Strikingly diverse reactivity of structurally identical silylene and stannylene

Article abstract of DOI:10.1039/c7dt01055a

The reactivity of structurally identical silylene and stannylene [PhC(NtBu)₂EN(SiMe₃)₂] (E = Si (1) and Sn (2)) towards coinage metals has been explored. While 1 has the propensity to form an adduct with coinage metals (4

Full text of DOI:10.1039/c7dt01055a

View Article Online
View Journal
Dalton
Transactions
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: N. Parvin, R.
Dasgupta, S. Pal, S. S. Sen and S. Khan, Dalton Trans., 2017, DOI: 10.1039/C7DT01055A.
This is an Accepted Manuscript, which has been through the
Volume 45 Number
1 7 January 2016 Pages 1–398
Royal Society of Chemistry peer review process and has been
accepted for publication.
Dalton
Transactions
Accepted Manuscripts are published online shortly after
An international journal of inorganic chemistry
www.rsc.org/dalton
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
author guidelines.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the ethical guidelines, outlined
in our author and reviewer resource centre, still apply. In no
event shall the Royal Society of Chemistry be held responsible
for any errors or omissions in this Accepted Manuscript or any
consequences arising from the use of any information it contains.
ISSN 1477-9226
PAPER
Joseph T. Hupp, Omar K. Farha et al.
Efficient extraction of sulfate from water using
framework
a Zr-metal–organic
rsc.li/dalton

Please do not adjust margins
Page 1 of 6
Dalton Transactions
View Article Online
DOI: 10.1039/C7DT01055A
Dalton Transactions
COMMUNICATION
Strikingly diverse reactivity of structurally identical silylene and
stannylene+
Nasrina Parvin,a Rajarshi Dasgupta,a Shiv Pal,a Sakya S. Sen*b and Shabana Khan*a
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
Abstract: Reactivity of structurally identical silylene and can form a simple adduct with coinage metal halides,8 which
stannylene [PhC(NtBu)2EN(SiMe3)2] (E=Si (1) and Sn (2)) towards rely solely on the Si TM dative bond to maintain complex
→
coinage metals have been explored. While 1 has the propensity to stability. Comparable adduct with stannylene has a modicum
form adduct with coinage metals (4 and 5), 2 undergoes ligand of precedence.10b This can be rationalized by greater σ-
exchange reaction with copper halides and silver triflate leading to donation ability of silylene than its heavier congener, where
PhC(NtBu)2SnX (X=Br (6), Cl (7), and OSO2CF3 (8)) with concomitant the lone pair of electrons has higher s-character.
formation of [M{N(SiMe3)2}] (M = Cu, Ag). However, with AgSbF6
The present study is intended to achieve two aims at once:
–
–
both 1 and 2 led to ion pairs, 9+·SbF6 and 10+·SbF6 displaying (a) explore a new stannylene ligand for coinage metal
weaker Ag····F interactions in the latter.
complexes and (b) an one-to-one comparison of the reactivity
study of silylenes and stannylenes towards transition metal
halides. To systematically compare the reactivity, both silylene
and stannylene should have exactly same ligands and
substituents as subtle modifications often induce structural or
chemical diversities.11
Compounds of a family of structurally similar derivatives often
display similar physical and chemical properties. Silylenes and
stannylenes are the heavier congener of N-heterocyclic
carbenes (NHCs).1 Coinage metal NHC complexes have been
extensively studied for their intriguing structural properties
and numerous applications.2 Going by the mushrooming
chemistry of silylene-transition metal complexes,3 one could
expect that one of the next targets would be to replace NHCs
by their heavier congeners as ligands for coinage metals.
