Synthesis and characterization of silver(i) adducts supported solely by 1,3,5-triazapentadienyl ligands or by triazapentadienyl and other N-donors

Article abstract of DOI:10.1039/c1dt10199d

Halogenated 1,3,5-triazapentadienyl ligands [N{(C₃F ₇)C(C₆F₅)N}₂]^-, [N{(CF₃)C(C₆F₅)N}₂]^- and [N{(C₃F₇)C(2,6-Cl₂C₆H ₃)N}₂]^-, alone or in combination with other N-donors like CH₃CN, CH₃(CH₂)₂CN, and N(C₂H₅)₃, have been used in the stabilization of thermally stable, two-, three- or four-coordinate silver(i) adducts. X-Ray crystallographic analyses of {[N{(C₃F ₇)C(C₆F₅)N}₂]Ag}_n, {[N{(C₃F₇)C(C₆F₅)N} ₂]Ag(NCCH₃)}_n, {[N{(C₃F ₇)C(2,6-Cl₂C₆H₃)N} ₂]Ag(NCCH₃)}_n, {[N{(CF₃)C(C ₆F₅)N}₂]Ag(NCCH₃)₂} _n and {[N{(C₃F₇)C(C₆F ₅)N}₂]Ag(NCC₃H₇)}_n revealed the presence of bridging 1,3,5-triazapentadienyl ligands bonded to silver through terminal nitrogen atoms. These adducts are polymeric in the solid state. [N{(C₃F₇)C(2,6-Cl₂C₆H ₃)N}₂]AgN(C₂H₅)₃ is monomeric and features a 1,3,5-triazapentadienyl ligand bonded to Ag(i) in a κ¹-fashion via only one of the terminal nitrogen atoms. The solid state structure of [N{(C₃F₇)C(C₆F ₅)N}₂]H has also been reported and it forms polymeric chains via inter-molecular N-H...N hydrogen-bonding.

Full text of DOI:10.1039/c1dt10199d

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PAPER
Synthesis and characterization of silver(I) adducts supported solely by
1,3,5-triazapentadienyl ligands or by triazapentadienyl and other N-donors†
Jaime A. Flores, Yoshihiro Kobayashi and H. V. Rasika Dias*
Received 4th February 2011, Accepted 23rd February 2011
DOI: 10.1039/c1dt10199d
Halogenated 1,3,5-triazapentadienyl ligands [N{(C3F7)C(C6F5)N}2]-, [N{(CF3)C(C6F5)N}2]- and
[N{(C3F7)C(2,6-Cl2C6H3)N}2]-, alone or in combination with other N-donors like CH3CN,
CH3(CH2)2CN, and N(C2H5)3, have been used in the stabilization of thermally stable, two-, three- or
four-coordinate silver(I) adducts. X-Ray crystallographic analyses of {[N{(C3F7)C(C6F5)N}2]Ag}n,
{[N{(C3F7)C(C6F5)N}2]Ag(NCCH3)} , {[N{(C3F7)C(2,6-Cl2C6H3)N}2]Ag(NCCH3)}n,
{[N{(CF3)C(C6F5)N}2]Ag(NCCH3)2}nn and {[N{(C3F7)C(C6F5)N}2]Ag(NCC3H7)}n revealed the
presence of bridging 1,3,5-triazapentadienyl ligands bonded to silver through terminal nitrogen atoms.
These adducts are polymeric in the solid state. [N{(C3F7)C(2,6-Cl2C6H3)N}2]AgN(C2H5)3 is monomeric
1
and features a 1,3,5-triazapentadienyl ligand bonded to Ag(I) in a k -fashion via only one of the
terminal nitrogen atoms. The solid state structure of [N{(C3F7)C(C6F5)N}2]H has also been reported
and it forms polymeric chains via inter-molecular N–H ◊ ◊ ◊ N hydrogen-bonding.
Introduction
1,5-Diazapentadienyl ligands (also known as b-diketiminates,
1) are one of the most useful group of monoanionic,
nitrogen-based ligands in chemistry. They have been utilized
widely in coordination chemistry1–10 and to isolate low-
valent and low-coordinate main group adducts,11–16 prepare
homogeneous catalysts, as well as for modelling active sites
of metalloenzymes.17–29 In contrast, 1,3,5-triazapentadienyl
ligands 2 (the trinitrogen analogues of 1,5-diazapentadienyl
systems) have received relatively little attention.30 This is
probably because facile and general synthetic methods for their
generation have been rather poorly developed. Recently, groups
led by Siedle and Dias reported the synthesis of fluorinated
triazapentadienes and their coinage metal (Cu, Ag, Au)
1,3,5-triazapentadienes like [N{(C3F7)C(Ph)N}2]H (3) and
[N{(C3F7)C(Dipp)N}2]H (4, where Dipp = 2,6-Pri2C6H3).31–33
These molecules have easily ionizable NH hydrogen atoms
and their conjugate bases have three basic nitrogen sites for
metal ion coordination. The ligand backbones are also fairly
flexible, and usually adopt W- or U-shaped conformations.
