whereby the coupling could
diminish to zero. The room temperature 31P{1H}-
/
/
/
/
/
W,
i
/
/
/
/
phosphite/phosphine complexes all have capped octahe-
dral geometry, with one carbonyl ligand in the unique
capping position over the face containing the other
carbonyl, the phosphite ligand, and one phosphorus of
the phosphine ligand. The crystal structure of complex
10 (Fig. 3) has a seven-coordinate molybdenum atom
bonded to two carbonyl atoms, two iodine atoms, a
triphenylphosphine ligand and a bidentate dppm ligand.
The geometry is best considered as capped octahedral,
NMR spectra of complexes 7ꢂ
different chemical environments, for example, complex 7
has resonances at ꢄ128.23, ꢃ7.51 and ꢃ43.39 ppm.
Using the proposed structure of complexes 7ꢂ9 (Fig. 2),
for complex 7, the lowfield doublet of doublets at
128.23 ppm is attributed to the P(OiPr)3 ligand, P1,
having cis-type coupling to one phosphorus of the dppm
ligand, P2, (JP1ÃP2
28.7 Hz) and trans-type coupling to
217.8 Hz). Similarly,
/
9, however, show three
/
/
/
/
with the carbonyl ligand [C(100)Ã
/
O(100)] capping the
ꢄ
/
face containing the other carbonyl ligand [C(200)Ã
/
O(200)], the PPh3 ligand [P(2)] and one phosphorus of
the dppm ligand [P(1)]. The uncapped face contains the
other phosphorus of the dppm ligand [P(3)] and the two
iodine atoms. The PPh3 ligand is positioned distally to
the dppm ligand, which minimises steric hindrance
between the two groups. The two carbonyl groups are
mutually cis, which avoids competition between them
for the metal d-electrons which are required for back
ꢀ
/
the dppm phosphorus P3 (JP1ÃP3
ꢀ
/
the dppm phosphorus, P3, shows a trans-type coupling
to P1 of the P(OiPr)3 ligand and a cis-type coupling to
the other phosphorus of the dppm ligand, P2, [ꢃ
/
43.39
217.8 Hz]. The P2
phosphorus has cis-type couplings to both P1 and P3,
[ꢃ7.51 ppm, dd, JP2ÃP1 28.7 Hz, JP2ÃP3 77.7 Hz].
ppm, dd, JP3ÃP2
ꢀ
/
77.7 Hz, JP3ÃP1
ꢀ
/
/
ꢀ
/
ꢀ
/
bonding to the metal centre. The MoÃ
/
P bonds to the
The coupling constants for complex 8 are comparable
with those of 7 (Table 4). A number of unsuccessful
PPh3 ligand [P(2)] and to the phosphorus atom of dppm
which is essentially trans to the PPh3 ligand, [P(3)], are
˚
identical [2.597(5) A]. The remaining phosphorus atom
attempts to grow single crystals of 7ꢂ
/
9 suitable for X-
ray analysis were made, however, the 31P{1H}-NMR
data discussed above give evidence for the structure
proposed in Fig. 2. It was surprising that the reaction of
of the dppm ligand has a slightly shorter MoÃ
/
P(1) bond
[2.542(5) A], and the iodine atom trans to P(1) has a
˚
˚
I(3) bond [2.873(3) A], than the iodine
shorter MoÃ
/
equimolar amounts of 1 with L {Lꢀ
/
NCEt, P(OR)3
Pr or Ph),
trans to the non-capping carbonyl, [MoÃ
/
I(2)ꢀ2.911(3)
/
(RꢀMe or Et)} and L {Lꢀ
/
/
P(OR)3 (Rꢀi
/
A].
Reaction of [MoI(CO)3(NCMe){Ph2P(CH2)PPh2}]-
[BF4] (1), with equimolar quantities of LfflL {LfflLꢀ
1,10-phen, 4,7-Me2-1,10-phen, 2,2?-bipy, Ph2P(CH2)n-
PPh2 (nꢀ1ꢂ3)} in dichloromethane at room tempera-
ture, afforded the cationic dicarbonyl complexes,
[MoI(CO)2(LfflL){Ph2P(CH2)PPh2}][BF4] (11ꢂ
16). Si-
˚
PPh3} gave different products, but this was probably
due to the increased steric bulk of the latter three
ligands.
