Cationic and neutral (Ar-BIAN)copper(I) complexes containing phosphane and arsane ancillary ligands: Synthesis, molecular structure and catalytic behaviour in cycloaddition reactions of azides and alkynes

Article abstract of DOI:10.1002/ejic.201201211

A series of new cationic and neutral (Ar-BIAN)copper(I) complexes [in which Ar-BIAN = bis(aryl)acenaphthenequinonediimine] was synthesised and characterised by elemental analysis, 1D and 2D NMR spectroscopy and single-crystal X-ray diffraction. The cation

Full text of DOI:10.1002/ejic.201201211

FULL PAPER
DOI:10.1002/ejic.201201211
Cationic and Neutral (Ar-BIAN)Copper(I) Complexes
Containing Phosphane and Arsane Ancillary Ligands:
Synthesis, Molecular Structure and Catalytic Behaviour in
Cycloaddition Reactions of Azides and Alkynes
Lidong Li,[a] Patrícia S. Lopes,[a] Cláudia A. Figueira,[a]
Clara S. B. Gomes,[a] M. Teresa Duarte,[a] Vitor Rosa,[b]
Christophe Fliedel,[b] Teresa Avilés,*[b] and Pedro T. Gomes*[a]
COVER PICTURE
Keywords: Copper / P ligands / As ligands / Homogeneous catalysis / Cycloaddition
A series of new cationic and neutral (Ar-BIAN)copper(I) com-
Ar-BIAN and EPh3 (E = P, As or Sb) in acetonitrile under re-
plexes [in which Ar-BIAN = bis(aryl)acenaphthenequinone- flux conditions. The type of ancillary ligand EPh3 and the aryl
diimine] was synthesised and characterised by elemental
analysis, 1D and 2D NMR spectroscopy and single-crystal X-
ray diffraction. The cationic complexes of the general for-
mula [Cu(Ar-BIAN)L2]BF4 [L2 = (PPh3)2 (1), dppe (2), dppf (3),
(AsPh3)2 (4); Ar = 4-iPrC6H4 (a), 4-MeOC6H4 (b), 4-NO2C6H4
(c), 2-iPrC6H4 (d), Ph2PCH2CH2PPh2 (dppe), (Ph2PC5H4)2Fe
(dppf)] were synthesised by reaction of [Cu(EPh3)4]BF4 (E =
P or As) and equimolar amounts of Ar-BIAN ligands, or by
reaction of equimolar amounts of [Cu(NCMe)4]BF4, 4-
iPrC6H4-BIAN (a) and diphosphanes dppe or dppf, in dichlo-
romethane, whereas the neutral complexes of the types
[CuX(Ar-BIAN)(EPh3)] [X = Cl, E = P (5); X = I, E = P (6); X
= Cl, E = As (9)] and [{CuX(Ar-BIAN)}2] [X = Cl (7), I (8); Ar
= a, b, c, d, 2,4,6-Me3C6H2 (e), 2,6-iPr2C6H3 (f)] were pre-
pared by reaction of CuCl or CuI with equimolar amounts of
substituents on Ar-BIAN play crucial roles in determining the
formation of cationic or neutral copper(I) complexes. No cop-
per(I) complexes containing coordinated SbPh3 were iso-
lated; all the corresponding attempts led to dimeric com-
plexes 7 or 8. Most of the complexes crystallised easily. Their
study by X-ray diffraction revealed distorted-tetrahedral
geometries around the copper(I) centres, which are quite in-
fluenced by the various aryl substituents on Ar-BIAN and the
ancillary ligands EPh3. All complexes 1–9 except cationic
dppf derivative 3a are active catalysts for cycloaddition reac-
tions of alkynes and azides, and also show good tolerance
towards functionalised substituents of alkynes and azides.
Among them, the PPh3-coordinated complexes 1, 5 and 6 af-
forded the highest catalytic activities [turnover frequency =
26.9–45.7 h–1].
sodium ascorbate[1a] and CuI/DIPEA (DIPEA = diisoprop-
ylethylamine).[5] Owing to the thermodynamic instability of
copper(I) species, an excess amount of reducing agents is
necessary to stabilise the in situ formed copper(I) species in
the former instance, whereas ancillary ligands are indispens-
able in the latter one. In consequence, such a multiple-com-
ponent catalyst system makes it more difficult to investigate
catalytic species and the mechanism for this transformation.