Examples of complexes having silylene to group 11 dative
interactions have been initially predicted by Frenking et al.4
and subsequently realized by the groups of Iwamoto,5
Lappert,6 Driess,7 Robinson,8 as well as by us9a,b. On the
contrary, the reaction of stannylene with copper complexes
have a modicum of precedence except the recent studies by
Klinkhammer, Baumgartner, and others.10 Moreover, silylene
u
u
tB
tB
X
X
,
N
N
=
,
u
r
)
Ph
C X
X
Cl B
(
u
tB
u
u
Si
C
C
Si
Ph
. .
t
o uene r
t l
N
=
N
N
N TMS
TMS 2N
E
Si
(
)
2
(
)
E
Ph
u
u
tB
tB
,
,
=
=
r
N
X
X
B
4
5
N TMS
(
)
2
Cl
u
tB
u
tB
=
=
N
;
1
Si
E
E
u
C X/AgOTf
. .
n
;
2
S
.
n
S
+
Ph
e
0 25 MN SiM
[
(
3)2]4
,
o uene r
t l
t
N
=
=
=
X
u
Ag f
or an
n
S
6
8
7
d
M
M
C
f
E
or
u
tB
,
,
O
=
r
6
( )
l
7
Tf
8
( )
X
B
C
( )
Scheme 1. Reactions of silylene and stannylene with copper halides
Hence, we zeroed in the previously reported
[PhC(NtBu)2SiN(SiMe3)2]12 ) and [PhC(NtBu)2SnN(SiMe3)2]13
) for the comparison study and reacted with coinage metals.
a Department of Chemistry
Indian Institute of Science Education and Research Pune
Dr. Homi Bhaba Road, Pashan, Pune - 411008, India
Phone: 0091-20-2590-8137
(1
(2
While the reaction of copper halides with
formation of anticipated
[{PhC(NtBu)2}Si{N(SiMe3)2}]2Cu2X2 [X=Br (
underwent a σ-bond metathesis leading to formation of
[PhC(NtBu)2SnX] [X=Br ( ) and Cl ( )]. In line with this
observation, the reaction of with AgOTf (Tf=SO2CF3) resulted
in [PhC(NtBu)2SnOTf] ( ). On the contrary, the reaction of
1
afforded the
E-mail: shabana@iiserpune.ac.in
adducts,
Homepage: http://www.iiserpune.ac.in/~shabana/
b Inorganic Chemistry and Catalysis Division
CSIR-National Chemical Laboratory
Dr. Homi Bhaba Road, Pashan, Pune - 411008, India
Phone: 0091-20-2590-3052
4
) and Cl (
5
)],
2
6
7
2
E-mail: ss.sen@ncl.res.in
Homepage: http://academic.ncl.res.in/ss.sen
8
+Dedicated to Prof. Jai Deo Singh
–
–
AgSbF6 with
complexes.
1 and 2
resulted in 9+·SbF6 and 10+·SbF6
Electronic supplementary information (ESI) available: Preparation of
crystallographic data for 4-6 , and 10. CCDC no. 1474385 ( ), 1474386 (
1535769( ), 1535770( ), 1535771 (10).
4
-
10 and X-ray
,
9
4
5
),
6
9
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
Please do not adjust margins

Please do not adjust margins
Dalton Transactions
Page 2 of 6
COMMUNICATION
Journal Name
View Article Online
DOI: 10.1039/C7DT01055A
4
5
Figure 1. Molecular structures of 4 and 5 with anisotropic displacement parameters depicted at the 50 % probability level. Hydrogen atoms are not shown for clarity. Selected
bond lengths (Å) and bond angles (°): 4: Cu1–Si1 2.222(2), Cu2–Si4 2.221(2), Cu1··Cu2 3.255(1), Cu1–Br1 2.4297(12), Cu1–Br2 2.4828(12), Cu2–Br1 2.4360(12), Cu2–Br2 2.4822(11);
Si1–Cu1–Br1 135.79(7), Si1–Cu1–Br2 128.08(7), Si4–Cu2–Br1 133.62(7), Si4–Cu2–Br2 130.21(7), Cu1–Br1–Cu2 83.96(4), Cu2–Br2–Cu1 81.92(4), Br1–Cu1–Br2 95.99(4), Br1–Cu2–
Br2 95.84(4); 5: Cu1···Cu2 3.1378(9), Cu1–Si1 2.1986(13), Cu1–Cl1 2.3003(11), Cu1–Cl2 2.3542(11), Cu2–Si4 2.2027(13), Cu2–Cl1 2.3022(11), Cu2–Cl2 2.3450(11); Si1– Cu1–Cl1
134.41(4), Si1–Cu1–Cl2 131.00(4), Cl1–Cu1–Cl2 94.20(4), Si4–Cu2–Cl1 136.75(4), Si4–Cu2–Cl2 128.81(4), Cl1–Cu2–Cl2 94.39(4), Cu2–Cl2–Cu1 83.79(4), Cu1–Cl1–Cu2 85.97.
