Synthesis and spectroscopic and X-ray structural characterisation of some para-substituted triaryltin(pentacarbonyl)manganese(I) complexes

Article abstract of DOI:10.1016/S0020-1693(01)00792-7

A series of para-substituted triaryltin(pentacarbonyl)manganese(I) compounds [(p-XC₆H₄)₃SnMn(CO)₅: II, X = CH₃; III, X = CH₃O; IV, X = CH₃S; V, X = F; VI, X = Cl; VII, X = CH

Full text of DOI:10.1016/S0020-1693(01)00792-7

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Inorganica Chimica Acta 329 (2002) 36–44
Synthesis and spectroscopic and X-ray structural characterisation
of some para-substituted triaryltin(pentacarbonyl)manganese(I)
complexes
Dharamdat Christendat, Ivor Wharf *, Anne-Marie Lebuis, Ian S. Butler *,
Denis F.R. Gilson *
Department of Chemistry, McGill Uni6ersity, 801, Sherbrooke Street, W. Montreal, Quebec, Canada H3A 2K6
Received 2 July 2001; accepted 31 October 2001
Abstract
A series of para-substituted triaryltin(pentacarbonyl)manganese(I) compounds [(p-XC6H4)3SnMn(CO)5: II, X=CH3; III,
X=CH3O; IV, X=CH3S; V, X=F; VI, X=Cl; VII, X=CH3S(O2)] is reported for comparison with the known phenyl analogue
I. IR data [w(CO)] as well as complete 119Sn/55Mn/13C solution NMR results are given for I–VII. Chemical shifts, 119Sn versus
55Mn, except I, correlate well, but have differing single parameter (SP) correlations, 119Sn versus |I and 55Mn versus |°. These
p
results are compared with previous SP studies of the 119Sn solution NMR spectra of the series, (p-XC6H4)4Sn and (p-XC6H4)3SnY
(Y=Cl, Br, I). Full crystal structures are reported for compounds II–VI. All are similar to that of I, with the Mn(CO)5 moiety
being a distorted tetragonal pyramid, and having a quasi-mirror plane through the central C4MnꢀSnC3 skeleton. The Ar3Sn are
distorted trigonal propellers with ring torsion angles in the range 30–80°, the exception being IV with one torsion angle of 22°.
© 2001 Elsevier Science B.V. All rights reserved.
Keywords: Triaryltin(pentacarbonyl)manganese(I) compounds; Crystal structures; IR spectra; 119Sn/55Mn/13C NMR
cleus (I=1/2) bound to one or more nuclei X (I\1/2)
provide much more information [5–7] than do the
1. Introduction
corresponding solution spectra where only the 119Sn
chemical shift of the solution species is obtained. How-
ever, for the complete analysis of solid-state NMR
data, a precise value of rSnꢀX must be known. Thus as
part of our solid-state study of Ar3SnMn(CO)5 deriva-
tives, crystal structures of all but one of the compounds
examined were obtained and compared with that of
(Ph3Sn)Mn(CO)5 [8]. Some aspects of the crystal struc-
tures determined have already been given [4]. Full
details of these structures are now reported here.
Substituent effects in the 119Sn and 13C NMR spectra
of aryltins have been reported recently for various
Ar4Sn and Ar3SnX (Ar=Aryl; X=Cl, Br, I, NCS)
compounds [1,2] as well as earlier for ArSn(CH3)3 [3].
We have extended these studies to the bimetallic sys-
tem, Ar3SnMn(CO)5, by observing for the first time the
solid-state 119Sn NMR spectra for a series of these
compounds containing a range of para-substituents [4].
In this work, use was made of para-substituents having
varying s- and p-interactions with the phenyl rings to
probe differences in the various NMR parameters that
can be obtained in this type of study.
Comprehensive solution NMR data (119Sn, 55Mn,
and 13C) have also been obtained for the various para-
substituted (Ar3Sn)Mn(CO)5 derivatives, enabling a
study of electronic substituent effects in this system,
independent of structural factors, to be realised. In
addition, a comparison with an earlier study [1] of
para-substituent effects in the 119Sn and 13C NMR
spectra of Ar4Sn and Ar3SnX (X=Cl, Br, I) enables
the bonding characteristics of Mn(CO)5 versus halogen
Solid-state (CP-MAS) NMR spectra of a 119Sn nu-
* Corresponding authors. Tel.: +1-514-398 6931; fax: +1-514-398
3797.
E-mail addresses: ivor.wharf@mcgill.ca (I. Wharf), ian.butler@
mcgill.ca (I.S. Butler), denis.gilson@mcgill.ca (D.F.R. Gilson).
0020-1693/02/$ - see front matter © 2002 Elsevier Science B.V. All rights reserved.