/
Treatment of the PPh3 complex [MoI(CO)2(NC-
Me)(PPh3){Ph2P(CH2)PPh2}][BF4] (9), prepared in
situ, with one equivalent of NaI in acetone gave the
highly crowded neutral complex [MoI2(CO)2(PPh3)-
{Ph2P(CH2)PPh2}] (10). Complex 10 was characterised
/
/
/
milar reactions of [MoI(CO)3(NCMe){Ph2P(CH2)2-
PPh2}][BF4] (2), and [MoI(CO)3(NCMe){Ph2P(CH2)3-
PPh2}][BF4] (3), with one equivalent of Ph2P(CH2)PPh2
in CHCl2 at room temperature gave [MoI(CO)2{Ph2P-
(CH2)PPh2}{Ph2P(CH2)nPPh2}][BF4] (17) and (18), re-
in the usual manner (Tables 1ꢂ
4). The 31P{1H}-NMR of
/
10 also has three resonances, attributable to the PPh3
and dppm ligands. Compared to the cationic precursor,
complex 9, there is an upfield shift for the PPh3 ligand
and the dppm phosphorus atom with higher chemical
shift (P1 and P3), whereas the other dppm phosphorus
spectively, in high yield. Complexes 11ꢂ18 were all fully
/
characterised by elemental analysis (C, H, N), IR
spectroscopy, and 1H-, 11B{1H}- and 31P{1H}-NMR
atom (P2) has moved downfield, [ꢄ
ppm (10); ꢄ29.29, ꢄ8.30, ꢃ34.81 ppm (9)], which is
probably due to the formation of a neutral complex
/
21.35, ꢃ
/
4.06, ꢃ
/
9.72
spectroscopy (Tables 1ꢂ/4). The complex, [MoI(CO)2-
/
/
/
{Ph2P(CH2)PPh2}2][BF4]×/CH2Cl2 (14) was also charac-
terised by X-ray crystallography (Fig. 4). Complex 12
was confirmed as a 0.5CH2Cl2 solvate and complex 14
as a CH2Cl2 solvate by repeated elemental analysis and
1H-NMR spectroscopy. In the solid state, all the
complexes showed deterioration after several hours
upon addition of the iodide.
Single crystals suitable for X-ray crystallography of
10 were grown from a CDCl3 solution (ꢃ17 8C), of
[MoI(CO)2(NCMe)(PPh3){Ph2P(CH2)PPh2}][BF4] (9).
Crystal data for all structures described in this paper,
10, 14, 25 and 26, are given in Table 6. The associated
bond lengths are given in Table 7. The crystal structure
of 10 (Fig. 3) is comparable to the literature complexes
/
when exposed to air. Solutions of complexes 11ꢂ18
/
decompose when exposed to air, with full decomposition
observed within 12 h. The complexes can be stored
under nitrogen at ꢃ17 8C in either solid or solution
/

P.K. Baker et al. / Journal of Organometallic Chemistry 664 (2002) 45ꢂ
/58
51
Table 6
Crystal data and structure refinement for complexes 10, 14, 25 and 26
10
14
25
26
Empirical formula
Formula weight
Temperature (K)
C
1052.4
45H37I2MoO2P3 C52H44BF4IMoO2P4×2CH2Cl2
C25.5H28.5Cl4.5MoO6P2 C75H66I3Mo3P6×1.5H2O
1304.25
293(2)
748.39
293(2)
1848.64
293(2)
293(2)
0.71073
Triclinic
˚
Wavelength (A)
0.71073
Monoclinic
C2/c
0.71073
Monoclinic
P21/n
0.71073
Monoclinic
P21/n
Crystal system
Space group
Unit cell dimensions
¯
P1
˚
a (A)
11.867(12)
13.111(15)
14.160(17)
87.22(1)
85.56(1)
82.33(1)
2175(4)
2
42.10(5)
11.569(13)
25.96(3)
16.66(2)
8.647(13)
23.09(2)
19.22(2)
18.82(2)
21.41(3)
˚
b (A)
˚
c (A)
a (8)
b (8)
g (8)
ꢂ/
ꢂ/
ꢂ/
115.97(1)
108.91(1)
90.35(1)
ꢂ/
ꢂ/
ꢂ/
3
˚
V (A )
Z
11 366(21)
3147(7)
7747(15)
8
16 624
9531
4
10 116
5477
4
16 839
11 485
Reflections collected
Unique reflections
Rint
7179
7179
ꢂ/
0.036
0.0245
0.0466
Data/restraints/parameters
Final R indices R1 [I ꢀ2s(I)], wR2
R indices (all data) R1, wR2
7179/0/479
0.1335, 0.2942
0.1965, 0.3235
9531/0/648
0.0742, 0.1969
0.1130, 0.2191
5477/4/349
0.1026, 0.2876
0.1339, 0.3176
11485/0/784
0.0905, 0.3240
0.1224, 0.3732
ligand resonances shifted slightly downfield from the
free ligands. The 11B{1H}-NMR spectra all show single
resonances as expected (Table 4). For example, the
Table 7
˚
Bond lengths (A) for complexes 10, 14, 25 and 26
10
14
bidentate nitrogen donor complexes 11ꢂ
nances at ꢃ1.13, ꢃ1.20 and ꢃ1.19 ppm, respectively.