Treatment of silylene
and CuCl in toluene at room temperature furnished the (1.769(7) Å),12 [PhC(NtBu)2SiNMe2] (1.724(2) Å),16 and
respective silylene-copper complexes and
(Scheme 1). As (1.731(9) Å).8 The Si→Cu bond lengths in
expected, the coordination of copper to the Si(II) center led to 2.222(2) Å, while in
the downfield shift in the respective 29Si NMR resonance (
: δ bond lengths are in good accordance with the Si–Cu bond
(δ –8.07 lengths in
(2.243(3) and 2.250(3) Å)9a and in other reported
that
of Si–Cu bond lengths [2.1981(12)–2.289(4) Å].5-8
) (δ 16.85 ppm).9a It is
that copper
halides with less electronegative substituents lead to a more
downfield shift. Surprisingly, the reactions of with copper
halides did not lead to the formation of the anticipated adduct
and instead resulted in amidinato Sn(II) bromide ( ) and
chloride ( ), generating from the metathesis reaction. The
1
with one molar equivalent of CuBr bond lengths in the previously reported Si(II) amides
1
3
4
5
4
are 2.221(2) and
5
these are 2.197(2) and 2.203(2) Å. These
4
5.72 and
ppm)
5
: δ 4.79 ppm) in comparison to that of
1
3
but upfield with respect to
[{PhC(NtBu)2}Si{N(SiMe3)2}]2Cu2I2 (
3
apparent from the 29Si NMR resonances of
3-5
2
6
7
concomitant formation of copper(I) bis(trimethylsilyl)amide,
[Cu{N(SiMe3)2}] as a by-product was spectroscopically and
structurally established (See Supporting Information). Such
metathetical reaction is reminiscent of the reactivity of
Sn[N(SiMe3)2]2, which undergoes facile metathesis reactions
with amines, alcohols, amides, carboxylic acids, amine
hydrochloride salts, and related compounds.14 To test the
Figure 2. Molecular structure of 6 with anisotropic displacement parameters depicted
at the 50 % probability level. Hydrogen atoms are not shown for clarity. Selected bond
lengths (Å) and bond angles (°):N2-Sn1 2.171(6); N1-Sn1 2.168(6); Sn1-Br1 2.620(2); N2-
Sn1-Br1 94.35(16); N1-Sn1-Br1 93.21(16); N2-Sn1-N1 60.20(2).
ligand exchange behaviour is an intrinsic property of
decided to investigate the reaction of with silver triflate
(AgOSO2CF3) which also undergo ligand exchange reaction
leading to LSnOTf (L = PhC(NtBu)2) (
).13
The corresponding structural parameters of
2, we
2
The structure of
studies. The structure of
6
was established by single crystal X-ray
is very similar to those of
8
6
4
and 5 are
PhC(NtBu)2ECl (E=Si,17 Ge,18 and Sn13) showing a distorted
trigonal pyramidal geometry with a lone pair of electrons on
the Sn(II) atom (Figure 2). The Sn-Br bond length is of
2.6197(13) Å, which is in good accordance with the regular Sn–
very much alike and the noticeable alterations of the bond
lengths and angles are attributed to the different halides. Both
4
and 5
crystallize in the triclinic space group P-115 and consists
of a four-membered Cu2X2 core, where each silylene ligand is
coordinated to a Cu atom. A two-fold symmetry axis passes
through the centroid of the four-membered Cu2X2 ring, which
Br bond lengths (ca. 2.59 Å).19 The 119Sn NMR spectrum of
exhibits a singlet resonance at δ 68.45 ppm, which is
significantly downfield that of
(δ 29.6 ppm).13 The structures
of compound and
were previously reported.13 Hence they
6
7
is almost planar. Each Si(II) center in
and exhibits a slightly distorted tetrahedral geometry (Figure
1). The Si–N(SiMe3)2 bond distances are 1.746(6) Å for and
1.732(3) Å for , which are in good agreement with the Si-N
4 and 5 is four coordinate
7
8
were only characterized by spectroscopic analyses and
compared to the samples prepared by previously reported
synthetic methods. Therefore, our method also provides new
4
5
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 3 of 6
Dalton Transactions
Please do not adjust margins
Journal Name
synthetic route to access such functionalized stannylene
COMMUNICATION
Although the formulation of
9
and 10 are akin to each
View Article Online
complexes which were otherwise only accessible via salt other but their structural parameters areDsOigI:n1i0fi.1c0a3n9t/lCy7dDiTf0fe10re55nAt
elimination methodology.