Recent work also shows that they are useful in the isolation
of coinage metal adducts like [N{(C3F7)C(Dipp)N}2]CuCO,32
[N{(C3F7)C(Dipp)N}2]Cu(C2H4),34 and [N{(C3F7)C(2,6-Cl2-
C6H3)N}2]Au(C2H4).35
complexes.32–37 For example, we have used fluorinated ligands like
[HB(3,5-(CF3)2Pz)3]- to stabilize rare organometallic complexes
of silver(I) such as Ag–CO,38 Ag–C2H2, and Ag–C2H4 adducts.39
Some of those silver(I) adducts show promising catalytic
properties (e.g., C–H and C–halogen bond activation)40–44
and antimicrobial activity,45–47 and serve as useful ligand
transfer agents.48 Our preliminary work involving fluorinated
1,3,5-triazapentadienyl ligands in silver led to three monomeric
silver(I) complexes (CH3CN)Ag[N{(C3F7)C(Dipp)N}2], (ButNC)-
Ag[N{(C3F7)C(Dipp)N}2], and[N{(C3F7)C(Dipp)N}2]Ag(PPh3).33
The isolation and antimicrobial properties of fluorinated
ligands like [N{(C3F7)C(C6F5)N}2]H and their silver adducts
were described in a recent patent.47 In addition, Siedle and
co-workers also described the use of triazapentadienyl
ligands to isolate silver adducts [N{(C3F7)C(Ph)N}2]Ag and
[N{(C3F7)C(Ph)N}2][Ag(diphos)] but no structural data were
reported.49 In this paper, we describe the use of halogenated
Over the last few years, we have been involved in the
study of polyhalogenated ligands including those of 1,3,5-
Department of Chemistry and Biochemistry, The University of Texas at
Arlington, Arlington, Texas, 76019, USA. E-mail: dias@uta.edu
† CCDC reference numbers 812156–812162. For crystallographic data in
CIF or other electronic format see DOI: 10.1039/c1dt10199d
This journal is
The Royal Society of Chemistry 2011
Dalton Trans., 2011, 40, 10351–10359 | 10351
©

1,3,5-triazapentadienyl ligands, [N{(C3F7)C(C6F5)N}2]- (5) and
[N{(C3F7)C(2,6-Cl2C6H3)N}2]- (6) to stabilize monomeric and
polymeric silver(I) complexes featuring silver sites supported solely
by 1,3,5-triazapentadienyl ligands or only by nitrogen-donor
ligands. We also demonstrate the rich diversity of coordination
modes of 1,3,5-triazapentadienyl ligands by providing examples
of a triazapentadienyl ligand acting as a bridging ligand and as a
bonds consistent with this observation. [N{(C3F7)C(C6F5)N}2]H
forms polymeric chains via intermolecular NH ◊ ◊ ◊ N hydrogen
bonding (Fig. 1). Such intermolecular NH ◊ ◊ ◊ N bonds and
polymeric chains have been observed for [N{(CF3)C(C6F5)N} ]H
and [N{(C3F7)C(2,6-Cl2C6H3)N}2]H.35 [N{(C3F7)C(Dipp)N}22]H
molecules (bearing much bulkier N-aryl groups) however do not
form such intermolecular NH ◊ ◊ ◊ N bonds but pack forming layers
of hydrocarbon and fluorocarbon domains.33,35
1
k donor via one of the terminal nitrogen atoms.
Silver(I) salts {[N{(C3F7)C(C6F5)N}2]Ag}n and {[N{(C3F7)-
C(2,6-Cl2C6H3)N}2]Ag}n were easily obtained by refluxing a
mixture of the corresponding fluorinated ligand and Ag2O
in THF.47 In none of the cases was a silver mirror observed
at the end of the reactions when the mixture was protected
from light. {[N{(C3F7)C(C6F5)N}2]Ag}n and {[N{(C3F7)C(2,6-
Cl2C6H3)N}2]Ag}n are white solids. They are air and light stable
for at least several days, and soluble in polar solvents like
acetone, acetonitrile and DMSO but somewhat less soluble in
halogenated or aromatic solvents. The X-ray crystal structure
For comparison, silver(I) complexes of 1,5-diazapentadienyl
ligands are also rare as they are often light and heat sensitive,
challenging to isolate, and decompose producing metallic silver.
Shimokawa and Itoh reported the first 1,5-diazapentadienyl
silver adducts, and the 1,5-diazapentadienyl ligand dimeriza-
tion products resulting from silver(I) mediated redox chem-
istry (silver adduct decomposition).50 Daugulis described several
isolable monomeric silver 1,5-dizapentadienyl adducts including
[HC{(CF3)C(3,5-(CF3)2C6H3)N}2]Ag(C2H4).51
of {[N{(C3F7)C(C6F5)N}2]Ag}n displays
a linear polymer
with the NCNCN ligand backbone in a slightly twisted W-
shaped configuration while the two-coordinate silver sites
are linear and bond to the terminal nitrogen atoms of the
neighboring ligand units (Fig. 2). [N{(C3F7)C(C6F5)N}2]-
therefore acts as a bidentate bridging ligand. To the best
of our knowledge linear polymers featuring two-coordinate
silver(I) in a linear geometry with nitrogen-based ligands
are rare—one such case concerns a polymeric silver(I)–2-
pyrimidinolate complex.52 There is no significant difference
Results and discussion
˚
in the N–Ag distances of this complex (2.117(3) A and
[N{(C3F7)C(C6F5)N}2]H and [N{(C3F7)C(2,6-Cl2C6H3)N}2]H
were synthesized as described previously using three equivalents of
triethylamine and two equivalents of the corresponding aniline per
equivalent of perfluoro-5-aza-4-nonene.35,36,47 These molecules are
white to pale yellow solids and soluble in ethers or halogenated and
polar solvents like CH2Cl2, DMSO or acetone but only sparingly
soluble in n-hexane. We also investigated the solid state structure of
[N{(C3F7)C(C6F5)N}2]H (Fig. 1). It crystallizes in the P21/c space
group with three independent [N{(C3F7)C(C6F5)N}2]H units in
the asymmetric unit. It features a twisted, W-shaped (approaching
an S-shape) NCNCN triazapentadiene ligand backbone. The
proton is located on one of the terminal nitrogen atoms and
the HNCNCN backbone displays long–short–long–short C–N
˚
2.114(3) A), and those of the {[N{(C3F7)C(C6F5)N} ]Ag}
˚
A
˚
(2.113(6)
and 2.120(6) A). {[HC{HC(Dipp)N}22]Ag}2n
and {[NCC{HC(Dipp)N}2]Ag}4 involving bridging 1,5-
diazapentadienyl ligands are dimeric and tetrameric aggregates of
the corresponding 1,5-diazapentadienylsilver(I) moiety and they
have 2-coordinate silver sites and W-shaped NCCCN backbones.50
We have also synthesized [N{(C3F7)C(2,6-Cl2C6H3)N}2]Ag which
presumably forms aggregates in the solid state. We have not
been able to obtain X-ray quality crystals to confirm this
assertion. However, the ESI–MS analysis of [N{(C3F7)C(2,6-
Cl2C6H3)N}2]Ag shows signals assignable to different oligomers.