Complexes 11ꢂ13 have a singlet resonance in their
/
13 have reso-
Mo(1)ÃC(200)
Mo(1)ÃC(100)
Mo(1)ÃP(1)
Mo(1)ÃP(3)
Mo(1)ÃP(2)
Mo(1)ÃI(3)
Mo(1)ÃI(2)
1.91(2)
Mo(1)ÃC(200)
Mo(1)ÃC(100)
Mo(1)ÃP(1)
Mo(1)ÃP(4)
Mo(1)ÃP(3)
Mo(1)ÃP(6)
Mo(1)ÃI(1)
1.943(9)
1.976(8)
2.524(3)
2.536(3)
2.617(3)
2.646(3)
2.854(2)
/
/
/
1.943(16)
2.542(5)
2.597(5)
2.597(5)
2.873(3)
2.911(3)
/
31P{1H}-NMR spectra (Table 4), similar to that of the
precursor complex, 1. The 31P{1H}-NMR spectrum of
the structurally characterised complex, [MoI(CO)2-
{Ph2P(CH2)PPh2}2][BF4]×
/
CH2Cl2 (14) has a single re-
25
26
sonance at ꢃ10.04 ppm due to the four equivalent
/
Mo(1)ÃO(12)
Mo(1)ÃO(11)
Mo(1)ÃCl(11)
Mo(1)ÃO(1)
Mo(1)ÃO(3)
Mo(1)ÃCl(12)
Mo(1)ÃCl(2)
Mo(1)ÃCl(1)
1.785(13)
1.795(16)
2.179(7)
2.152(6)
2.163(7)
2.265(5)
2.387(4)
2.394(4)
Mo(1)ÃP(7)
Mo(1)ÃP(4)
Mo(1)ÃI(1)
Mo(1)ÃI(2)
Mo(2)ÃP(9)
Mo(2)ÃP(1)
Mo(2)ÃI(1)
Mo(2)ÃI(2)
Mo(2)ÃMo(3)
I(1)ÃMo(3)
I(2)ÃMo(3)
Mo(3)ÃP(3)
Mo(3)ÃP(6)
2.455(5)
2.461(5)
2.938(3)
3.023(3)
2.483(5)
2.498(5)
2.962(3)
3.032(3)
3.155(4)
2.919(3)
3.009(3)
2.496(6)
2.505(5)
phosphorus atoms of the two dppm ligands (Fig. 4).
This data is comparable to that of the related complex,
[MoI(CO)2{Me2P(CH2)PMe2}2]I [37], which has a sin-
gle resonance at ꢃ
/
28 ppm.
The structure of [MoI(CO)2{Ph2P(CH2)PPh2}2][BF4]×
/
2CH2Cl2 (14) (Fig. 4) is the first reported crystal
structure of a seven-coordinate cation containing two
dppm ligands, both of which are coordinated to the
molybdenum centre in a bidentate manner. Complex 14
has capped trigonal prismatic geometry, with iodine
capping the quadrilateral face containing the four
phosphorus atoms. The four MoÃ
/
P bonds differ by a
˚
state for up to 2 months. All complexes 11ꢂ
/
18 are
˚
maximum of 0.122 A [P(1)ꢀ
/
2.524(3) A; P(3)ꢀ
/
2.617(3)
˚
˚
˚
soluble in polar chlorinated solvents such as CH2Cl2 or
CHCl3 and in acetone, but are insoluble in Et2O and
hydrocarbon solvents.
A; P(4)ꢀ
/
2.536(3) A; P(6)ꢀ
/
2.646(3) A] and the MoÃ
/I
˚
bond is 2.854(2) A.
Neutral seven-coordinate complexes containing two
dppm ligands such as [WI2(CO)(dppm)2] [38], prepared
by reaction of [{W(m-I)I(CO)4}2] and dppm in toluene at
room temperature for 24 h, and [MoBr2(CO)2(dppm-
P)(dppm-P,P?)] [39], prepared by addition of two
equivalents of dppm (in CH2Cl2 or THF) to
The IR spectra of complexes 11ꢂ/16 all show two
carbonyl stretching bands (Table 2). They also have two
strong, broad n(BÃ
/
F) bands, confirming the cationic
nature of the complexes. The 1H-NMR spectra (Table 3)
all show the expected features, with the coordinated

52
P.K. Baker et al. / Journal of Organometallic Chemistry 664 (2002) 45ꢂ58
/
Fig. 3. Crystal structure of [MoI2(CO)2(PPh3){Ph2P(CH2)PPh2}] (10), with the atomic numbering scheme. Ellipsoids shown at 20% probability.
and the latter molybdenum complex having one mono-
dentate and one bidentate dppm ligand [39]. Cationic
six-coordinate complexes, [MI(CO)2(dppe-P)(dppe-
P,P?)]I (MꢀMo, W), have also been reported [10,40],
/
containing one monodentate and one bidentate dppe
ligand. Preparation of dppm complexes of the type
[MX(CO)2(dppm-P)(dppm-P,P?)]ꢄ, are well-repre-
sented [10,41ꢂ
containing two bidentate dmpe ligands, namely
[MI(CO)2(dmpe)2]ꢄ
(MꢀMo, W) [37] and
/
43]. However, seven-coordinate cations
/
[MoCl(CO)2(dmpe)2]ꢄ [44], have been reported, with
the latter shown, by X-ray crystallography, to have
capped trigonal prismatic geometry. The similar diars
complex, [MoCl(CO)2(diars)2]ꢄ, was also crystallogra-
phically determined and shown to have capped trigonal
prismatic geometry [1].