PII: S0020-1693(01)00792-7

D. Christendat et al. / Inorganica Chimica Acta 329 (2002) 36–44
37
as a substituent on tin in Ar3SnX complexes to be
assessed. Although 55Mn NMR solution data for
R3SnMn(CO)5 derivatives, including Ph3SnMn(CO)5,
have been known for some time [9–13], only one 119Sn
study, of Ph3SnMn(CO)5, is available [14] at this time.
g crushed ice. Extracting the pale green solid obtained,
using boiling hexane, followed by evaporation of the
filtrate and cooling gave the triaryltin(pentacar-
bonyl)manganese(I) compound in 65–85% yield. Re-
crystallisation gave crystals suitable for X-ray analysis.
Further details of the (Ar3Sn)Mn(CO)5 I–VI prepared
in this work are given in Tables 1–3.
2. Experimental
2.1.1. Tris(p-methylsulphonylphenyl)tin(pentacarbonyl)-
manganese(I) (VII)
All experimental procedures, including the synthesis
of triaryltin chlorides, and the solution (CDCl3) NMR
(
A slurry of m-chloroperbenzoic acid (15.5 g; 85%) in
dichloromethane (CH2Cl2) (50 ml) was added slowly to
a well-stirred solution of IV (6.95 g) over 2 h at
−10 °C. Further CH2Cl2 (60 ml) was added and the
stirred mixture was allowed to warm up slowly to r.t.
The white suspension was separated, redissolved in
(1:1) CH2Cl2/ether (150 ml), and then addition of ether
(125 ml) to the filtrate precipitated the off-white
product. This product was then dissolved in the least
amount of CH2Cl2 and reprecipitated by slow addition
of benzene: yield, 73%; m.p. (dec) 260–264 °C. Anal.
Calc. for C26H21MnO11S3Sn: C, 40.07; H, 2.72; S, 12.43.
Found: C, 40.33; H, 2.56; S, 12.25%. NMR (ppm):
l(119Sn) (CDCl3): 6.63(0.05), (solid) −6.63 (0.2);
l(55Mn) [w1/2(Hz)] (THF): −2435 [8642]. Vibrational
[IR/Raman] and 13C NMR data are reported in Tables
2 and 3, respectively.
119Sn and 13C) measurements were as given earlier
[1,15,16]. Microanalyses were performed by the Micro-
analysis Service of the University of Montreal. All
syntheses and manipulations were done under dry ni-
trogen. NMR (55Mn) spectra of THF-d8 solutions were
obtained using a Varian XL-300 spectrometer and ref-
erenced against external KMnO4 in D2O. Mid-IR spec-
tra of powders were acquired using a Bruker IFS-48
instrument equipped with a A-590 microscope. Raman
spectra of powders in the standard sample cup were
recorded in a Bruker IFS-88 FT-IR spectrometer fitted
with a FRA-106 Raman module, using the CaF2
beamsplitter.
2.1. Synthesis
All the para-substituted triaryltin(pentacarbonyl)-
manganese(I) compounds, with the exception of that
given below, were obtained using the procedure re-
ported earlier for the triphenyltin compound [17]. Thus
dimanganese decacarbonyl (7.5 mmol) in dry THF (35
ml) was stirred with sodium amalgam (0.95 g Na/10 ml
Hg) for 35 min at room temperature (r.t.) and the
amalgam was then separated. Triaryltin chloride (15.5
mmol) was added to the THF solution of NaMn(CO)5,
the mixture stirred for 40 min and then poured on 100
2.2. Crystal structure determinations
For compounds II–VI a suitable crystal was selected
from those available (Table 1) and X-ray data were
collected [T=293(2) K] on a Rigaku AFC6S diffrac-
,
tometer using Mo Ka (u=0.70930 A) radiation. Cell
measurements were by standard methods and during
each data collection, intensities of three standard reflec-
tions checked after every 200 reflections, showed essen-
Table 1
Synthesis and characterisation details for triaryltin(pentacarbonyl)manganese(I) complexes ([(p-XC6H4)3SnMn(CO)5])
Complex
X
Solvent
Yield (%) m.p. (°C)
Colour
l(119Sn) (ppm)
l(55Mn) (ppm)
b
CDCl3 Solid a
THF
(Dw1/2)
I
H
hexane
85
150–152
(148–150) c
137–138
146–148
126–128
128–130
143–145
white
−11.93 −13.6 (×2), 2.8, 5.7 −2502 (−2530) d 4470 (3000) d
II
CH3
CH2Cl2/hexane 67
75
SCH3 CH2Cl2/hexane 74
white
white
pale-yellow −4.84
white
white
−10.37
−6.33
−16.6
11.4
−2526
−2524
−2498
−2493
−2479
5662
5736
9089
5588
6407
III
IV
V
OCH3 hexane
12.0
F
Cl
benzene/heptane 70
CH2Cl2/butanol 73
−0.19
1.13
6.6, 16.0
−32.1
VI
a Ref. [7].
b Peak width at half-height.
c Ref. [17].
d Ref. [13].