Additionally, ligand rate-accelerating effects have been ob-
served in a number of CuAAC reactions,[6] and, in some
cases, the resulting polytriazole products autocatalyse the
reaction [e.g., tris(benzyltriazolylmethyl)amine].[7,8] How-
ever, the real role of such ligands in the catalytic cycles still
remains elusive. Therefore, the preparation and characteri-
sation of well-defined homogeneous copper(I) complexes,
which are active catalysts for the CuAAC reaction in the
absence of any in situ added ancillary ligands, may be re-
garded as important mechanistic tools.
Introduction
Over the past decade, the copper(I)-catalysed azide–alk-
yne cycloaddition reaction (CuAAC; click chemistry[1]) has
found a broad spectrum of applications in chemical synthe-
sis,[2] medicinal chemistry[3] and materials science.[4] The
studies showed that the presence and stability of copper(I)
species in the CuAAC catalyst system is crucial to ensure
the reaction proceeds with high efficiency and regioselectiv-
ity. These copper(I) species are commonly generated from
a multiple-component catalyst system, for example, CuSO4/
[a] Centro de Química Estrutural, Departamento de Engenharia
Química, Instituto Superior Técnico,
Universidade Técnica de Lisboa,
Av. Rovisco Pais, 1049-001 Lisboa, Portugal
Fax: +351-218417246
E-mail: pedro.t.gomes@ist.utl.pt
Homepage: http://cqe.ist.utl.pt/
[b] REQUIMTE, Departamento de Química, Faculdade de
Ciências e Tecnologia, Universidade Nova de Lisboa,
Caparica 2829-516, Portugal
Just a few cases have been reported to date in which well-
defined cationic or neutral copper(I) complexes were used
as catalysts to promote the CuAAC reaction,[9] for example,
Homepage: http://www.requimte.pt
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.201201211.
Eur. J. Inorg. Chem. 2013, 1404–1417
1404
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

www.eurjic.org
FULL PAPER
[Cu(C186tren)]Br [C186tren = tris(2-dioctadecylaminoeth- characterisation of a series of new cationic Ar-BIAN-based
yl)amine],[10]
[TBTA
[CuI2(μ-TBTA-κ4-N2,N3,N3Ј,N3ЈЈ)2](BF4)2 copper(I) complexes of the type [Cu(Ar-BIAN)L2]BF4
=
tris(benzyltriazolylmethyl)amine],[11] [CuCl- bearing neutral donor ancillary ligands such as PPh3, di-
(TBTM)] [TBTM = tris(1-benzyl-1H-1,2,3-triazol-4-yl)- phosphanes [Ph2PCH2CH2PPh2, dppe (2a); (Ph2PC5H4)2-
methanol],[12] [CuI(BBCD)] [BBCD = trans-N,NЈ-bis(1- Fe, dppf (3a); Scheme 1] or the more labile AsPh3. In ad-
ethyl-2-benzimidazolylmethylene)cyclohexane-1,2-diimine],[13] dition, the syntheses and characterisation of a series of new
[Cu2I2(SNS)]n {SNS = bis[2-(benzylthio)ethyl]amine},[14] neutral (Ar-BIAN)copper(I) complexes of the type
[Cu(Tpmx)(NCMe)]BF4 [Tpmx = tris(pyrazolyl)methane],[15] [CuX(Ar-BIAN)(EPh3)], containing a neutral donor ligand
[CuI(PTA)]PF6 (PTA
= 1,3,5-triaza-7-phosphaadaman- EPh3 (E = P or As) and a halide ligand X, are also re-
tane),[16] [CuBr(PPh3)3],[17] [CuX(NHC)] (NHC=N-hetero- ported. For both types of complexes, aryl groups of various
–
cyclic carbene; X = Cl, Br),[18] [Cu(NHC)2]X (X = BF4 , electronic and steric natures were used in the Ar-BIAN
– [19]
PF6 ) and [Cu{2-(CH2N(CH3)2)C6H4S}].[20]
backbones, which led to marked effects on the preparation
Owing to our interest in complexes encompassing bis- and molecular structures of the resulting copper(I) com-
(aryl)acenaphthenequinonediimine ligands (Ar-BIAN),[21] plexes. The catalytic behaviour of both series of complexes
in a recent paper[22] we reported the synthesis of a series of in cycloaddition reactions of azides and alkynes are also
mono- or bis-chelated Ar-BIAN-based cationic copper(I) studied and discussed.