As noted in the introduction section, [N{(C3F7)C(Ph)N}2]Ag
Fig. 1 Molecular structure of [N{(C3F7)C(C6F5)N}2]H showing the atom numbering scheme and extended structure. Thermal ellipsoids drawn at the
◦
˚
50% level. Selected bond lengths (A) and angles ( ): N(1)–C(1) 1.347(4), N(2)–C(1) 1.274(4), N(2)–C(2) 1.368(4), N(3)–C(2) 1.269(4), N(1)–C(1)–N(2)
120.8(3), C(1)–N(2)–C(2) 130.6(3), N(2)–C(2)–N(3) 127.7(3).
10352 | Dalton Trans., 2011, 40, 10351–10359
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The Royal Society of Chemistry 2011
©

Fig. 2 Molecular structure of {[N{(C3F7)C(C6F5)N}2]Ag}n showing the atom numbering scheme and extended structure. Thermal ellipsoids drawn at
◦
˚
the 50% level. Selected bond lengths (A) and angles ( ): N(3)–C(2) 1.298(9), C(2)–N(2) 1.318(10), N(2)–C(1) 1.327(10), C(1)–N(1) 1.278(10), N(1)–Ag
2.113(6), Ag–N(3a) 2.120(6), Ag–N(3)–C(2) 127.2(5), N(3)–C(2)–N(2) 124.4(7), C(2)–N(2)–N(1) 131.7(7), N(2)–C(1)–N(1) 124.4(7), C(1)–N(1)–Ag
130.6(6), N(1)–Ag–N(3a) 174.7(2).
and [N{(C3F7)C(2-F,6-CF3C6H3)N}2]Ag are also known but
structural data are not available.47,49
The X-ray crystal structure of {[N{(C3F7)C(C6F5)-
N}2]Ag(NCCH3)}n which exists as helical chains is illustrated
in Fig. 3. It shows the presence of three-coordinate silver atoms
(with almost T-shaped geometry, with an N1–Ag–N4 angle
of 154.28(10)◦) coordinated to the terminal nitrogen atoms
of bridging, bidentate triazapentadienyl ligands. The third
coordination site is occupied by an acetonitrile ligand which
coordinates to silver at an angle (Ag–N–C angle = 160.4(3)◦). The
coordination of acetonitrile in a non-linear fashion may be a sign
of a weak s-donor type interaction. The NCNCN core of the
triazapentadienyl ligand adopts a twisted S-shaped configuration.
Polymeric {[N{(C3F7)C(2,6-Cl2C6H3)N}2]Ag(NCCH3)}n crys-
tallizes in the P21/c space group with two different
[N{(C3F7)C(2,6-Cl2C6H3)N}2]Ag(NCCH3) moieties in the asym-
metric unit (one of those is shown in Fig. 4). The angle of
acetonitrile coordination to Ag(I) is noticeably different in the two
Silver(I) acetonitrile adducts {[N{(C3F7)C(C6F5)N}2]Ag-
(NCCH3)}n and {[N{(C3F7)C(2,6-Cl2C6H3)N}2]Ag(NCCH3)}n
were prepared by refluxing the corresponding triazapentadienes
with Ag2O in pure acetonitrile or a mixture of acetonitrile–
THF. The products were obtained as dark oils initially but
slowly crystallized upon standing in a ventilated hood. Loss
of acetonitrile from {[N{(C3F7)C(C6F5)N}2]Ag(NCCH3)}n and
{[N{(C3F7)C(2,6-Cl2C6H3)N}2]Ag(NCCH3)}n or prolonged ex-
posure to light leads to some decomposition as is evident from the
formation of black material on the walls of the sample container.
These compounds are not soluble in n-hexane and slightly soluble
in aromatic solvents or THF. They also decompose in halogenated
solvents like CHCl3 and CH2Cl2 over a period of several hours as
is evident from the formation of a metallic silver mirror.
Fig. 3 Molecular structure of {[N{(C3F7)C(C6F5)N}2]Ag(NCCH3)}n showing the atom numbering scheme and extended structure. Thermal ellipsoids
◦
˚
drawn at the 50% level. Selected bond lengths (A) and angles ( ): N(3)–C(2) 1.296(4), C(2)–N(2) 1.328(4), N(2)–C(1) 1.306(4), C(1)–N(1) 1.319(4),
N(1)–Ag 2.191(3), Ag–N(3a) 2.436(3), Ag–N(4) 2.189(3), N(4)–C(21) 1.135(5), N(3)–C(2)–N(2) 131.8(3), C(2)–N(2)–C(1) 133.2(3), N(2)–C(1)–N(1)
124.7(3), N(1)–Ag–N(4) 154.28(10), N(1)–Ag–N(3a) 119.24(9), N(3a)–Ag–N(4) 86.24(10), Ag–N(4)–C(21) 160.4(3).