(Figure 5). Most strikingly, the Sn-Ag-Sn framework is severely
bent with an angle of 147.57°. Moreover, 10+ is weakly bound
u
u
tB
tB
-
to the SbF6 counter anion through the fluorine atoms with the
N
N
A
bF
gS
tB
shortest Ag–F bond distance of 2.733 Å. The 19F spectrum of
9
u
6
i
S
A
i
S
g
Ph
Ph
. .
t
,
o uene r
t l
and 10 exhibits resonances at around δ –121 (
(
9) and –120 ppm
N
=
N
N
N TM
S
( )
2
(
E
i
S
TM 2N
S
)
10), respectively. However signals in the 19F NMR spectra of
9
E
Ph
u
u
S
bF
tB
tB
N
tB
6
and 10 can only be seen at low temperature which could be
due to some dynamic behavior. Compound 10 shows signals in
the form of two doublets appearing around δ 99.15 ppm with
N
N TM
(
S
)
2
9
u
u
tB
u
tB
N TM
TM 2N
S
)
S
(
)
2
(
=
=
N
;
1
i
E
E
S
S
A
bF
6
gS
1J119Sn to 109Ag = 4176.96 and J 119Sn to 107Ag = 3668.40 Hz in
n
1
;
2
n
n
S
A
g
S
Ph
Ph
. .
t
,
o uene r
t l
the 119Sn NMR spectrum. The downfield shift in the latter than
N
N
=
n
F
Sb
F
E
S
F
F
those in
6 and 7 can be attributed to the cationic nature of 10.
u
u
tB
tB
F
F
To the best of our knowledge, compound 10 is the first Ag
cation stabilized by stannylene ligand with two Sn(II)→Ag
10
dative bonds. Upon comparison of
9 and 10 with the
21a
analogous [(NHC)2Ag]+
(A
)
(NHC=IDipp, IMe, IEt) and
21b complexes, it is apparent that
Scheme 2. Reactions of silylene and stannylene with AgSbF6.
[{PhC(NtBu)2Ge(tBu)}2Ag]+ (
B
)
moving from top to bottom within the group the coordination
behaviour varies dramatically (Figure 3) and this can be
attributed to the higher s-character of the lone pair of
electrons down the group. These differences are indicative of
weaker σ-donation of the stannylene ligand than that of
silylene. Silylene may provide sufficient stabilization to
attenuate the Lewis acidity of the Ag+ cation and hence there
A different reactivity pattern was observed for the
coordination of
with and
2
to Ag[SbF6]. When the latter was reacted
–
1
2
, cationic silylene-silver complex 9+·SbF6 and
stannylene-silver complex 10+·SbF6 were obtained. The
–
dichotomic behavior of
2 towards AgOTf and AgSbF6 can be
rationalized from the greater Lewis acidity of Ag atom in
AgSbF6 as well as the bulkier nature of the latter.
is no interaction with the counter-anion in
9. However,
–
–
Single crystals of 9+·SbF6 and 10+·SbF6 suitable for X-ray
stannylene may not render σ-donation to that extent and
thereby the Ag+ cation is stabilized by further interaction with
the fluorine atoms. The Sn(II)→Ag bond distance is 2.6217 Å,
which is longer than that in [HB(3,5-(CF3)2Pz)3]AgSn(Cl)[(n-
Pr)2ATI] [ATI=aminitroponiminate] [2.5863(6) Å]22 and other
structurally characterized Sn-Ag bond distances such as
[MeSi{Si(Me)2N(p-Tol)}3-SnAg]2 (2.6567(7) Å),23 [(thf)Ag(μ-
analysis were obtained by recrystallization from toluene at 0 °C
–
in a refrigerator. X-ray analysis shows that 9+·SbF6 exists as an
ion pair (Figure 4): the closest distance between the F atom in
the SbF6– moiety and the Ag atom is 6.087 Å, which is greater
than the sum of the van der Waals radii of F and Ag (3.2 Å).