complexes, and found they were active catalysts for the
CuAAC reaction in the absence of any extra in situ added
ancillary ligands, with moderate or high activities. In par-
ticular, the copper(I) complex bearing labile PPh3 ligands,
Results and Discussion
[Cu(4-iPrC6H4-BIAN)(PPh3)2]BF4 (1a; Scheme 1), exhib-
ited high catalytic activity comparable with that of the typi-
Synthesis and Characterisation
cal CuSO4/sodium ascorbate catalyst system.
Cationic copper(I) complex salts 1b–d and 4a–d bearing
PPh3 or AsPh3 ancillary ligands, respectively, were synthe-
sised by treatment of [Cu(PPh3)4]BF4 or [Cu(AsPh3)4]BF4
with equimolar amounts of the corresponding Ar-BIAN li-
gands in dichloromethane, at room temperature, in moder-
ate to high yields (51–91%; Scheme 1). The same synthetic
procedure failed to prepare copper(I) complex analogues
coordinated by much bulkier Ar-BIAN ligands [Ar = 2,4,6-
Me3C6H2 (e), 2,6-iPr2C6H3 (f)], even if reflux conditions
(ca. 60 °C) were employed. Likewise, such a synthetic strat-
egy did not succeed in the preparation of copper(I) complex
salts bearing SbPh3 ancillary ligands. Copper(I) Ar-BIAN
complexes 2a and 3a, containing chelating ancillary ligands
dppe and dppf, respectively, were prepared by reaction of
equimolar amounts of [Cu(NCMe)4]BF4, 4-iPrC6H4-BIAN
(a) and the corresponding diphosphanes in dichlorometh-
ane, in high yields (81 and 91%, respectively; Scheme 1).
Complexes 1–4 were characterised by elemental analysis,
1H and 13C{1H} NMR spectroscopy, 2D homo- and het-
eronuclear correlation NMR spectroscopy (COSY, HSQC
and HMBC) and 31P{1H} NMR spectroscopy (for com-
1
plexes 1–3). All the H and characteristic 13C resonances
1
were assigned. The H resonances of Ar-BIAN backbones
of complexes apparently shifted to lower field relative to
their corresponding free ligands owing to their coordination
1
to cationic CuI. Noteworthy is that two sets of H and 13C
resonances were observed in complexes 1d and 4d, respec-
tively. These two sets of resonances could be assigned to the
syn and anti conformers of complexes, respectively, re-
sulting from rotation of their aryl groups around Caryl–N
bonds.[21j] No 31P resonances were observed for complexes
1a–d, whereas complexes 2a and 3a, containing diphos-
Scheme 1. Syntheses of cationic copper(I) complexes bearing PPh3,
diphosphanes or AsPh3. (i) [Cu(PPh3)4]BF4 or [Cu(AsPh3)4]BF4
(1.0 equiv.), CH2Cl2; (ii) [Cu(NCMe)4]BF4 (1.0 equiv.), dppe or
dppf (1.0 equiv.), CH2Cl2; (iii) [Cu(SbPh3)4]BF4 (1.0 equiv.),
CH2Cl2.
Following this work, and also in view of the limited phane ligands, showed resonances at δ = –0.43 and
number of Ar-BIAN copper(I) complexes containing phos- –10.92 ppm, respectively. These two 31P resonances are
phane ligands[23] or the absence of such complexes contain- comparable with those of other previously reported (dppe)-
ing arsane or stibine ligands, we report the syntheses and copper(I)[24] and (dppf)copper(I)[25] complexes, respectively.