38
D. Christendat et al. / Inorganica Chimica Acta 329 (2002) 36–44
Table 2
Vibrational data [w(CO)] (cm−1) for [(p-XC6H4)3SnMn(CO)5]
Complex
Assignment
a(12)
b1
{e+a(11)
}
I
IR
Raman
IR
Raman
IR
Raman
IR
Raman
IR
Raman
IR
Raman
IR
Raman
2092
2093
2090
2091
2095
2093
2095
2093
2096
2095
2096
2096
2106
2107
2029
2024
2030
2026
2033
2023
2034
2023
2031
2031
2035
2033
2051
2051
2012
2013
2009
2006
2014
2014
1998
1983
1991
1975
1975
1981
1986
1983
1988
1979
1991
1991
1991
1983
1994
1980
1981
II
1992
1991
1998
2001
2001
III
IV
V
2008
2012
2012
2012
2022
2027
2029
1999
2002
1998
2001
VI
VII
2009
2015
1989
1991
Table 3
13C NMR data [l (ppm); nJ(119Sn–13C)] for [(p-XC6H4)3SnMn(CO)5]
Complex
l(Ci) 1J(SnC)
l(Co) 2J(SnC)
l(Cm) 3J(SnC)
l(Cp)
l(COeq
)
l(COax
)
l(CH3)
I
II
141.2 (382.3)
137.4 (393.5)
131.7 (405.2)
137.0 (388.9)
135.7 (383.5)
137.4 (372.8)
148.5 (336.2)
136.7 (37.6)
136.6 (38.3)
137.7 (43.4)
136.7 (38.5)
138.0 (43.8)
137.7 (41.3)
137.6 (38.3)
128.5 (46.6)
129.3 (48.6)
114.4 (51.8)
126.1 (47.5)
115.7 (51.1)
128.9 (47.1)
127.1 (43.8)
128.6
138.3
160.1
139.4
163.5
135.5
141.7
213.4
213.4
213.6
212.9
212.6
212.3
211.8
211.6
211.7
211.7
211.2
210.8
210.6
210.2
21.4
54.9
15.1
III
IV
V a
VI
VII
44.5
a 1J(19F–13C), 247.9 Hz; 2J(19F–13C), 19.5 Hz; 3J(19F–13C), 6.5 Hz; 4J(19F–13C), 3.9 Hz.
tially no decomposition over the data collection period.
Full crystal parameters and data collection information
are listed in Table 4.
The structures were solved by direct methods with
SHELXS-86 [18] and refined on F2 using SHELXL-93 [19].
Atom scattering factors and anomalous scattering
terms were from the usual sources [20]. For all struc-
tures, all non-hydrogen atoms in the structure were
refined anisotropically with the hydrogen atoms calcu-
from the corresponding (p-XC6H4)3SnCl, as white or
pale-yellow solids (Table 1) using the standard proce-
dure first used for I, Ph3SnMn(CO)5 [17]. The products
are relatively stable crystalline solids but do react
slowly over 2–3 months in air to give discoloured
materials presumably containing MnO2 as well as other
decomposition products. However, VII where p-X=
CH3S(O2), could not be made directly from the
Ar3SnCl precursor [22] possibly due to the strong elec-
tron-withdrawing ability of p-H3S(O2)ꢀ causing the
SnꢀCl bond to be less polar. This would then hinder the
displacement of chloride by the nucleophile,
[Mn(CO)5]−. Instead, the sulphone complex was pre-
pared by an alternate route, viz. mild oxidation of IV
using m-chloroperbenzoic acid [15] with the tempera-
ture at −10 °C or below, to avoid formation of
MnO2.
,
lated at idealised positions, d(CꢀH)=0.93–0.98 A.
More details of the refinement are given in Table 4.
Pertinent geometric parameters for Ar3Sn and
Mn(CO)5 units of molecules II–VI are given in Table 5.
An ORTEP [21] view of the molecule of IV (Fig. 1)
provides the general numbering scheme used and that
in Fig. 2 shows the numbering scheme for the second
molecule in the asymmetric unit of V.