The silicon center is tetra-coordinate and exhibits a distorted
tetrahedral geometry. Two silylene moieties almost linearly
coordinate to the Ag atom with the Si1–Ag1–Si1 angle of
171.85(3)°. The Si–Ag bond lengths [2.4249(13) Å and
2.4243(12) Å] significantly surpass those in our
[{PhC(NtBu)2}Si{N(SiMe3)2}]2Ag2[OTf]2 [2.337(2) Å and 2.346(2)
Å]9a and Iwamoto's dialkylsilylene-silver complex (2.4015(16)
SCN)Sn{CH(SiMe3)2}2]2
(2.598(1)
Å),24
and
[HB(3,5-
(CF3)2Pz)3]AgSn(N3)[(n-Pr)2-ATI] (2.5943(6) Å).25
In summary, we have reported a series of reactions with
structurally identical silylene and stannylene and the first one-
to-one compared their reactivity. All reactions with silylene
follow the same pattern either forming the neutral adduct (
3-
Å).5 In the 29Si NMR spectrum of
9
, signals in the form of two
5
) or ionic complex ( ) depending the transition metal
9
1
doublets appearing around δ 11.62 ppm with with J 29Si to
precursors. However, this is not the case with stannylene. It
undergoes metathesis reaction with copper halides and silver
triflate leading to the formation of different functionalized
1
109Ag = 333.05 and J 29Si to 107Ag = 288.50 Hz.20 The SiMe3
substituents resonate at δ 7.17 and 8.61 ppm.
.
.
.
-
~
°
°
°
°
163 70
stannylenes
(6
-
8
)
with simultaneous formation of
171 85
147 57
176 180
n
n
S
S
corresponding metal amides. This is a new synthetic route to
access various functionalities at stannylenes. However, the
e
G
e
G
i
S
i
S
A
g
A
A
g
g
S
A
g
C
C
.
.
.
3 02
2 733
Å
Å
>
6 087
Å
4
reaction of stannylene
2 with AgSbF6 led to the first
Å
F
F
F
F
F
F
F
stannylene-silver ionic complex where two stannylene units
donate the electron density to stabilize the Ag+ cation. Our
result also mirrors on the greater donor ability of silylene than
that of stannylene as the former form the cationic silver
complex without any interaction of the counter-anion while
corresponding silver cation with stannylene is being
coordinated to the counter-anion. All the isolated complexes
were structurally characterized.
F
B
b
Sb
P
F
F
F
F
F
F
F
F
F
F
F
F
F
F
A
B
10
9
Figure 3. Schematic representation of the comparison of C(II), Si(II), Ge(II) and Sn(II)
supported dimeric Ag+ cations.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

Please do not adjust margins
Dalton Transactions
Page 4 of 6
COMMUNICATION
Journal Name
Notes and references
View Article Online
DOI: 10.1039/C7DT01055A
1
(a) S. Nagendran and H. W. Roesky, Organometallics, 2008,
27, 457-492; (b) M. Asay, C. Jones and M. Driess, Chem. Rev.,
2011, 111, 354-396; (c) Y. Mizuhata, T. Sasamori and
N.Tokitoh, Chem. Rev., 2009, 109, 3479-3511; (d) S. S. Sen. S.
Khan, P. P. Samuel and H. W. Roesky, Chem. Sci., 2012,
659–682; (e) S. Yadav, S. Saha, and S. S. Sen, ChemCatChem,
2016, , 486–501.
3,
8
2
3
J. C. Y. Lin, R. T. W. Huang, C. S. Lee, A. Bhattacharyya, W. S.
Hwang and I. J. B. Lin, Chem. Rev., 2009, 109, 3561–3598.
(a) B. Blom, S. Enthaler, S. Inoue, E. Irran and M. Driess, J.