This journal is
The Royal Society of Chemistry 2011
Dalton Trans., 2011, 40, 10351–10359 | 10353
©

Fig. 4 Molecular structure of [N{(C3F7)C(2,6-Cl2C6H3)N}2]Ag(NCCH3) showing the atom numbering scheme and extended structure. Thermal
◦
˚
ellipsoids drawn at the 50% level. Selected bond lengths (A) and angles ( ): N(3)–C(2) 1.304(5), C(2)–N(2) 1.321(5), N(2)–C(1) 1.324(5), C(1)–N(1)
1.307(5), N(1)–Ag(1) 2.178(3), Ag(1)–N(4) 2.350(5), Ag(1)–N(3a) 2.227(3), N(4)–C(21) 1.158(8), N(3)–C(2)–N(2) 124.8(4), C(2)–N(2)–N(1) 131.6(3),
N(2)–C(1)–N(1) 125.1(3), C(1)–N(1)–Ag(1) 136.5(3), N(1)–Ag(1)–N(3a) 150.28(12), N(1)–Ag(1)–N(4) 118.52(14), N(3a)–Ag(1)–N(4) 90.69(14),
Ag(1)–N(4)–C(21) 150.9(6).
units with Ag–N–C angles of 132.9(5)◦ and 150.9(6)◦, respectively.
The triazapentadienyl ligand backbones adopt twisted W-shaped
configurations. Three-coordinate silver atoms feature distorted
T-shaped geometry and coordinate to the terminal nitrogen
atoms of bridging, bidentate triazapentadienyl ligands. The third
coordination site is occupied by an acetonitrile ligand.
{[N{(CF3)C(C6F5)N}2]Ag(NCCH3)2}n which has the smaller
–CF3 group on the triazapentadienyl ligand backbone was
synthesized using [N{(CF3)C(C6F5)}2]H and Ag2O in a mix-
ture of acetonitrile and THF. Removal of the solvent
yielded an oily material which solidified upon standing.
{[N{(CF3)C(C6F5)N}2]Ag(NCCH3)2}n showed good solubility
in chloroform and CH2Cl2. Colorless rod shaped crystals of
{[N{(CF3)C(C6F5)N}2]Ag(NCCH3)2}n were obtained by slow
diffusion of hexane into a solution of the compound in CH2Cl2
Fig. 5 Molecular structure of {[N{(CF3)C(C6F5)N}2]Ag(NCCH3)2}n
showing the atom numbering scheme. Thermal ellipsoids drawn at the
at room temperature (some product decomposition was also
observed during the recrystallization leaving black material on the
wall of the container). The crystals were stable in air for several
minutes, but prolonged exposure to light turned the crystals dark
brown.
◦
˚
50% level. Selected bond lengths (A) and angles ( ): Ag(1a)–N(8) 2.382(2),
N(6)–Ag(2) 2.429(2), Ag(2)–N(9) 2.311(2), N(9)–C(37) 1.134(3),
Ag(2)–N(10) 2.364(2), N(10)–C(39) 1.125(4), Ag(2)–N(3) 2.397(2),
N(1)–Ag(1) 2.4404(19), Ag(1)–N(4) 2.294(2), Ag(1)–N(5) 2.318(3),
N(4)–C(17) 1.138(3), N(5)–C(19) 1.136(4), N(3)–Ag(2)–N(10) 102.66(8),
N(3)–Ag(2)–N(9) 135.33(8), N(3)–Ag(2)–N(6) 92.53(7), N(9)–Ag(2)–
N(10) 96.52(9), N(9)–Ag(2)–N(6) 104.60(8), N(6)–Ag(2)–N(10)
131.00(8), N(1)–Ag(1)–N(5) 117.68(8), N(1)–Ag(1)–N(8a) 98.19(7),
N(1)–Ag(1)–N(4) 108.23(8), N(5)–Ag(1)–N(8a) 105.95(8), N(5)–Ag(1)–
N(4) 103.14(9), N(4)–Ag(1)–N(8a) 124.74(8), Ag(2)–N(9)–C(37)
170.7(2), Ag(2)–N(10)–C(39) 150.1(2), Ag(1)–N(5)–C(19) 160.6(2),
Ag(1)–N(4)–C(17) 164.6(2).
The X-ray data of {[N{(CF3)C(C6F5)N}2]Ag(NCCH3)2}n
(Fig. 5) show that the asymmetric unit contains two moieties
of [N{(CF3)C(C6F5)N}2]Ag(NCCH3)2. The overall structure is
a polymer, featuring tetrahedral silver sites linked by bridging
bidentate triazapentadienyl ligands. The NCNCN core adopts
a helical configuration. Each silver atom is coordinated to
two acetonitrile molecules with Ag–N–C angles ranging from
150.1(2)◦ to 170.7(2)◦. The Ag(NCCH3)2 moiety is flanked by the
two –CF3 groups of the triazapentadienyl ligands. Interestingly,
{[N{(C3F7)C(C6F5)N}2]Ag(NCCH3)}n, which has larger –C3F7
substituents on the triazapentadienyl ligand backbone, crystallizes
as a mono-acetonitrile adduct rather than a di-acetonitrile system.
This is probably the result of a steric effect caused by the bulkier
–C3F7 substituents preventing the coordination of an additional
acetonitrile molecule to the silver.
and shows a very different triazapentadienyl ligand coordination
mode in which the central nitrogen atom binds to silver (which is
1
two-coordinate) in a k -fashion (Scheme 1).
We have also synthesized {[N{(C3F7)C(C6F5)N}2]Ag-
(NCC3H7)}n which has a relatively large ligand, butyronitrile.