Eur. J. Inorg. Chem. 2013, 1404–1417
1405
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

www.eurjic.org
FULL PAPER
As illustrated in Scheme 1, it is apparent that ancillary the 31P NMR spectra seems to be consistent with the fact
ligand EPh3 (E = P, As, Sb) and the aryl substituents of Ar- that an extensive dissociation of complexes 1a–d and a fast
BIAN are two key factors in determining the formation of exchange of free and coordinated PPh3 occur in solution,
cationic copper(I) complexes. Coordination of EPh3 to which led to a mixture of species in solution; see Equa-
transition metals involves both electronic and steric contri- tion (1).
butions, which can be rationalised by the still widely used
classical Tolman electronic ν {the frequency of the A1 carb-
onyl mode of [Ni(CO)3L] in dichloromethane; L denoting
phosphorus ligands} and steric θ (cone angle of phosphorus
(1)
ligands) parameters.[26] By extending this model to other
elements (As, Sb, Bi) of Group 15, the following sequence Analogous behaviours have also been observed for phos-
for both σ-donor ability and steric bulk was established: phorus-coordinated nickel(0) complexes of the type
PPh3 Ͼ AsPh3 Ͼ SbPh3.[26] The tendency for the former [Ni(PR3)4], in which PR3 = PEt3, PMePh2 or PPh3.[31] One
effect could be rationalised in terms of the increased loss of could assume that the weaker electron-donating ligand
σ-bond energy when descending in Group 15, which has AsPh3 would be even more labile and exhibit a similar be-
been substantiated by experimental evidence.[27–29] The lat- haviour to that shown in Equation (1). In the case of di-
ter effect seems to be confusing since it is inversed with the phosphane complexes 2a and 3a, stable cationic complexes
atomic radius sequence (P Ͻ As Ͻ Sb). Nonetheless, Tol- were obtained as a consequence of strong electron-donating
man’s cone-angle model could afford an unambiguous ex- abilities and significantly reduced steric bulks of bidentate
planation, thereby concluding that increasing M–E or E–C ligands dppe and dppf (θ = 126.7 and 132.9°, respecti-
bond lengths by approximately 0.1 Å decreases cone angles vely)[32] relative to PPh3 (θ = 145°).[26] Additionally, the
by 3 to 5°.[26] Since Pauling’s tetrahedral covalent radii for “chelating effect” in which the bidentate phosphane ligands
P, As and Sb are 1.10, 1.18 and 1.36 Å,[26] respectively, li- exhibit an enhanced affinity for cationic copper(I) relative
gand SbPh3 bearing the heavier element Sb gives rise to a to the monodentate phosphanes, also makes a great contri-
smaller cone angle than that for PPh3 and AsPh3. This is bution to their stabilities. Their observable 31P resonances
clearly exemplified in complexes [Ag(EPh3)n]+, in which co- indicate a less fluxional/labile character and afford further
ordination numbers of 4 for SbPh3 and 2 for PPh3 are ob- evidence for their preference for stable cationic complexes.
served.[30]
Different from the ancillary ligands EPh3, the steric ef-
In the present case, by considering both the electronic fects of the Ar-BIAN ligand seem to be predominant in
and steric sequences of EPh3 ligands, it can be concluded determining the formation of cationic complexes. As can be
that the formation of cationic complexes 1–4 is mainly seen from complexes 1a–d or 4a–d, the bulkier ligands with
dominated by the electronic nature of EPh3 ligands. The 2,6-disubstituted aryl groups e and f failed to form cationic
PPh3 and AsPh3 ligands, with relatively stronger electron σ- copper(I) complexes, whereas the less bulky ones with o-
donating abilities although their steric bulks are larger, led unsubstituted or o-monosubstituted aryl groups a–d suc-
to stable cationic complexes 1 and 4, whereas their SbPh3 ceeded. In contrast, the electronic nature of the ligands ex-
analogues failed to be obtained owing to the relatively hibit minor influences, as demonstrated in the case of 1a–c
weaker electron-donating ability of SbPh3 (see Scheme 1).
or 4a–c, the ligands of which show an insignificant effect
The absence of 31P NMR spectroscopy resonances, ob- on their reactivities (see below).