3.2. IR and Raman spectra
3. Results and discussion
Both IR and Raman solid-state data for the carbonyl
stretching region for compounds I–VII are given in
Table 2. An idealised Mn(CO)5 moiety has local C46
symmetry giving rise to four w(CO) peaks, a(12) (IR, R)
(eq), b1 (R), E (IR, R), and a(11) (IR, R) (ax) [23]. In fact
3.1. Syntheses
The new para-substituted triaryltin(pentacar-
bonyl)manganese(I) compounds II–VI were obtained

D. Christendat et al. / Inorganica Chimica Acta 329 (2002) 36–44
39
the R3SnMn(CO)5 molecules have no symmetry but in
solution with free rotation about the SnꢀMn bond, they
behave as symmetric-tops (Cꢀ6) with the w(CO) stretch-
ing modes assigned as 3a1 and e modes, all IR and
Raman active [24]. However, since the mode equivalent
to b1 is weaker in the IR and stronger in the Raman,
which e is split is strongly IR active while the other is
only observed in the Raman spectrum.
The spectra of I and VII are more complex. For I,
this is expected since there are four independent
molecules in the cell [8]. However, there are several
pseudo-symmetry elements in the cell which cause pairs
of molecules to be effectively equivalent, giving a situa-
tion like that for V where IR and Raman data also do
not distinguish between molecules differing only slightly
in their conformations. For VII there are six modes
observed in both the IR and Raman spectra with some
evidence of mutual exclusion. Thus, the packing of the
asymmetric R3SnMn(CO)5 units of VII in the crystal
may well differ from that found for I–IV. However,
to-date, crystals of VII suitable for X-ray study have
not been available.
w(CO) solution data have usually been assigned as a1(2)
,
b1, e, and a(11), in that order, although the latter pair can
overlap or interchange [25]. Thus, for Ph3SnMn(CO)5,
w(CO) IR-data (cm−1) in hexane are 2095 m (a(12)),
2029 w (b(1)), and 2004 s (e, and a(11)).
In the solid state, all symmetry is lost and five w(CO)
peaks are expected, both IR and Raman active. The
results for II–VI (Table 2) agree with this analysis
while the mutual exclusion for IR and Raman data,
particularly for e, and a(11) modes, is consistent with the
inversion centres present in the unit cells. However, the
peak assigned to b1 is still weaker in the IR and more
prominent in the Raman spectrum. The results for IV
are consistent with a more symmetric solid-state struc-
ture, which is not borne out by the X-ray data. In this
case, we propose that one of the components into
3.3. Solution NMR data
All NMR data sets have been examined for correla-
tion with various substituent parameters (SP) [26]. As
shown earlier for several series of para-disubstituted
Table 4
Crystal data and structure refinement parameters for [(p-XC6H4)3SnMn(CO)5]
Compound
II
III
IV
V
VI
Empirical formula
Formula mass
Crystal system
Space group
C26H21MnO5Sn
587.06
triclinic
C26H21MnO8Sn
635.06
monoclinic
P21/c
C
683.24
monoclinic
P21/n
26H21MnO5S3Sn C23H12F3MnO5Sn
C23H12Cl3MnO5Sn
648.31
monoclinic
P21/c
589.96
triclinic
(
(
P1
P1
Unit cell dimensions
,
a (A)
8.815(2)
14.096(2)
11.161(2)
17.000(10)
90
91.71(2)
90
2673(2)
4; 1
1.578
10.966(1)
21.229(2)
12.297(3)
90
101.22(1)
90
2808.0(8)
4; 1
1.616
10.636(5)
11.450(3)
21.992(7)
83.20(3)
78.30(4)
63.03(2)
2336(2)
4; 2
9.918(2)
22.940(4)
11.718(2)
90
109.78(1)
90
2508.8(8)
4; 1
1.716
,
b (A)
11.160(3)
13.689(2)
98.28(2)
,
c (A)
h (°)
i (°)
k (°)
V (A )
91.11(2)
106.31(2)
1276.5(5)
2; 1
3
,
Z; Z%
Dcalc (g cm−1
)
1.527
1.703
Crystal size (mm)
0.36×0.18×0.13
1.505
0.35×0.22×0.12
1.452
0.45×0.25×0.22 0.52×0.35×0.12
0.51×0.49×0.09
1.849
v (mm−1
)
1.596
1.664
Tmax, Tmin
0.71; 0.67
ꢀ scans
0.76; 0.64
ꢀ–2q scans
c method
2.18; 24.98
−175h517,
05k513,
−205l520
1264
0.66; 0.57
ꢀ–2q scans
c method
2.12; 24.99
−135h512,
05k525,
05l514
1360
0.66; 0.45
ꢀ scans
0.62; 0.33
ꢀ scans
c method
2.04; 24.97
−115h511,
05k527,
05l513
1264
Data collection method
Absorption correction
qmin; qmax (°)
c method
2.25; 24.96
−105h510,
−135k513,
−165l516
584
c method
2.18; 25.00
−115h512,
05k513,
−255l526
1168
Index ranges
F(000)
Number of reflections
measured
9016
9414
9864
16 582
8805
Number of unique reflections 4508 (0.025)
(Rint
4716 (0.083)
2891
4961 (0.077)
3188
8291 (0.079)
5383
4412 (0.062)
3381
)
Number of observed
reflections [I]2|(I)]
R1 observed (total)
wR2 observed (total)
Goodness-of-fit (S)
3314
0.0400 (0.0680)
0.0723 (0.0788)
1.044
0.0546 (0.1121)
0.0918 (0.1033)
1.023
0.0544 (0.1073)
0.1079 (0.1240)
1.037
0.0518 (0.0988)
0.0997 (0.1108)
1.101
0.0474 (0.0748)
0.1192 (0.1264)
1.068
R1=ꢀ(ꢁꢁFoꢁ−ꢁFcꢁꢁ)/ꢀꢁFoꢁ. wR2=[ꢀ[w(Fo2−Fc2)2/ꢀ(wFo2)2]1/2. S=[ꢀ[w(Fo2−Fc2)2/(number of reflections−number of parameters)]1/2. Function
minimised, ꢀ[w(Fo2−Fc2].