The X-ray structure of {[N{(C3F7)C(C6F5)N}2]Ag(NCC3H7)}n
is depicted in Fig. 6. It is also a polymeric adduct with
three-coordinate, distorted T-shaped silver sites. In contrast
We also reported
a mono-acetonitrile silver(I) complex
(CH3CN)Ag[N{(C3F7)C(Dipp)N}2] bearing larger aryl groups
on the triazapentadienyl terminal nitrogen atoms and –C3F7
substituents on the ligand backbone carbons.33 It is a monomer
to
{[N{(C3F7)C(2,6-Cl2C6H3)N}2]Ag(NCCH3)}n,
but
as
the
observed
for
{[N{(C3F7)C(C6F5)N}2]Ag(NCCH3)}n,
larger N–Ag–N angle (155.62◦) at the silver atom in
10354 | Dalton Trans., 2011, 40, 10351–10359
This journal is
The Royal Society of Chemistry 2011
©

Fig. 6 Molecular structure of {[N{(C3F7)C(C6F5)N}2]Ag(NCC3H7)}n showing the atom numbering scheme and extended structure. Thermal ellipsoids
◦
˚
drawn at the 50% level. Selected bond lengths (A) and angles ( ): N(3)–C(2) 1.313(3), C(2)–N(2) 1.315(3), N(2)–C(1) 1.329(3), C(1)–N(1) 1.299(3),
N(1)–Ag 2.437(2), Ag–N(3a) 2.181(2), Ag–N(4) 2.169(2), N(4)–C(21) 1.147(4), N(3)–C(2)–N(2) 125.2(2), C(2)–N(2)–C(1)134.9(2), N(2)–C(1)–N(1)
132.7(2), C(1)–N(1)–Ag 131.72(17), N(1)–Ag–N(4) 87.87(8), N(1)–Ag–N(3a) 116.41(8), N(3a)–Ag–N(4) 155.62(8), Ag–N(4)–C(21) 170.2(2).
THF did not produce THF or toluene coordinated complexes.
A different coordination mode of the fluorinated triazapenta-
dienyl ligand was observed when N(C2H5)3 was used as the
additional N-donor. Reaction of [N{(C3F7)C(2,6-Cl2C6H3)N}2]H
with Ag2O in the presence of triethylamine gave [N{(C3F7)C(2,6-
Cl2C6H3)N} ]AgN(C2H5)3. The X-ray data of [N{(C3F7)C(2,6-
Cl2C6H3)N}22]AgN(C2H5)3 revealed the presence of a monomeric
structure and a two-coordinate silver center with a slightly bent N–
Ag–N angle of 169.86(8)◦ (Fig. 7). There are two intra-molecular
˚
Ag ◊ ◊ ◊ F contacts at 2.892 and 3.083 A (cf. sum of the van
˚
der Waals radii of Ag and F = 3.19 A) on the wider side of
the N–Ag–N angle, perhaps causing this slight distortion. The
1
[N{(C3F7)C(2,6-Cl2C6H3)N}2]- ligand binds to silver in a k -
fashion via one of the terminal N-atoms. 19F NMR analysis in
CDCl3 indicated that the –C3F7 chains sit in different chemical
environments in solution at room temperature. The NCNCN core
adopts a distorted W-shaped configuration. The triethylamine
ligand forms an umbrella-like covering over the silver(I) atom.
Scheme
(CH3CN)Ag[N{(C3F7)C(Dipp)N}2],
Ag(NCCH3)}n and [N{(C3F7)C(2,6-Cl2C6H3)N}2]AgN(C2H5)3.
1
1,3,5-Triazapentadienyl ligand coordination modes in
˚
˚
The N–Ag–N(C2H5)3 distances are 2.1170(19) A and 2.163(2) A,
respectively. The X-ray crystal structures of silver(I) N(C2H5)3
complexes are not available for comparison. Monomeric metal
{[N{(C3F7)C(2,6-Cl2C6H3)N}2]-
1
adducts with k -coordinated side-bonded 1,5-diazapentadienyl
{[N{(C3F7)C(C6F5)N}2]Ag(NCC3H7)}n
results
from
the
ligands have not been reported to our knowledge. One of the
isomers of [N{(C3F7)C(Ph)N}2]HgMe is believed to feature a side-
bonded 1,3,5-triazapentadienyl ligand in solution.55
coordination of one of the terminal nitrogen atoms of the
triazapentadienyl ligand and the nitrile nitrogen center. The
Ag–N(nitrile) distances in {[N{(C3F7)C(C6F5)N}2]Ag(NCCH3)}n
and {[N{(C3F7)C(C6F5)N}2]Ag(NCC3H7)}n are similar at
˚
˚
2.189(3) A and 2.169(2) A, respectively. The corresponding
Conclusions
values for {[N{(C3F7)C(2,6-Cl2C6H3)N}2]Ag(NCCH3)}n are
˚
˚
significantly larger at 2.350(5) A and 2.535(5) A (two molecules).
For comparison, the Ag–N distances of the tricoordinated
Overall, we report the isolation and full characterization of a series
of silver(I) adducts supported solely by 1,3,5-triazapentadienyl
ligands or by triazapentadineyl and other nitrogen donors
like acetonitrile, butyronitrile and triethylamine. The poly-
meric salts {[N{(C3F7)C(C6F5)N}2]Ag}n and {[N{(C3F7)C(2,6-
Cl2C6H3)N}2]Ag}n show high air and light stability for days. We
also described the first structures of bridging, bidentate triaza-
and tetracoordinated species (PPh3)2Ag(NCCH3) and
53,54
˚
˚
[Ag(NCCH3)4]BF4 are 2.321(2) A and 2.266 A, respectively.