served in the present work for complexes 1b–d in solution,
Neutral copper(I) complexes 5a–e and 6a–e, bearing the
was also previously observed and studied by us for complex same PPh3 ancillary ligand, were prepared by reaction of
1a.[22] In fact, the 31P NMR spectroscopy resonances of CuCl or CuI with equimolar amounts of the corresponding
complexes 1a were not observed in CD2Cl2 at room tem- Ar-BIAN ligands and PPh3 in acetonitrile at reflux in high
perature. Upon cooling to –80 °C, except for the anticipated yields (72–89%) [Scheme 2, route (i)]. The same synthetic
1
shifts of H NMR spectroscopy resonances owing to en- procedure did not lead to the formation of copper(I) ana-
hanced anisotropic shielding, the 31P NMR spectroscopy logues ligated by the bulkier Ar-BIAN ligand [Ar = 2,6-
resonances were still absent. As five equivalents of free PPh3 iPr2C6H3 (f)]. When AsPh3 was used as the ancillary ligand
were added into the solution of the complex in CD2Cl2 at in place of PPh3, a mixture of a copper(I) dimer complex
20 °C, except for the appearance of the corresponding ad- and AsPh3-coordinated complex was obtained [Scheme 2,
ditional aromatic hydrogen resonances in the 1H NMR route (ii)]. In most of the cases, dimer complexes 7 and 8
spectra, neither coordinated nor free PPh3 were observed in were isolated as the main products in high yields (Ͼ50%),
the 31P NMR spectra. On cooling this solution to –80 °C, except in the reaction of CuCl, AsPh3 and 4-iPrC6H4-BIAN
the 31P NMR spectra remained invariant with no visible (a). In the latter case, AsPh3-coordinated complex 9a was
resonances. Since the solution colour (deep red) and the 1H isolated as the main product in high yield (76%). In the
chemical shifts of the complex in CD2Cl2 did not change presence of SbPh3, the same reactions led to the exclusive
with time and temperature, except for the anisotropic formation of dimer complexes 7 and 8 in moderate to high
shielding shifts, we exclude the possibility of complex de- yields (40–92%) [Scheme 2, route (iii)]. Complexes 7 and 8
composition or other side reactions upon the addition of can also be prepared by the reaction of equimolar amounts
an excess amount of PPh3. This absence of resonances in of CuCl or CuI and Ar-BIAN in the absence of AsPh3 or
Eur. J. Inorg. Chem. 2013, 1404–1417
1406
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

www.eurjic.org
FULL PAPER
SbPh3, as demonstrated by the formation of 7d and 8d cationic complexes. The 31P resonances of complexes 5 and
[Scheme 2, route (iv)], which is consistent with the results 6 vary in the range of δ = –3.71 to –0.39 ppm, consistent
reported recently by Knör and co-workers.[23b] Similarly to with characteristic resonances of (PPh3)xcopper(I) (x = 1–
cationic copper(I) complexes 1–4, it also can be concluded 3) complexes.[33] Compared with cationic complexes 1, the
that, in the case of neutral copper(I) complexes 5–8, the presence of a resonance in the 31P NMR spectra of com-
electronic nature of ancillary ligands EPh3 dominate the plexes 5 and 6 indicates a weak tendency of dissociation of
formation of complexes. The ligand PPh3, with stronger their PPh3 ligands.
electron-donating ability, results in the formation of com-
plexes 5 and 6 coordinated by PPh3, whereas the weaker
donor ligands AsPh3 and SbPh3 fail to coordinate to CuI,
thereby giving rise to dimer complexes 7 and 8 regardless
of the halogen atoms used (Cl or I).