Reaction of [MoI(CO)3(NCMe){Ph2P(CH2)PPh2}]-
[BF4] (1), with one equivalent of either sodium dithio-
carbamates, Na[S2CNR2]×
/
xH2O (RꢀMe, Et), or
/
[NH4][S2CNC4H8], in CH2Cl2 at room temperature,
gave the neutral complexes, [MoI(CO)2(S2CX){Ph2P-
Fig. 4. Crystal structure of [MoI(CO)2{Ph2P(CH2)PPh2}2][BF4]×
CH2Cl2 (14), with the atomic numbering scheme. Ellipsoids shown at
20% probability.
/
(CH2)PPh2}] (Xꢀ
spectively, in very good yields. The complexes 19ꢂ
were characterised in the usual manner (Tables 1ꢂ4).
Complexes 19ꢂ21 are moderately air-stable, decompos-
/
NMe2, NEt2, NC4H8) (19ꢂ/21), re-
/
21
?
[MoBr2(CO)(H2CPz2)] in CH2Cl2 or THF at room
/
temperature, have been previously reported [38,39].
Both of these complexes were structurally characterised
by X-ray methods, with the former tungsten complex
possessing two bidentately coordinated dppm ligands,
/
ing within 24 h on exposure to air, with a more marked
affect when in solution. The three complexes were stored
under nitrogen at 17 8C for up to 2 months, with no

P.K. Baker et al. / Journal of Organometallic Chemistry 664 (2002) 45ꢂ
/58
53
as solid samples. No crystals of 22ꢂ
/
24 were obtained,
despite repeated crystallisation attempts, but their
structures should be comparable to the similar complex,
[MoBr2(CO)3(dppe)], which was shown to have dis-
torted capped octahedral geometry [45]. Thus, a struc-
Fig. 5. Proposed structure of [MoI(CO)2(S2CX){Ph2P(CH2)PPh2}]
{XꢀNMe2 (19), NEt2 (20) and NC4H8 (21)}.
ture for the neutral complexes 22ꢂ24, can be proposed
/
/
(Fig. 6), having one carbonyl ligand capping the face
containing one phosphorus of the dppm ligand and the
other two carbonyl ligands, and an uncapped face,
which contains the two halide atoms, or one halide and
the thiocyanate ligand, plus the remaining phosphorus
of the dppm ligand. The IR spectra of complexes 22 and
23 are comparable to the analogous di-iodide com-
obvious deterioration. Single crystals of 19ꢂ21 were not
/
obtained despite repeated attempts, therefore, the struc-
ture of the complexes can only be proposed (Fig. 5). The
IR spectra for 19ꢂ21 have two carbonyl stretching
/
frequencies at similar wavenumbers [1946 and 1882
cmꢃ1 for 19; 1945 and 1880 cmꢃ1 for 20; 1946 and
1880 cmꢃ1 for 21]. The n(CS) stretch for 19 was
plexes, [MI2(CO)3{Ph2P(CH2)nPPh2}] (MꢀMo, W)
/
[35], and the IR spectra of complex 1 (Table 2).
Complexes 22 and 23 have three carbonyl stretching
frequencies; a medium intensity band at 2043 cmꢃ1 (22)
or 2040 cmꢃ1 (23), a strong band at 1972 cmꢃ1 (22) or
1950 cmꢃ1 (23), and a medium stretch at 1885 cmꢃ1
(22) or 1871 cmꢃ1 (23). The IR spectrum of complex 24
has three strong carbonyl stretches at 2071, 1955, 1880
observed at 1786 cmꢃ1 and for 21 at 1789 cmꢃ1
,
whereas complex 20 showed a doublet at 1792 and 1771
cmꢃ1 due to the n(CS) stretch. A representation of the
proposed structure of 19ꢂ
carbonyl arrangement was confirmed by the two differ-
ent n(CÅO) stretching frequencies observed in the IR
spectra of complexes 19ꢂ21 (Table 2). As for the
bis(dppm) complex 14, it is possible that complexes
19ꢂ21 will have capped trigonal prismatic geometry,
/
21 is shown in Fig. 5. The cis-
/
cmꢃ1 and a medium intensity band at 2133 cmꢃ1
which is indicative of an N-bonded thiocyanate ligand.
,
/
1
/
The H-NMR spectra of complexes 22ꢂ24 all show the
/
with the bidentate ligands occupying both edges of the
face capped by the iodide ligand. The 31P{1H}-NMR
expected resonances due to the coordinated dppm
ligand. The room temperature 31P{1H}-NMR spectra
of complexes 23 and 24 both have one singlet resonance,
spectra of complexes 19ꢂ
17.38 ppm, JPÃP 86.0 Hz (19); ꢄ
JPÃP 86.0 Hz (20); ꢄ0.35 ppm, ꢃ17.05 ppm, JPÃP
/
21 are also very similar [ꢄ
/
0.40,
ꢃ
/
ꢀ
/
/
0.17, ꢃ17.34 ppm,
/
at ꢃ
/
1.59 and ꢃ10.98 ppm, respectively, which suggests
/
ꢀ
/
/
/
ꢀ
/
that the complexes are fluxional at room temperature, as
previously observed.