It should be noted that, in contrast to the formation of nitrile
adducts described above, silver adducts prepared using fluorinated
triazapentadienes with Ag2O in either THF or THF–toluene or by
using lithium salts of the triazapentadienyl ligands and AgSbF6 in
1
pentadienyl systems as well as a rare side bonded k -coordination
This journal is
The Royal Society of Chemistry 2011
Dalton Trans., 2011, 40, 10351–10359 | 10355
©

Fig. 7 Molecular structure of [N{(C3F7)C(2,6-Cl2C6H3F5)N}2]AgN(C2H5)3 showing the atom numbering scheme and the conformation of the ligand
◦
˚
backbone. Thermal ellipsoids drawn at the 50% level. Selected bond lengths (A) and angles ( ): N(3)–C(2) 1.279(3), C(2)–N(2) 1.353(3), N(2)–C(1)
1.292(3), C(1)–N(1) 1.327(3), N(1)–Ag 2.1170(19), Ag–N(4) 2.163(2), N(3)–C(2)–N(2) 127.8(2), C(2)–N(2)–C(1) 133.7(2), N(2)–C(1)–N(1) 123.8(2),
C(1)–N(1)–Ag 129.15(16), N(1)–Ag–N(4) 169.86(8).
of a triazapentadienyl ligand (Scheme 1). In these adducts, the
triazapentadienyl ligands use terminal nitrogen atoms for metal
ion coordination. In contrast, (MeCN)Ag[N{(C3F7)C(Dipp)N}2]
shows metal coordination via the central nitrogen atom of
the triazapentadienyl ligand. We are currently exploring the
ligand transfer chemistry and catalytic properties of silver–
triazapentadienyl systems.
needles were obtained by slow evaporation from a solution in
acetone–toluene. Yield: 41%. ESI–MS: m/z 802, 804 (Ag–L·H+);
908, 910 (Ag–L·Ag+); 1497, 1499 (H–L–Ag–L·H+); 1603, 1605
(Ag–L–Ag–L·H+); 2298, 2300 (H–L–Ag–L–Ag–L·H+); 2404,
2406 (Ag–L–Ag–L–Ag–L·H+). M.p.: 220–225 ◦C (dec.). 19F
NMR (470.62 MHz, DMSO-d6, 25 ◦C): d -79.5 (t, JFF = 8.6 Hz,
6F, CF3), -111.2 (s, 4F, CF2), -123.9 (s, 4F, CF2). 1H NMR
(500.16 MHz, DMSO-d6, 25 ◦C): d 7.20 (br, 4H, m-Ar), 6.85 (br,
2H, p-Ar). Anal. calcd for C20H6Cl4F14N3Ag C, 29.88; H, 0.75; N,
5.23; found C, 30.47; H, 1.06; N, 5.19%.
Experimental
General procedures
{[N{(C3F7)C(C6F5)N}2]Ag(NCCH3)}n. [N{(C3F7)C(C6F5)N}2]-
H (0.5 g, 0.68 mmol), Ag2O (0.09 g, 0.41 mmol), acetonitrile
10 mL and THF 20 mL were heated at 75 ◦C for 12 h in an
oil bath. The solution was filtered over a bed of Celite and
concentrated. Transparent needles are obtained after three days
by slow evaporation at room temperature. Yield: 58%.◦ M.p.
All manipulations were carried out under an inert atmosphere of
purified nitrogen using standard Schlenk techniques. Reactions
involving silver(I) starting materials were performed in flasks
covered with aluminium foil (to protect from light). Solvents were
purchased from commercial sources, distilled from conventional
drying agents, and degassed by the freeze–pump–thaw method
twice prior to use. Glassware was oven-dried at 150 ◦C overnight.
NMR spectra were recorded in CDCl3 at 25 ◦C on JEOL Eclipse
500 and 300 spectrometers (1H: 500.16 MHz, 300.53 MHz and 19F:
470.62 MHz, 282.78 MHz). Proton chemical shifts are reported in
ppm versus Me4Si. 19F NMR chemical shifts were referenced rela-
tive to external CFCl3. Elemental analyses were performed using
a Perkin Elmer Series II CHNS/O analyzer. Melting points were
obtained on a Mel-Temp II apparatus and were not corrected. Sil-
ver(I) oxide, triethylamine and butyronitrile were purchased from
commercial sources. [N{(C3F7)C(C6F5)N}2]H, [N{(C3F7)C(2,6-
Cl2C6H3)N}2]H and [N{(CF3)C(C6F5)N}2]H were prepared as
described previously.31,35,47
◦
120–125 C (dec). 19F NMR (282.78 MHz, DMSO-d6, 25 C): d
-80.1 (t, JFF = 8.7 Hz, 6F, CF3), -113.5 (s, 4F, CF2), -125.4 (s, 4F,
CF2), -149.0 (d, JFF = 19.5 Hz, 4F, CF), -166.5 (t, JFF = 19.5 Hz,
21.7 Hz, 4F, CF), -167.6 (t, JFF = 21.7 Hz, 23.8 Hz, 2F, CF). 1H
NMR (300.53 MHz, DMSO-d6, 25 ◦C): d 2.05 (s, 3H, CH3CN).
Anal. calcd for C22H3F24N4Ag C, 29.79; H, 0.34; N, 6.32; found
C, 29.04; H, 0.22; N, 6.93%.
{[N{(CF3)C(C6F5)}2]Ag(NCCH3)2}n. [N{(CF3)C(C6F5)}2]H
(0.100 g, 0.185 mmol) was added to a suspension of Ag2O (0.032 g,
0.14 mmol) in a mixture of acetonitrile (5 mL) and THF (10 mL);
the mixture was refluxed for 16 h. The solution was filtered over a
bed of Celite and the solvent was removed from the filtrate under
reduced pressure to leave light yellow crystalline solid. The solid
was dissolved in minimum amount of CH2Cl2 and layered with
hexanes to obtain colorless crystals. Yield: 90.6%. M.p. 100 ◦C
(dec.), 19F NMR (DMSO-d6, 293 K): d -71.9 (s, CF3), -150.9
(s, CF), -168.4 (t, JFF = 22.0 Hz, CF), -169.6 (t, JFF = 22.0 Hz,
{[N{(C3F7)C(2,6-Cl2C6H3)N}2]Ag}n. [N{(C3F7)C(2,6-Cl2C6H3)-
N}2]H (1 eq.) and silver(I) oxide (0.75 eq., 50% excess) were
refluxed in THF for 12 h. The solution was filtered over a bed
of Celite and the solvent was evaporated to dryness. The residue
was washed with n-hexane, decanted and pumped dry to afford
{[N{(C3F7)C(2,6-Cl2C6H3)N}2]Ag}n as a white solid. Small
1
CF). H NMR (CDCl3, 293 K): 2.05 (s, CH3). Anal. calcd for
C17.6H2.4AgF1.6N3.8: C, 31.14; H, 0.36; N, 7.84%; found: C, 30.70;
H, 0.36; N, 7.90%.