Structural Studies
All the copper(I) complexes described in this paper, re-
gardless of their cationic or neutral nature, show good tend-
encies to crystallise. Slow diffusion of hexane into a dilute
solution of complexes 1b–d, 3a, 4a, 4d, 5a–c, 6a, 6b, 6e, 7f,
8a, 8e, 8f and 9a in dichloromethane, at –20 °C, afforded
crystals suitable for single-crystal X-ray diffraction. Com-
plexes 1c, 5a–c, 8a, 8f and 9a crystallise in the triclinic sys-
¯
tem with space group P1; 1b and 4a in the orthorhombic
system with space group Pbca; 1d and 6b in the monoclinic
system with space group P21/c; 3a, 4d, 6a and 7f in the
monoclinic system with space group P21/n; 6e in the mono-
clinic system with space group P21; and 8e in the tetragonal
system with space group P41212. Their molecular structures
are presented in Figures 1, 2, 3 and 4 and Figures S1–S13
(see the Supporting Information). Selected bond lengths,
bond angles and dihedral angles are given in Table 1. The
structure data of complexes 5b and 8f, which were reported
by other groups with different crystal systems (monoclinic
with space group P21/c and monoclinic with space group
P21/n, respectively),[23] are also presented in Table 1 for
comparison. Complex 7f was reported to crystallise in the
same crystal system as that of this study, but data were col-
lected at a different temperature (296 K).[23b] The differ-
ences in their molecular structures are also shown in
Table 1.
Scheme 2. Syntheses of neutral copper(I) complexes. (i) PPh3
(1.0 equiv.), CuCl or CuI (1.0 equiv.), CH3CN at reflux, 3 h; (ii)
AsPh3 (1.0 equiv.), CuCl or CuI (1.0 equiv.), CH3CN at reflux, 3 h;
(iii) SbPh3 (1.0 equiv.), CuCl or CuI (1.0 equiv.), CH3CN at reflux,
3 h; (iv) CuCl or CuI (1.0 equiv.), CH3CN at reflux, 3 h (for 7d and
8d).
Complexes 5–9 were characterised by elemental analysis,
1H and 13C{1H} NMR spectroscopy, 2D homo- and het-
eronuclear correlation NMR spectroscopy (COSY, HSQC
and HMBC) and 31P{1H} NMR spectroscopy (for com-
plexes 5 and 6). All the 1H and characteristic 13C reso-
Figure 1. An ORTEP diagram of complex 3a with 50% probability
–
ellipsoid displacement. The counteranion (BF4 ) and calculated hy-
drogen atoms were omitted for clarity.
1
nances were assigned. The H resonances of Ar-BIAN li-
As can be seen in Table 1, the Cu–N bond lengths (ca.
gands are comparable with those of their corresponding 2.1 Å) and the angles N–Cu–N (ca. 80°) are almost con-
Eur. J. Inorg. Chem. 2013, 1404–1417
1407
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

www.eurjic.org
FULL PAPER
Figure 2. An ORTEP diagram of complex 4a with 50% probability
–
ellipsoid displacement. The counteranion (BF4 ) and calculated hy-
drogen atoms were omitted for clarity.
Figure 4. An ORTEP diagram of complex 8a with 50% probability
ellipsoid displacement. A dichloromethane solvate molecule and
the calculated hydrogen atoms were omitted for clarity.
majority of four-coordinate copper(I) complexes.[24,25] The
degrees of distortion of tetrahedral geometries can be de-
scribed by the dihedral angle ω between the copper(I)–di-
imine five-membered ring plane and the plane bearing the
copper, X and Y (see Table 1), an ideal tetrahedral geome-
try giving ω = 90°. As can be seen in Table 1, the angle ω
varies remarkably with the aryl substituents of Ar-BIAN
and the ancillary ligands. In principle, the angles ω for cat-
ionic complexes are noticeably smaller than those for the
corresponding neutral complexes, the latter being closer to
90°. It indicates that cationic complexes significantly deviate
from an ideal tetrahedral geometry, whereas neutral com-
plexes just present slight deviations, possibly owing to the
higher bulk of both EPh3 ligands in the former compounds.