87.3 Hz (21)], with the addition of the bidentate sulfur
ligands resulting in the two phosphorus atoms of the
dppm ligand appearing as two distinct singlets. Thus,
the complexes are no longer fluxional at room tempera-
ture, as was observed for the cationic precursor,
complex 1.
The reaction of 1 with one equivalent of the metal
salts, NaF, NaCl and KSCN, in acetone at room
temperature, afforded the neutral complexes [MoX-
A
concentrated CDCl3 solution of the cation
[MoI(CO)3(NCMe){Ph2P(CH2)PPh2}][BF4] (1), pre-
pared for NMR analysis, gave two decomposition
products upon standing, namely the Mo(V) complex,
[MoCl3O{Ph2PO(CH2)POPh2}] (25) and the unusual
triangular complex, [Mo3(m3-I)2{m2-Ph2P(CH2)PPh2}3]I
(26), which have both been crystallographically char-
acterised. Single crystals suitable for X-ray crystal-
lography of these complexes were obtained from the
NMR tube. The structures of 25 and 26 are shown in
Figs. 7 and 8, respectively. In the crystal structure of
complex 25 (Fig. 7), the terminal Cl(12) and O(11) sites
are disordered with Cl(11) and O(12); the latter, how-
ever, is not represented in the structure shown in Fig. 7.
Both disordered sites are trans to an oxygen atom
bonded to a phosphorus atom of the dppm ligand. The
bond lengths between molybdenum and the two oxygen
I(CO)3{Ph2P(CH2)PPh2}] {XꢀF (22), Cl (23) and
/
NCS (24)}, in very good yields. All three complexes
were characterised by elemental analysis, IR spectro-
1
scopy, H- and 31P{1H}-NMR spectroscopy (Tables 1ꢂ
/
4) {31P{1H}-NMR spectra for complexes 23 and 24}.
The neutral complexes rapidly decompose upon expo-
sure to air, within 30 min for solid samples and within 15
min for samples in solution. The complexes can be
stored under nitrogen at ꢃ
/
17 8C for up to 3 weeks
atoms inserted into the MoÃ
/
P bonds, MoÃ
/
O(1) and
˚
without any obvious deterioration, both in solution and
MoÃO(3), are identical [2.15(7) and 2.163(7) A, respec-
/
tively]. The two ordered chlorine atoms also have
equivalent bond lengths to the molybdenum centre
˚
˚
[MoÃ
/
Cl(1)ꢀ
/
2.394(4) A and MoÃ
/
Cl(2)ꢀ2.387(4) A].
/
The preparation of the homologue of complex 25,
namely [MoCl3O{Ph2PO(CH2)2OPPh2}], was reported
by Lewis and Whyman in 1965 [46], from the treatment
of [Mo(CO)4(dppe)] with excess chlorine in chloroform,
Fig. 6. Proposed structure of [MoXI(CO)3{Ph2P(CH2)PPh2}] {Xꢀ
(22), Cl (23) and NCS (24)}.
/F

54
P.K. Baker et al. / Journal of Organometallic Chemistry 664 (2002) 45ꢂ58
/
(dppe)] and excess bromine, in chloroform at room
temperature, has also been described [46]. However,
reaction of the tungsten complex, [W(CO)4(dppe)], with
excess bromine or chlorine gave the W(VI) complexes,
[WX2O2{Ph2PO(CH2)2OPPh2}] (XꢀCl, Br), rather
/
than the analogous tungsten(V) complexes [46]. Similar
oxidised Mo(IV) complexes, [MoX2O{Ph2P(CH2)2PPh-
(CH2)2POPh2-P,P?,O}] (Xꢀ
and crystallographically characterised [47], by refluxing
[MoBr(CO)(L-P,P?,P??)(h2-RC2R)]Br, {Lꢀ
Ph2P(CH2-
/Br, I), have been prepared
/
CH2PPh2), RꢀMe, Ph}, in chloroform or by refluxing
/
[MoI2(CO)(L-P,P?)(h2-MeC2Me)] in wet acetonitrile,
respectively [47].
The crystal structure of the unusual molybdenum
‘trimer’ [Mo3(m3-I)2{m2-Ph2P(CH2)PPh2}3]I (26) is
shown in Fig. 8. The cation consists of three molybde-
num atoms, each bonded to two phosphorus atoms and
two iodine atoms, in a tetrahedral arrangement, with
both of the iodine atoms bonded to three molybdenum
atoms each. The two phosphorus atoms of each dppm
ligand are bonded to a different molybdenum atom,
with each dppm forming a bridge between two molyb-
denum atoms. The crystal structure also contains one
and a half molecules of water solvate (which is not
included in Fig. 8), probably arising from slightly wet d-
Fig. 7. Crystal structure of [MoCl3O{Ph2OP(CH2)POPh2}] (25), with
the atomic numbering scheme. Ellipsoids shown at 20% probability.
chloroform. The six MoÃ
/P bond lengths are all between
˚
2.455(5) and 2.498(5) A, and are therefore very similar
to one another. Similarly, the bonds between the three
molybdenum atoms and I(1) are all comparable
˚
[2.938(3) A to Mo(1), 2.962(3) A to Mo(2) and
˚
˚
2.919(3) A to Mo(3)] and are slightly shorter than those
˚ ˚
of MoÃ
and 3.009(3) A to Mo(3)], which are comparable to one
another. The two MoÃI bonds are longest for Mo(2),
then Mo(1), with Mo(3)ÃI being the shortest. However,
/I(2), [3.023(3) A to Mo(1), 3.032(4) A to Mo(2)
˚
/
/
˚
these differences are quite small (less than 0.05 A), with
the actual structure of 26 appearing to be symmetrical.