40
D. Christendat et al. / Inorganica Chimica Acta 329 (2002) 36–44
Table 5
C(4)ꢀMnꢀSn
C(5)ꢀMnꢀSn
85.9(2)
177.4(3)
88.9(2)
174.4(3)
,
Bond lengths (A) and bond angles (°) for [(p-XC6H4)3SnMn(CO)5]
C(12)C(11)SnMn
C(22)C(21)SnMn
C(32)C(31)SnMn
−101.3(5)
48.3(7)
(a) Compounds II and VI
II (X=CH3)VI (X=Cl)
54.64(10) −116.3(6)
31.3(6)
−22.0(7)
SnꢀMn
2.693(1)
1.829(5)
1.847(5)
1.839(6)
1.845(5)
1.812(7)
2.150(4)
2.159(4)
2.145(4)
2.6814(12)
1.821(10)
1.841(8)
1.836(9)
1.824(9)
1.821(10)
2.142(6)
2.143(6)
2.151(7)
MnꢀC(1)
MnꢀC(2)
MnꢀC(3)
MnꢀC(4)
MnꢀC(5)
SnꢀC(11)
SnꢀC(21)
SnꢀC(31)
C(4)MnSnC(11)
C(4)MnSnC(21)
C(4)MnSnC(31)
−116.2(3)
8.1(3)
125.9(3) −118.8(3)
124.6(3)
6.3(3)
C(15)C(14)Z a(1x)
C(17)
7.4(11)
176.6(7)
1.3(12)
−5.4
C(25)C(24)Z a(2x)
C(27)
168.5(6)
33.2(8)
C(35)C(34)Z a(3x)
C(37)
C(1)ꢀO(1)
C(2)ꢀO(2)
C(3)ꢀO(3)
C(4)ꢀO(4)
C(5)ꢀO(5)
1.141(5)
1.138(5)
1.137(6)
1.137(5)
1.143(6)
1.153(10)
1.130(9)
1.152(10)
1.141(9)
1.130(10)
(c) Compound V (X=F)
Molecule A
Molecule B
Sn(2)ꢀMn(2)
Mn(2)ꢀC(6)
Mn(2)ꢀC(7)
Mn(2)ꢀC(8)
Mn(2)ꢀC(9)
Mn(2)ꢀC(10)
Sn(2)ꢀC(41)
Sn(2)ꢀC(51)
Sn(2)ꢀC(61)
Sn(1)ꢀMn(1)
Mn(1)ꢀC(1)
Mn(1)ꢀC(2)
Mn(1)ꢀC(3)
Mn(1)ꢀC(4)
Mn(1)ꢀC(5)
Sn(1)ꢀC(11)
Sn(1)ꢀC(21)
Sn(1)ꢀC(31)
2.656(2)
2.664(2)
1.847(9)
1.826(8)
1.834(9)
1.852(10)
1.841(9)
2.145(7)
2.153(7)
2.155(7)
1.848(9)
1.823(9)
1.842(9)
1.838(9)
1.820(8)
2.147(6)
2.143(7)
2.151(7)
C(11)ꢀSnꢀC(21)
C(11)ꢀSnꢀC(31)
C(21)ꢀSnꢀC(31)
C(11)ꢀSnꢀMn
C(21)ꢀSnꢀMn
C(31)ꢀSnꢀMn
106.0(2)
107.7(2)
108.2(2)
112.63(12) 105.2(2)
110.34(11) 114.5(2)
111.66(11) 113.2(2)
108.3(2)
109.5(3)
105.9(3)
C(1)ꢀMnꢀSn
C(2)ꢀMnꢀSn
C(3)ꢀMnꢀSn
C(4)ꢀMnꢀSn
C(5)ꢀMnꢀSn
84.2(2)
84.3(2)
86.2(2)
87.7(2)
179.0(2)
85.6(3)
82.5(3)
89.3(3)
86.6(3)
177.5(3)
C(1)ꢀO(1)
C(2)ꢀO(2)
C(3)ꢀO(3)
C(4)ꢀO(4)