For cationic complexes, the angle ω decreases as the bulki-
ness of the o-aryl substituent increases, for example, 1d with
2-iPr [ω = 74.45(8)°] Ͻ 1b with 2-H [ω = 76.5(2)°] and 4d
with 2-iPr [ω = 71.59(16)°] Ͻ 4a with 2-H [ω = 78.27(16)°],
whereas for neutral complexes a reverse tendency was ob-
Figure 3. An ORTEP diagram of complex 5a with 50% probability
ellipsoid displacement. Two dichloromethane solvate molecules
and the calculated hydrogen atoms were omitted for clarity.
stant for all the complexes owing to the rigidities of their served, for example, 6b with 2-H [ω = 81.7(2)°] Ͻ 6e with
acenaphthenequinonediimine backbones. For cationic com- 2,6-Me2 [ω = 89.91(7)°] and 8a with 2-H [ω = 86.1(2)°] Ͻ
plexes 1b–d and 3a and neutral complexes 5a–c, 6a, 6b and 8f with 2,6-iPr2 [ω = 89.26(16)°]. Complexes 8e, 8f and 9a
6e containing PPh3 donor ligands, their Cu–P bond lengths, possess two molecules in each asymmetric unit cell, the for-
varying in the range of 2.182 to 2.276 Å (see Table 1), are mer presenting two molecules with remarkably different
comparable with those of other known copper(I) com- geometrical distortions [ω = 88.0(4)° for molecule a, and ω
plexes,[24,25] but the bond lengths of cationic complexes are = 74.4(4) and 72.4(4)° for molecule b] and the latter two
slightly larger than those of neutral ones, which is somehow exhibiting two molecules with comparable distortions [ω =
in agreement with the PPh3 dissociation behaviour observed 89.26(16)° for molecule a and ω = 87.08(16) and 89.66(15)°
in cationic complexes 1a–d. Complexes 4a, 4d and 9a have for molecule b in complex 8f, and ω = 86.7(3)° for molecule
Cu–As bond lengths around 2.3 Å, which are characteristic a and ω = 89.2(3)° for molecule b in complex 9a]. Complex
of the few known arsane-containing copper(I) complex 4d containing AsPh3 ligands [ω = 71.59(16)°] is more dis-
structures.[34]
torted than complex 1d containing PPh3 ligands [ω =
For all the complexes, the copper(I) centres are coordi- 74.45(8)°], which contradicts the above-mentioned cone-an-
nated by four atoms consisting of two iminic nitrogen gle sequence of ancillary ligands (PPh3 Ͼ AsPh3). The halo-
atoms, X and Y (see Table 1), adopting distorted-tetrahe- gen atoms show inconsistent effects on the geometries of
dral geometries, which are in agreement with those of the complexes, for example, 5b with Cl [ω = 86.3(2)°] Ͼ 6b with
Eur. J. Inorg. Chem. 2013, 1404–1417
1408
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

www.eurjic.org
FULL PAPER
Table 1. Selected bond lengths [Å], bond angles [°] and dihedral angles [°].
Cu–N [Å]
Cu–X(Y) [Å][c]
N–Cu–N [°]
79.3(2)
ω [°]
φ [°]
1b
1c
2.101(6)
2.261(2)
76.5(2)
123.23(8)
114.87(11)
121.63(3)
108.84(10)
121.74(4)
116.47(3)
109.69(8)
108.85(9)
117.09(5)
125.54(5)
115.09(3)
112.48(7)
106.603(18)
105.994(16)
105.74(3)
116.43(3)
106.91(6) (a)
2.123(6)
2.119(6)
2.092(7)
2.165(2)
2.123(2)
2.060(7)
2.021(7)
2.092(5)
2.085(5)
2.120(4)
2.113(5)