10356 | Dalton Trans., 2011, 40, 10351–10359
This journal is
The Royal Society of Chemistry 2011
©

{[N{(C3F7)C(2,6-Cl2C6H3)N}2]Ag(NCCH3)}n. [N{(C3F7)C-
(2,6-Cl2C6H3)N}2]H (0.25 g, 0.36 mmol) and Ag2O (0.04 g,
[N{(C3F7)C(2,6-Cl2C6H3)N}2]AgN(C2H5)3. [N{(C3F7)C(2,6-
Cl2C6H3)N}2]H (0.5 g, 0.72 mmol), Ag2O (0.083 g, 0.36 mmol)
and triethylamine (0.1 mL, 0.72 mmol) were refluxed in THF for
12 h in an oil bath. The solution was filtered over a bed of Celite
and concentrated. Yellow cubes grew at -20 ◦C after 2 days. Yield:
56%. M. p. 125–127 ◦C (dec.). 19F NMR (470.62 MHz, CDCl3,
25 ◦C): d -80.0 and -80.4 (s, 6F, CF3), -109.5 (s, CF2),◦-122.8 and
◦
0.18 mmol) were heated at 90 C for 12 h in acetonitrile 20 mL.
The solution was filtered over a bed of Celite and concentrated
until an oily residue was obtained. This was dissolved in CH2Cl2,
filtered and left to evaporate at air at room temperature. Crystals
were observed after 24 h. Yield: 39%. M. p. 242–250 ◦C (dec.). 19
F
NMR (282.78 MHz, DMSO-d6, 25 ◦C): d -79.6 (t, JFF = 8.7 Hz,
-124.9 (s, CF2). H NMR (500.16 MHz, CDCl3, 25 C): d 7.32
1
1
10.8 Hz, 6F, CF3), -111.4 (s, 4F, CF2), -124.0 (s, 4F, CF2). H
to 7.17 (multiplet, 4H, m-Ar), 6.95 to 6.84 (multiplet, 2H, p-Ar),
2.06 (br, 6H, CH2CH3), 0.87 (br, 9H, CH2CH3). Anal. calcd for
C26H21Cl4F14N4Ag C, 34.50; H, 2.34; N, 6.19; found C, 34.58; H,
2.29; N, 6.17
NMR (300.53 MHz, DMSO-d6, 25 ◦C): d 7.18 (d, 3JHH = 8.3 Hz,
4H, m-Ar), 6.82 (t, 3JHH = 7.9, 2H, p-Ar), 2.08 (s, NCCH3). Anal.
calcd for C22H9Cl4F14N4Ag C, 31.27; H, 1.07; N, 6.63; found C,
31.24; H, 1.17; N, 6.49%.
X-Ray data collection and structure determinations
{[N{(C3F7 )C(C6F5 )N}2 ]Ag(NCC3H7 )}n. [N{(C3F7 )C(C6F5 )-
N}2]H (0.5 g, 0.68 mmol), Ag2O (0.09 g, 0.41 mmol), butyronitrile
(6 mL, 67.7 mmol) and THF 20 mL were stirred for 12 h at 75 ◦C.
Once cooled the reaction mixture was filtered and concentrated up
to 2 mL. It was left to crystallize in darkness by slow evaporation at
room temperature. Transparent plates are obtained after one week
(0.47 g, 76%). M.p. 150–152 ◦C (dec). 19F NMR (282.78 MHz,
DMSO-d6, 25 ◦C): d -79.9 (s, 6F, CF3), -113.3 (s, 4F, CF2), -125.3
Suitable crystals covered with a layer of paratone-N oil, were
selected and mounted within a cryo-loop and immediately placed
in the low-temperature nitrogen stream. The X-ray intensity data
were measured at 100(2) K on a Bruker SMART APEX CCD
area detector system equipped with a Oxford Cryosystems 700
Series cooler, a graphite monochromator, and a Mo Ka fine-focus
˚
sealed tube (l = 0.71073 A). The data frames were integrated with
the Bruker SAINT-Plus software package. Data were corrected
for absorption effects using the multi-scan technique (SADABS).
Structures were solved and refined using Bruker SHELXTL
(Version 6.14) software package. X-Ray files in cif-format are
available as supporting information,† and crystallographic data
are summarized in Table 1.
(s, 4F, CF2), -149.0 (d, JFF = 19.5 Hz, 4F, CF), -166.3 (t, JFF
=
21.7 Hz, 4F, CF), -167.4 (t, JFF = 23.8 Hz, 21.7 Hz, 2F, CF).
19F NMR (470.62 MHz, C6D6, 25 ◦C): d -80.3 (t, 8.6 Hz, 6F,
CF3), -112.4 (m, JFF = 734.2, 4F, CF2), -124.4 (m, JFF = 394.4 Hz,
4F, CF2), -147.8 (broad, 4F, CF), -164.4 (apparent triplet, JFF
=
23.0 Hz, 20.2 Hz, 2F, CF), -165.2 (apparent triplet, JFF = 17.3 Hz,
23.0 Hz, 4F, CF). 1H NMR (500.16 MHz, C6D6, 25 ◦C): d 1.35 (t,
[N{(C3F7)C(C6F5)N}2]H. Crystallized in space group P21/c
with three independent [N{(C3F7)C(C6F5)N}2]H molecules in the
asymmetric unit. The hydrogens on N-atoms were located and
refined. The fluorine atoms of one of the C2F3 moieties show
3JHH = 6.9 Hz, 2H, a-CH2), 0.94 (m, 2H, b-CH2), 0.55 (t, 3JHH
=
7.3 Hz, 3H, CH3). Anal. calcd for C24H7F24N4Ag C, 31.50; H, 0.77;
N, 6.12; found C, 32.47; H, 1.08; N, 5.98%.