Am. Chem. Soc., 2013, 135, 6703–6713; (b) C. I. Someya, M.
Haberberger, W. Wang, S. Enthaler and S. Inoue, Chem. Lett.,
2013, 42, 286–288; (c) D. Gallego, A. Brück, E. Irran, F. Meier,
M. Kaupp, M. Driess and J. F. Hartwig, J. Am. Chem. Soc.,
2013, 135, 15617–15626; (d) M. Stoelzel, C. Präsang, B. Blom
and M. Driess, Aust. J. Chem., 2013, 66, 1163–1170; (e) A.
Brück, D. Gallego, W. Wang, E. Irran, M. Driess and J. F.
Hartwig, Angew. Chem., Int. Ed., 2012, 51, 11478–11482; (f)
W. Wang, S. Inoue, S. Enthaler and M. Driess, Angew. Chem.,
Int. Ed., 2012, 51, 6167–6171; (g) W. Wang, S. Inoue, E. Irran
and M. Driess, Angew. Chem., Int. Ed., 2012, 51, 3691–3694.
4
5
6
7
8
C. Boehme and G. Frenking, Organometallics, 1998, 17
,
5801–5809.
Y. Inagawa, S. Ishida and T. Iwamoto, Chem. Lett., 2014, 43
,
Figure 4. Molecular structure of 9 with anisotropic displacement parameters depicted
at the 50 % probability level. Hydrogen atoms and N(SiMe3)2 moieties are not shown
for clarity. Selected bond lengths (Å) and bond angles (°): N1-Si1 1.839(3); N2-Si1
1.842(3); Si1-Ag1 2.4249(13); Si4-Ag1 2.4243(12); Si1-Ag1-Si4 171.85(3); N1-Si1-Ag1
113.28(10); N2-Si1-Ag1 111.61(10); N3-Si4-Ag1 110.57(10); N4-Si4-Ag1 110.86(10).
1665–1667.
A. G. Avert, B. Gehrhus, P. B. Hitchcock, M. F. Lappert and H.
Maciejewski, J. Organomet. Chem., 2003, 686, 321–331.
G. Tan, B. Blom, D. Gallego and M. Driess, Organometallics,
2014, 33, 363–369.
M. Chen, Y. Wang, Y. Xie, P. Wei, R. J. Gilliard, Jr., N. A.
Schwartz, H. F. Schaefer III, P. v. R. Schleyer and G. H.
Robinson, Chem. Eur. J., 2014, 20, 9208–9211.
(a) S. Khan, S. K. Ahirwar, S. Pal, N. Parvin and N. Kathewad,
Organometallics, 2015, 34, 5401-5406; (b) S. Khan, S. Pal, N.
Kathewad, P. Parameswaran, S. De and I. Purushothaman,
Chem. Commun., 2016, 52, 3880–3882.
9
10 (a) J. Klett, K. W. Klinkhammer and M. Niemeyer, Chem. Eur.
J., 1999, , 2531 2536; (b) J. Hlina, H. Arp, M. Walewska, U.
Flörke, K. Zangger, C. Marschner, and J. Baumgartner,
Organometallics, 2014, 33, 7069 7077; (c) U. Anandhi and
5
−
−
P. R. Sharp, Inorg. Chim. Acta 2006, 359, 3521–3526.
11 Effects of substituent in [PhC(NtBu)2SiX] for P4 activation: (a)
S. S. Sen, S. Khan, H. W. Roesky, D. Kratzert, K. Meindl, J.
Henn, D. Stalke, J.-P. Demers and A. Lange, Angew. Chem.
Int. Ed., 2011, 50, 2322–2325; (b) S. Khan, R. Michel, S. S.
Sen, H. W. Roesky and D. Stalke, Angew. Chem. Int. Ed.,
2011, 50, 11786-11789.
12 S. S. Sen, J. Hey, R. Herbst-Irmer, H. W. Roesky and D. Stalke,
J. Am. Chem. Soc., 2011, 133, 12311-12316.
13 S. S. Sen, M. P. Kritzler-Kosch, S. Nagendran, H. W. Roesky, T.
Beck, A. Pal and R. Herbst-Irmer, Eur. J. Inorg. Chem., 2010,
5304–5311.