C(5)ꢀO(5)
1.120(9)
1.150(9)
1.126(9)
1.151(9)
1.133(8)
C(6)ꢀO(6)
C(7)ꢀO(7)
C(8)ꢀO(8)
C(9)ꢀO(9)
C(10)ꢀO(10)
1.134(8)
1.126(8)
1.131(9)
1.131(9)
1.120(9)
C(12)C(11)SnMn
C(22)C(21)SnMn
C(32)C(31)SnMn
56.4(4)
−121.0(3)
−109.5(4) −116.9(6)
−96.2(5)
56.0(6)
C(11)ꢀSn(1)ꢀC(21)
C(11)ꢀSn(1)ꢀC(31)
C(21)ꢀSn(1)ꢀC(31)
C(11)ꢀSn(1)ꢀMn(1)
C(21)ꢀSn(1)ꢀMn(1)
C(31)ꢀSn(1)ꢀMn(1)
104.8(3) C(41)ꢀSn(2)ꢀC(51)
104.0(2) C(41)ꢀSn(2)ꢀC(61)
107.8(3) C(51)ꢀSn(2)ꢀC(61)
114.8(2) C(41)ꢀSn(2)ꢀMn(2)
114.1(2) C(51)ꢀSn(2)ꢀMn(2)
110.5(2) C(61)ꢀSn(2)ꢀMn(2)
107.8(3)
104.6(3)
104.0(3)
113.8(2)
110.5(2)
115.3(2)
C(4)MnSnC(11)
C(4)MnSnC(21)
C(4)MnSnC(31)
121.6(2)
3.4(2)
−117.0(2) −116.6(4)
123.9(3)
5.0(4)
(b) Compounds III and IV
C(1)ꢀMn(1)ꢀSn(1)
C(2)ꢀMn(1)ꢀSn(1)
C(3)ꢀMn(1)ꢀSn(1)
C(4)ꢀMn(1)ꢀSn(1)
C(5)ꢀMn(1)ꢀSn(1)
83.6(3) C(6)ꢀMn(2)ꢀSn(2)
84.5(3) C(7)ꢀMn(2)ꢀSn(2)
87.6(2) C(8)ꢀMn(2)ꢀSn(2)
86.0(2) C(9)ꢀMn(2)ꢀSn(2)
178.4(2) C(10)ꢀMn(2)ꢀSn(2)
85.6(2)
86.5(3)
83.5(3)
87.9(3)
178.9(3)
III
IV (X=SCH3)
(X=OCH3)
SnꢀMn
2.669(2)
1.854(9)
1.849(8)
1.837(8)
1.824(8)
1.808(9)
2.144(6)
2.153(4)
2.163(6)
2.6596(12)
1.827(8)
1.849(9)
1.867(8)
1.856(9)
1.832(9)
2.156(7)
2.145(7)
2.171(7)
MnꢀC(1)
MnꢀC(2)
MnꢀC(3)
MnꢀC(4)
MnꢀC(5)
SnꢀC(11)
SnꢀC(21)
SnꢀC(31)
C(12)C(11)Sn(1)Mn(1) −141.3(5) C(42)C(41)Sn(2)Mn(2) 111.7(6)
C(22)C(21)Sn(1)Mn(1)
C(32)C(31)Sn(1)Mn(1)
59.6(6) C(52)C(51)Sn(2)Mn(2) −54.0(6)
66.0(6) C(62)C(61)Sn(2)Mn(2) 131.0(6)
C(4)Mn(1)Sn(1)C(11)
C(4)Mn(1)Sn(1)C(21)
C(4)Mn(1)Sn(1)C(31) −120.4(3) C(9)Mn(2)Sn(2)C(61) −123.9(4)
122.3(3) C(9)Mn(2)Sn(2)C(41)
1.2(3) C(9)Mn(2)Sn(2)C(51)
115.2(4)
−6.3(4)
C(1)ꢀO(1)
C(2)ꢀO(2)
C(3)ꢀO(3)
C(4)ꢀO(4)
C(5)ꢀO(5)
1.129(8)
1.140(8)
1.136(8)
1.144(8)
1.129(8)
1.153(9)
1.133(9)
1.125(8)
1.133(8)
1.133(9)
a Z=O, x=4, or Z=S, No x.