It is difficult to speculate on the formation of
complexes 25 and 26 as they are both very different
from the precursor cation 1. It is probable that traces of
water and/or air have got into the NMR solution
affording the described complexes. However, unusual
decompositions are very commonly observed in molyb-
denum chemistry [46,47].
3. Conclusions
In conclusion, as often observed in molybdenum
chemistry, not only do new reactive starting materials
such as the seven-coordinate cation, [MoI(CO)3(NC-
Me){Ph2P(CH2)PPh2}][BF4] undergo predictable sub-
stitution chemistry as we report here (Scheme 1), but
also unusual rearrangements are often observed, such as
that of 1 in CDCl3 to form the oxidised complex,
[MoCl3O{Ph2PO(CH2)POPh2}] (25) and the novel tri-
Fig. 8. Crystal structure of [Mo3(m3-I)2{m2-Ph2P(CH2)PPh2}3]I (26),
with atomic numbering scheme. Ellipsoids shown with 20% prob-
ability.
at room temperature. The preparation of the analogous
molybdenum(V) oxotribromo-complex, [MoBr3O{Ph2-
PO(CH2)2OPPh2}], from the reaction of [Mo(CO)4-

P.K. Baker et al. / Journal of Organometallic Chemistry 664 (2002) 45ꢂ
/58
55
Scheme 1. A summary of the chemistry detailed in this paper. Reaction conditions: (i) one equivalent Ag[BF4], NCMe, 4 h, under foil (1, 2 and 3); (ii)
one equivalent NCEt, CH2Cl2, 20 h (4); (iii) LꢀP(OR)3, {RꢀMe, Et}, one equivalent P(OR)3, CH2Cl2, 1 h (5 and 6); Lꢀ Pr, Ph}
P(OR)3, {Rꢀi
one equivalent P(OR)3, CH2Cl2, 1 h, (7 and 8); LꢀPPh3, one equivalent PPh3, CH2Cl2, 2 h (9); (iv) one equivalent NaI, acetone, 2 h (10); (v) one
equivalent 1,10-phen,4,7-Me2-1,10-phen or 2,2?-bipy, CH2Cl2, 5 h, (11ꢂ13); (vi) nꢀ1, one equivalent dppm (mꢀ1), dppe (mꢀ2) or dpppr (mꢀ3),
CH2Cl2, 2 h (14ꢂ16); nꢀ2, one equivalent dppm (mꢀ1), CH2Cl2, 2 h (17); nꢀ3, one equivalent dppm (mꢀ1), CH2Cl2, 2 h (18); (vii) one equivalent
Na[S2CNR2] {RꢀMe, Et}, acetone, 18 h (19 and 20); one equivalent [NH4][S2CNC4H8], acetone, 18 h (21); (viii) one equivalent NaF, acetone, 2 h
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
(22); one equivalent NaCl, acetone, 4 h (23); one equivalent KSCN, acetone, 20 h (24); (ix) the complex, [MoI(CO)3(NCMe){Ph2P(CH2)PPh2}][BF4]
(1), dissolved in CDCl3 in an NMR tube.
angular complex [Mo3(m3-I)2{m2-Ph2P(CH2)PPh2}3]I
(26).
silver iodide by-product. The solvent was removed in
vacuo to yield the product, [MoI(CO)3(NCMe)-
{Ph2P(CH2)PPh2}][BF4] (1) as an orangeꢂ/brown solid,
yieldꢀ7.661 g, 95%.
/
Cationic complexes [MoI(CO)3(NCMe){Ph2P(CH2)2-
PPh2}][BF4] (2) and [MoI(CO)3(NCMe){Ph2P(CH2)3-
PPh2}][BF4] (3) were prepared by similar reactions of
equimolar quantities of the neutral complexes
4. Experimental
4.1. General remarks
[MoI2(CO)3{Ph2P(CH2)nPPh2}] (nꢀ2 and 3) with silver
tetrafluoroborate in MeCN. Refer to Table 1 for
physical and analytical data.
/
All reactions described in this paper were carried out
under an atmosphere of dry nitrogen using standard
vacuum/Schlenk line procedures. The starting materials,
[MoI2(CO)3{Ph2P(CH2)nPPh2}] (nꢀ
pared by the published method [35]. All chemicals
were purchased from commercial sources.