Figure 5. Molecular structure of 10 with anisotropic displacement parameters depicted
at the 50 % probability level. Hydrogen atoms and N(SiMe3)2 moieties are not shown
for clarity. Selected bond lengths (Å) and bond angles (°): N1-Sn1 2.176(6); N2 Sn1
2.153(7); Sn1-Ag1 2.6217(8); N1-Sn1-Ag1 112.17(15); N2-Sn1-Ag1 117.60(19); Sn1-Ag-
Sn1 147.57(4)
14 (a) M. Veith, Chem. Rev., 1990, 90, 3-16; (b) W. P. Neumann,
Chem. Rev., 1991, 91, 311-334.
15 (a) T. Kottke and D. Stalke, J. Appl. Crystallogr., 1993, 26
,
615–619; (b) D. Stalke, Chem. Soc. Rev., 1998, 27, 171–178;
(c) G. M. Sheldrick, Acta Crystallogr. Sect. A, 2008, 64, 112–
122.
Acknowledgements
16 C.-W. So, H. W. Roesky, P. M. Gurubasavaraj, R. B. Oswald,
M. T. Gamer, P. G. Jones and S. Blaurock, J. Am. Chem. Soc.
2007, 129, 12049-12054.
17 (a) C.-W. So, H. W. Roesky, J. Magull and R. B. Oswald,
Angew. Chem., Int. Ed., 2006, 45, 3948-3950; (b) S. S. Sen, H.
W. Roesky, D. Stern, J. Henn and D. Stalke, J. Am. Chem. Soc.,
SK thanks SERB (India), DST-FIST and IISER Pune for financial
support. NP and SP thank UGC for providing fellowships. RDG
thanks CSIR for fellowship. SSS thanks the Ramanujan research
grant (SB/S1/RJN-073/2014) for financial support. We thank
the reviewers for their valuable inputs to improve the quality
of the manuscript.
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 5 of 6
Dalton Transactions
Please do not adjust margins
Journal Name
COMMUNICATION
2010, 132, 1123-1126; (c) H.-X. Yeong, K.-C. Lau, H.-W. Xi, K.
H. Lim and C.-W. So, Inorg. Chem. 2010, 49, 371-373.
18 S. Nagendran, S. S. Sen, H. W. Roesky, D. Koley, H.
Grubmüller, A. Pal and R. Herbst-Irmer, Organometallics
2008, 27, 5459-5463.
View Article Online
DOI: 10.1039/C7DT01055A
19 B. Cordero, V. Gomez, A. E. Platero-Prats, M. Reves, J.
Echeverria, E. Cremades, F. Barragan and S. Alvarez, Dalton
Trans., 2008, 2832–2838.
20 T. G. Driver and K. A. Woerpel, J. Am. Chem. Soc., 2004, 126
,
9993-10002.
21 (a) M. Kriechbaum, J.Hӧlbling, H.-G. Stammler, M. List, R. J.
F. Berger and U. Monkowius, Organometallics, 2013, 32
2876 2884; (b) L. Álvarez-Rodríguez, J. A. Cabeza, P. García-
Álvarez and D. Polo, Organometallics, 2015, 34, 5479 5484.
,
−
−
22 A. E. Ayers and H. V. R. Dias, Inorg. Chem., 2002, 41, 3259-
3268.
23 B. Findeis, L. H. Gade, I. J. Scowen and M. McPartlin, Inorg.
Chem., 1997, 36, 960-961.
24 P. B. Hitchcock, M. F. Lappert and L. J.-M. Pierssens,
Organometallics, 1998, 17, 2686-2688.
25 A. E. Ayers and H. V. R. Dias, Polyhedron, 2002, 21, 611–618.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
Please do not adjust margins

Dalton Transactions
Page 6 of 6
View Article Online
DOI: 10.1039/C7DT01055A
TOC
Strikingly diverse reactivity of structurally identical silylene
and stannylene
Nasrina Parvin,a Rajarshi Dasgupta,a Shiv Pal,a Sakya S. Sen*b and Shabana Khan*a
Divergent reactivity of structurally similar silylene and stannylene was observed with coinage
metal halides. While the former tends to form adduct, the latter undergoes ligand exchange
reaction.