Table 1 Crystallographic data
{[N{(C3F7)-
C(C6F5)N}2]-
(C6F5)N}2]Ag}n Ag(NCCH3)}n
{[N{(C3F7)-
{[N{(CF3)C-
(C6F5)N}2]-
{[N{(C3F7)C-
(C6F5)N}2]-
[N{(C3F7)C-
[N{(C3F7)C-
(C6F5)N}2]H
{[N{(C3F7)C-
C(2,6-Cl2C6H3)-
(2,6-Cl2C6H3)-
Compound
N}2]Ag(NCCH3)}n Ag(NCCH3)2}n Ag(NCC3H7)}n N}2]AgN(C2H5)3
Formula
FW
Temperature (K) 100(2)
C20HF24N3
739.24
C20AgF24N3
846.10
100(2)
C22H3AgF24N4
887.15
100(2)
C22H9AgCl4F14N4 C20H6AgF16N5
C24H7AgF24N4
915.21
100(2)
C26H21AgCl4F14N4
905.14
100(2)
845.00
728.17
100(2)
100(2)
Crystal system
Space group
Cell dimensions
Monoclinic
P2(1)/c
Monoclinic
P2(1)/n
Monoclinic
P2(1)/n
Monoclinic
P2(1)/c
Triclinic
P1
Orthorhombic
P2(1)2(1)2(1)
Monoclinic
¯
P2(1)/n
˚ ˚ ˚ ˚ ˚
˚ ˚
a = 19.7349(8) A a = 12.2939(6) A a = 10.1781(6) A a = 20.1753(12) A a = 9.5740(9) A a = 10.5771(6) A a = 11.0348(7) A
˚
˚
˚
˚
˚
˚
˚
˚
b = 17.2001(7) A b = 14.3955(6) A b = 14.2903(8) A b = 16.8846(10) A b = 13.1644(12) A b = 14.5688(9) A b = 26.8261(17) A
˚ ˚ ˚ ˚ ˚ ˚
c = 21.5731(8) A
c = 14.8014(7) A c = 18.6323(10) A c = 18.9949(11) A c = 19.7396(18) A c = 18.7937(11) A c = 11.6999(7) A
a = 90◦
b = 94.326(1)◦
g = 90◦
7302.0(5)
12
a = 90◦
a = 90◦
a = 90◦
a = 84.958(1)◦
b = 89.652(1)◦
g = 71.234(1)◦
2345.9(4)
4
a = 90◦
b = 90◦
a = 90◦
b = 103.430(1)◦ b = 93.876(1)◦
b = 116.350(1)◦
g = 90◦
b = 105.503(1)◦
g = 90◦
g = 90◦
2547.9(2)
4
g = 90◦
2703.8(3)
4
2.179
0.936
g = 90◦
3
˚
V (A)
5798.3(6)
8
1.936
2896.0(3)
4
3337.4(4)
4
1.801
Z
dcalcd (g cm-3)
2.017
2.206
0.987
2.062
1.009
2.099
0.878
Abs coeff (mm-1) 0.251
1.177
1.029
F (000)
4296
1.57 to 26.00
58302
1616
2.00 to 25.50
18231
0.0325(4734)
4734/24/454
1.197
1704
1.80 to 26.00
20097
0.0291(5273)
5273/31/483
1.039
3280
1.70 to 26.00
40248
0.0355(11119)
11119/0/813
1.039
1408
1.64 to 26.50
20452
0.0202(9670)
9670/0/761
1.039
1768
1.77 to 26.00
22557
0.0273 (5674)
5674/30/501
1.068
1784
2.06 to 28.28
29716
0.0291(8016)
8016/48/458
1.026
q range (◦)
Reflns collected
Rint (ind reflns)
0.0294(14338)
Data/restr/params 14338/72/1299
GOF on F2
R1 [I > 2s(I)]/
all data
1.017
0.0677/0.0758
0.0736/0.0799 0.0316/0.0364
0.0451/0.0572
0.0310/0.0356
0.0228/0.0551
0.0369/0.0458
wR2 [I > 2s(I)]/ 0.1837/0.1921
all data
0.1930/0.1979 0.0726/0.0796
0.1113/0.1212
0.0748/0.0783
0.0233/0.0554
0.0878/0.0933
This journal is
The Royal Society of Chemistry 2011
Dalton Trans., 2011, 40, 10351–10359 | 10357
©

positional disorder. The disorder of the “CF2” unit was modelled
successfully with an occupancy ratio of 80 : 20. All the non-
hydrogen atoms, except the minor occupancy fluorines (F3c and
Acknowledgements
This work was supported by the National Science Foundation
(CHE-0845321 to H.V.R.D) and the Robert A. Welch Foundation
(Grant Y-1289 to H.V.R.D). The NSF (CHE-0840509) is thanked
for providing funds to upgrade the NMR spectrometer used in
this work. The X-ray crystallography was performed in the Center
for Nanostructured Materials (CNM) at the University of Texas
at Arlington. We also thank Dr Muhammed Yousufuddin (CNM)
for collecting X-ray data on one of the compounds reported here.
F4c) were refined anisotropically. The largest maximum (positive)
-3
˚
residual density of 1.90 e A and minimum (negative) residual
-3
˚
˚
˚
density of -0.92 e A were observed at 0.54 A from F4c and 0.77 A
from F2b, respectively. We have repeated the data collection using
a fresh crystal from a different batch but the residual densities did
not change significantly.
{[N{(C3F7)C(C6F5)N}2]Ag}n. Crystallized in space group
P21/n. All the non-hydrogen atoms were refined with anisotropic
displacement parameters.
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