/
1ꢂ3), were pre-
/
4.3. [MoI(CO)3(NCEt){Ph2P(CH2)PPh2}][BF4] (4)
To a solution of [MoI(CO)3(NCMe){Ph2P(CH2)-
PPh2}][BF4] (0.503 g, 0.614 mmol) in CH2Cl2 (30 cm3),
propionitrile (0.043 cm3, 0.034 g, 0.617 mmol) was
added and the solution stirred for 20 h. The resultant
solution was filtered over celite and the solvent removed
under vacuum to afford the product [MoI(CO)3(N-
Elemental analyses (C, H, N) were performed using a
Carlo Erba Elemental Analyser MOD 1108 (using
helium as a carrier gas). Infrared spectra were recorded
on a PerkinꢂElmer 1600 series FTIR spectrophot-
/
ometer. 1H-, 11B{1H}-, 13C{1H}- and 31P{1H}-NMR
spectra were recorded on a Bruker AC 250 CP/MAS
NMR spectrometer. 1H- and 13C{1H}-NMR spectra
were referenced to SiMe4, 11B{1H}-NMR spectra to
CEt){Ph2P(CH2)PPh2}][BF4] (4), as an orangeꢂ
crystalline powder, yieldꢀ0.463 g, 90%. Refer to Table
1 for physical and analytical data.
/brown
/
BF3×
/
OEt2 and 31P{1H}-NMR spectra to 85% H3PO4.
4.2. [MoI(CO)3(NCMe){Ph2P(CH2)PPh2}][BF4]
(1)
4.4. [MoI(CO)3{P(OEt)3}{Ph2P(CH2)PPh2}][BF4]
(6)
To
a
solution of [MoI2(CO)3{Ph2P(CH2)PPh2}]
To a solution of [MoI(CO)3(NCMe){Ph2P(CH2)-
PPh2}][BF4] (0.472 g, 0.576 mmol) in CH2Cl2 (30 cm3),
triethylphosphite (0.100 cm3, 0.096 g, 0.577 mmol) was
added and the solution stirred for 1 h. The resultant
(7.500 g, 9.167 mmol) in MeCN (60 cm3), in a foil-
covered Schlenk tube, silver tetrafluoroborate Ag[BF4],
(1.784 g, 9.164 mmol) was added and the solution stirred
for 4 h. The solvent was removed under vacuum and the
crude product dissolved in CH2Cl2 (30 cm3), then
filtered three times over celite to remove all traces of
yellowꢂbrown solution was filtered over celite and the
/
solvent reduced under vacuum to minimum volume (3
cm3). The concentrated solution was layered with Et2O

56
P.K. Baker et al. / Journal of Organometallic Chemistry 664 (2002) 45ꢂ58
/
(2 cm3) and cooled to
[MoI(CO)3{P(OEt)3}{Ph2P(CH2)PPh2}][BF4] (6) was
ꢃ
/
17 8C. The product
4.8. [MoI(CO)2{Ph2P(CH2)PPh2}2][BF4] (14)
obtained as a yellow crystalline powder, yieldꢀ
g, 73%.
Complex
PPh2}][BF4], and the related phosphite complexes,
[MoI(CO)2(NCMe){P(OiPr)3}{Ph2P(CH2)PPh2}][BF4]
(7) and [MoI(CO)2(NCMe){P(OPh)3}{Ph2P(CH2)-
PPh2}][BF4] (8), were prepared by the same method.
Refer to Table 1 for physical and analytical data.
/
0.398
To a solution of [MoI(CO)3(NCMe){Ph2P(CH2)-
PPh2}][BF4] (0.512 g, 0.625 mmol) in CH2Cl2 (30 cm3),
bis(diphenylphosphino)methane (0.240 g, 0.625 mmol)
was added and the solution stirred for 2 h. The resultant
5,
[MoI(CO)3{P(OMe)3}{Ph2P(CH2)-
yellowꢂbrown solution was filtered over celite and the
/
solvent volume reduced under vacuum to minimum
volume (4 cm3). The concentrated solution was layered
with Et2O (4 cm3) and cooled to ꢃ
17 8C for 1 week. The
product, [MoI(CO)2{Ph2P(CH2)PPh2}2][BF4] (14), was
obtained as yellow crystals, suitable for X-ray crystal-
/
4.5. [MoI(CO)2(NCMe)(PPh3){Ph2P(CH2)PPh2}]-
[BF4] (9)
lography, yieldꢀ
Complexes,
/
0.536 g, 76%.
[MoI(CO)2{Ph2P(CH2)nPPh2}{Ph2P-
(CH2)PPh2}][BF4], {nꢀ2 (15) and 3 (16)}, were pre-
/
To a solution of [MoI(CO)3(NCMe){Ph2P(CH2)-
PPh2}][BF4] (0.512 g, 0.625 mmol) in CH2Cl2 (30 cm3),
triphenylphosphine (0.164 g, 0.625 mmol) was added
and the solution stirred for 2 h. The resultant orange
solution was filtered over celite and the solvent removed
under vacuum to give [MoI(CO)2(NCMe)(PPh3-
){Ph2P(CH2)PPh2}][BF4] (9), as an orange crystalline
pared from [MoI(CO)3(NCMe){Ph2P(CH2)PPh2}][BF4]
by the same method, and the related complexes,
[MoI(CO)2{Ph2P(CH2)PPh2}{Ph2P(CH2)nPPh2}][BF4]
{nꢀ
reacting complexes
{Ph2P(CH2)nPPh2}][BF4], (nꢀ
/
2 (17) and 3 (18)}, were similarly prepared by
and 3, [MoI(CO)3(NCMe)-
2 and 3), with one
2
/
equivalent of Ph2P(CH2)PPh2 in CH2Cl2 at room
temperature. Refer to Table 1 for physical and analy-
tical data.
powder, yieldꢀ0.466 g, 72%. Refer to Table 1 for
/
physical and analytical data.