benzenes [27] and for Ar4Sn and Ar3SnX [8], 13C chem-
C(11)ꢀSnꢀC(21)
C(11)ꢀSnꢀC(31)
C(21)ꢀSnꢀC(31)
C(11)ꢀSnꢀMn
C(21)ꢀSnꢀMn
C(31)ꢀSnꢀMn
109.5(2)
103.6(3)
100.9(3)
108.4(3)
114.8(2)
ical shift data (Table 3) correlate well with |° (Fig.
103.0(2)
103.5(2)
113.0(2)
112.15(12) 112.8(2)
115.0(2)
R
3(a)). In contrast, 1J(119Sn–13C) values are less than
those for the corresponding Ar4Sn and Ar3SnX deriva-
tives, and correlate with |p [Fig. 3(b)] or |° (r= −
0.970) rather than |R, as was found for Ar4Sn and
Ar3SnX. Both 119Sn and 55Mn chemical shifts show the
same trend with para-substituent (Fig. 4), especially if
the phenyl data point is omitted. This requirement
p
115.1(2)
C(1)ꢀMnꢀSn
C(2)ꢀMnꢀSn
C(3)ꢀMnꢀSn
86.7(3)
85.3(2)
83.8(2)
83.5(2)
84.9(2)
88.3(2)

D. Christendat et al. / Inorganica Chimica Acta 329 (2002) 36–44
41
would suggest that the 119Sn and 55Mn chemical shifts
have different SP behaviour. Thus, l(119Sn) depends on
|I (Fig. 5(a)) while l(55Mn) varies almost equally with
|° [Fig. 5(b)] or |p (r=0.9909). The same correlation
p
of l(55Mn) with Hammett constant values was reported
earlier for the series CH3−nFnMn(CO)5 [9] as well as
for
the
RMn(CO)5,
RMn(PPh3)(CO)4,
and
RCOMn(PPh3)(CO)4 (R=XC6H4CH2) series [28]. By
comparison, inverse correlations are found with
l(119Sn) data for Ar4Sn (|R or |° ) and for Ar3SnI (|p
R
or |°) [1]. There are even substituent effects in
p
l(13COax) [|°; r= −0.935] and l(13COeq) [|°; r= −
p
p
0.945] although the variation in chemical shifts is small
in these cases. Dual substituent parameter (DSP) analy-
ses for I–VII (Table 6) confirm the strong dependence
of l(119Sn) on the inductive parameter while compara-
Fig. 3. Correlation of 13C NMR data for I–VII with substituent
parameters: (a) l(Cipso) vs. |° (r=0.9668; n=7). (b) 1J(119Sn–13C)
R
vs. |p (r=0.9903; n=7).
Fig. 1. ORTEP view of the molecule of IV showing the general
numbering scheme adopted for II–VI. Ellipsoids are drawn at 40%
probability level.
Fig. 4. Plot of l55Mn vs. l119Sn for the series II–VII; omitting the
data point for I gives r=0.9533 (n=6).
ble resonance and inductive parameters for l(55Mn) are
also consistent with the SP behaviour.
The electronic environment around the tin atom in
Ar3SnX systems may be simply considered in terms of
the resonance structures A–C below. With X=Ar, B is
Fig. 2. ORTEP view of the second molecule of V showing the number-
ing scheme adopted. Ellipsoids are drawn at 40% probability level.

42
D. Christendat et al. / Inorganica Chimica Acta 329 (2002) 36–44
1
In contrast with Ar3SnMn(CO)5, J(119Sn–13C) values
are less than for a given Ar4Sn, implying that the
SnꢀMn bond has more tin-5s character than SnꢀAr in
Ar4Sn due to the lower effective electronegativity of
Mn(CO)5 compared with an aryl group [14], and that C
is now an important contributor to the overall struc-
ture. This result is seemingly contradicted by the trend
in l(119Sn) data for the same series which suggest that
tin in Ar3SnMn(CO)5 is even less shielded than in the
corresponding Ar3SnCl. Shielding of heavy atom nu-
clei, including tin, is considered to be dominated by the
paramagnetic term which is represented by the expres-
sion, |p= −A(dE)−1[Qp+Qd], where A is a numerical
constant, dE is the average excitation energy, and Qp
and Qd depend on the size of and electron imbalance in
the valence shell p- and d-orbitals, respectively [1,14].
For tin, it is usually assumed that dE is constant for a
series of related molecules and participation of tin 5d
orbitals in bonding is insignificant [1]. Thus, |p for
Ar3SnX varies mainly with Qp consistent with the sim-
ple bonding picture given above.