4.6. [MoI2(CO)2(PPh3){Ph2P(CH2)PPh2}] (10)
4.9. [MoI(CO)2(S2CNMe2){Ph2P(CH2)PPh2}] (19)
To a solution of [MoI(CO)3(NCMe){Ph2P(CH2)-
PPh2}][BF4] (0.500 g, 0.610 mmol) in CH2Cl2 (30 cm3),
triphenylphosphine (0.160 g, 0.610 mmol) was added,
after stirring for 2 h, sodium iodide (0.092 g, 0.614
mmol) and acetone (30 cm3) were added in situ and the
resultant solution stirred for a further 20 h. The solvents
were removed under vacuum, the crude product dis-
solved in CH2Cl2 (30 cm3), then filtered three times over
celite and the solvent removed to yield the product
[MoI2(CO)2(PPh3){Ph2P(CH2)PPh2}] (10), as a bright
To a solution of [MoI(CO)3(NCMe){Ph2P(CH2)-
PPh2}][BF4] (0.455 g, 0.555 mmol) in acetone (30 cm3),
Na[S2CNMe2]×
/
2H2O, (0.099 g, 0.554 mmol) was added
and the solution stirred for 18 h. The solvent was
removed in vacuo, the crude product dissolved in
CH2Cl2 (30 cm3) and filtered three times over celite.
The solvent was removed, under vacuum, to give the
neutral product, [MoI(CO)2(S2CNMe2){Ph2P(CH2)-
PPh2}] (19), as a brown solid, yieldꢀ/0.389 g, 86%.
Complexes 20, [MoI(CO)2(S2CNEt2){Ph2P(CH2)-
orange powder, yieldꢀ0.411 g, 64%. Refer to Table 1
for physical and analytical data.
/
PPh2}], and 21, [MoI(CO)2(S2CNC4H8){Ph2P(CH2)-
PPh2}], were prepared by the same method. Refer to
Table 1 for physical and analytical data.
4.7. [MoI(CO)2(1,10-phen){Ph2P(CH2)PPh2}][BF4]
(11)
4.10. [MoFI(CO)3{Ph2P(CH2)PPh2}] (22)
To a solution of [MoI(CO)3(NCMe){Ph2P(CH2)-
PPh2}][BF4] (0.507 g, 0.619 mmol) in CH2Cl2 (30 cm3),
1,10-phenanthroline (0.112 g, 0.621 mmol) was added
and the solution stirred for 5 h. The resultant dark
brown solution was filtered over celite and the solvent
removed under vacuum to afford the product (11), as
To a solution of [MoI(CO)3(NCMe){Ph2P(CH2)-
PPh2}][BF4] (0.520 g, 0.635 mmol) in acetone (30 cm3),
sodium fluoride, (0.027 g, 0.643 mmol) was added and
the solution stirred for 2 h. The solvent was removed
from the resultant cloudy brownꢂgreen solution, in
/
vacuo, and the crude product dissolved in CH2Cl2 (30
cm3). Filtration of the solution three times over celite,
followed by removal of the solvent under vacuum, gave
the neutral product, [MoFI(CO)3{Ph2P(CH2)PPh2}]
dark brown crystalline powder, yieldꢀ0.434 g, 75%.
/
The novel complexes, [MoI(CO)2(4,7-Me2-1,10-phen)-
{Ph2P(CH2)PPh2}][BF4] (12) and [MoI(CO)2(2,2?-bi-
py){Ph2P(CH2)PPh2}][BF4] (13), were prepared by the
same method. Refer to Table 1 for physical and
analytical data.
(22), as a brownꢂ
/
green solid, yieldꢀ0.336 g, 75%.
/
Neutral complexes, [MoClI(CO)3{Ph2P(CH2)PPh2}]
(23), and [Mo(NCS)I(CO)3{Ph2P(CH2)PPh2}] (24),

P.K. Baker et al. / Journal of Organometallic Chemistry 664 (2002) 45ꢂ
/58
57
were prepared by the same method. Refer to Table 1 for
physical and analytical data.
Acknowledgements
D.S.M. thanks the EPSRC for a studentship. We also
thank the EPSRC and the University of Reading for
funds to purchase the Image Plate System and A.W.
Johans for his assistance with the X-ray crystallographic
investigations.
4.11. X-ray crystallographic study
Crystal data for the complexes 10, 14, 25 and 26 are
given in Table 6, together with refinement details. Data
were collected with MoꢂKa radiation using the MAR-
/
References
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