With X=Mn(CO)5, these two assumptions are no
longer valid since Mn(CO)5 is both a s-acceptor and
p-donor ligand. The latter behaviour involves interac-
tion between filled 3d orbitals on manganese with
empty orbitals (perhaps 5d or s*) on tin which results
in a decrease in dE and a shift to high field for the tin
resonance. The completely different substituent effects
given by l(119Sn) data for Ar3SnX (X=Cl, Br, I) and
Ar3SnMn(CO)5 systems are also consistent with this
picture. Thus, if the para-substituent is a strong p-
donor, e.g. CH3O, the resulting increase in p-electron
density at tin will be compensated by decrease in p-
back-donation from the manganese therefore nullifying
any resonance effect. This then leaves only the through-
Fig. 5. Correlation of l119Sn and l55Mn data for I–VII with
substituent parameters: (a) l119Sn vs. |I (r=0.9726; n=7). (b)
l
55Mn vs. |° (r=0.9914; n=7).
p
the principal contributor but as Ar is replaced by I, Br,
and then Cl, A becomes more significant.
bond inductive effect with increasing
|
I
causing
deshielding at tin, as is the case. In contrast, both
resonance and inductive substituent effects contribute
Ar3Sn+X−lAr3(SBn) ꢀXlAr3Sn−X+
(A)
(C)
Table 6
Chemical shifts regression analysis parameters for compounds I–VII (n=7)
a
c
zI zR
C
r
SD b
f
l=zI|I+zR|R+C
l(119Sn)
25.78
104.1
7.81
5.61
85.53
20.62
−10.73
−2507
140.8
0.991
0.996
0.995
0.999
0.800
2.59
0.481
0.909
0.138
0.084
0.098
0.045
l(55Mn)
l(13Cipso
)
1J(119Sn–13C)
−60.54
−72.96
382.1
l=zI|I+zR|° +C
R
l(119Sn)
l(55Mn)
25.54
100.7
7.01
6.52
103.13
25.14
−10.86
−2508
0.988
0.990
0.994
0.995
0.900
3.96
0.518
1.97
0.154
0.129
0.106
0.098
l(13Cipso
)
140.6
383.2
1J(119Sn–13C)
−57.67
−88.54
a Multiple correlation coefficient.
b Standard deviation of residuals.
c Goodness-of-fit parameter, SD/RMS [29].

D. Christendat et al. / Inorganica Chimica Acta 329 (2002) 36–44
43
to l(55Mn) again with the more electron withdrawing
4. Supplementary material
groups, e.g. CH3S(O2), causing concommitant deshield-
ing at manganese.
Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
Data Centre, CCDC Nos. 163789–163793, for com-
pounds V, VI, II, IV and III, respectively. Copies of
this information may be obtained free of charge from
The Director, CCDC, 12 Union Road, Cambridge,
CB2 1EZ, UK (fax: +44-1223-336-033; e-mail: de-
posit@ccdc.cam.ac.uk or www: http://www.ccdc.
cam.ac.uk).
3.4. X-ray diffraction results
The structures of II–VI closely resemble that of the
archetype I, Ph3SnMn(CO)5, and the exhaustive de-
scription of I [8] is still relevant. All bond lengths and
angles are within the same range of these parameters
for I and where there are differences between I, and
II–VI, these may be simply due to the lower precision
of the earlier structure determination. The Mn(CO)5
moiety in all cases is a distorted tetragonal pyramid
with the equatorial CO groups inclined towards the tin.
In fact, the principal structural differences between
molecules, including the molecules A and B of V, lie in
the phenyl ring torsion angles. The relevance of these to
the solid-state 119Sn NMR parameters of these com-
pounds has already been discussed [4]. It is likely this
variation in phenyl ring torsion angles that may be the
main determinant of the detailed electronic environ-
ment at tin and account for the lack of correlation of
solid-state l(119Sn) data with substituent constants. In
particular, the structure of IV shows the most deviation
from the norm, with one aryl ring torsion angle being
unusually small (−22°) while the p-CH3S group at-
tached to this ring is out-of-plane by 33° rather than
the more usual value of ꢁ10° [30]. The offset of the
data point for IV from the linear relation between
1J(119Sn–55Mn) and the quadrupole coupling constant,
(55Mn) generally observed for these systems was ear-
lier ascribed to this errant conformation of the phenyl
Acknowledgements
The financial assistance of FCAR (Quebec) and
NSERC (Canada) is most gratefully acknowledged.
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A of V, with
C(4)Mn(1)Sn(1)C(21)=1.2(3)°, this is nearly exactly
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