2.062(5)
2.100(6)
2.082(7)
2.076(6)
2.090(3)
2.110(3)
2.078(4)
2.109(3)
2.096(3)
2.124(3)
2.075(6)
2.102(6)
2.0969(17)
2.0953(18)
2.0846(13)
2.0853(14)
2.1021(19)
2.1256(17)
2.120(5)
2.276(2)
2.235(2)
2.266(3)
2.2699(7)
2.2650(7)
2.233(3)
2.214(3)
2.3620(9)
80.6(3)
89.3(3)
1d
3a
4a
4d
5a
5b
5b[a]
5c
79.32(8)
80.9(3)
74.45(8)
82.2(3)
79.7(2)
78.27(16)
71.59(16)
89.5(2)
2.3444(9)
2.3621(9)
2.3625(9)
80.33(18)
80.2(2)
2.182(2) (P)
2.276(2) (Cl)
2.186(2) (P)
2.271(2) (Cl)
2.1976(12) (P)
2.3087(15) (Cl)
2.1882(12) (P)
2.2473(13) (Cl)
2.2001(11) (P)
2.5848(5) (I)
2.2071(19) (P)
2.6010(12) (I)
2.2113(6) (P)
2.5987(3) (I)
2.2722(5)
79.7(3)
86.3(2)
78.58(13)
79.39(14)
79.40(12)
80.1(2)
83.11(13)
86.07(14)
88.58(11)
81.7(2)
6a
6b
6e
80.56(7)
81.32(5)
80.68(7)
79.25(19)
80.6(4) (a)
89.91(7)
83.80(5)
86.97(7)
86.1(2)
7f
2.2898(5)
2.2738(8)
2.3187(8)
2.5594(9)
7f[b]
8a
8e
2.100(5)
2.5933(10)
2.132(10) (a)
2.107(10) (a)
2.102(12) (b)
2.115(10) (c)
2.123(4) (a)
2.146(4) (a)
2.154(4) (b)
2.112(4) (b)
2.103(4) (c)
2.168(4) (c)
2.114(3)
2.5719(18) (a)
2.6044(17) (a)
2.5970(15) (b)
2.5682(14) (c)
2.5533(8) (a)
2.6020(8) (a)
2.5900(8) (b)
2.5882(8) (b)
2.5509(8) (c)
2.6225(8) (c)
2.5526(5)
88.0(4) (a)
79.5(6) (b)
79.1(6) (c)
79.75(16) (a)
74.4(4) (b)
72.4(4) (c)
89.66(15) (a)
114.37(9) (b)
116.39(9) (c)
117.87(3) (a)
8f
79.32(16) (b)
79.50(16) (c)
80.29(10)
87.08(16) (b)
89.26(16) (c)
89.86(9)
117.04(3) (b)
113.09(3) (c)
119.61(2)
8f[b]
9a
2.110(3)
2.5932(6)
2.078(7) (a)
2.131(7) (a)
2.102(7) (b)
2.090(7) (b)
2.3217(13) (As) (a)
2.264(2) (Cl) (a)
2.3316(13) (As) (b)
2.279(2) (Cl) (b)
78.8(3) (a)
78.5(3) (b)
86.7(3) (a)
89.2(3) (b)
113.87(7) (a)
114.63(7) (b)
[a] Ref.[23a] [b] Ref.[23b] [c] (a) = molecule a; (b) = molecule b; (c) = molecule c.
Eur. J. Inorg. Chem. 2013, 1404–1417
1409
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

www.eurjic.org
FULL PAPER
I [ω = 81.7(2)°] and 7f with Cl [ω = 83.80(5)°] Ͻ 8f with I
[ω = 89.26(16)°].
The angle φ of X–Cu–Y (see Table 1) is another impor-
tant parameter to evaluate the geometrical distortions of
such complexes. As can be seen in Table 1, the effects of
the aryl substituents of Ar-BIAN and the type of ancillary
ligands on angle φ are very irregular, for example, 1c with
2-H [φ = 114.87(11)°] Ͻ 1d with 2-iPr [φ = 121.63(3)°] ver-
sus 4a with 2-H [φ = 121.74(4)°] Ͼ 4d with 2-iPr [φ =
116.47(3)°], and 1d with PPh3 [φ = 121.63(3)°] Ͼ 4d with
AsPh3 [φ = 116.47(3)°] versus 5a with PPh3 [φ = 109.69(8)°]
Ͻ 9a with AsPh3 [φ = 113.87(7)°]. Complex 3a, containing
ligand dppf, shows a much smaller angle φ [φ = 108.84(10)°]
owing to the bidentate nature of this angle, which is com-
parable with other known complexes bearing dppf li-
gands.[25b–25d,35]
Figure 5. Comparison of the catalytic activities of complexes of the
general formulae [Cu(Ar-BIAN)L2]BF4 [L2 = (PPh3)2 (1), dppe (2),
dppf (3), (AsPh3)2 (4)], [CuX(Ar-BIAN)(EPh3)] [X = Cl, E = P (5);
X = I, E = P (6); X = Cl, E = As (9)], and [CuX(Ar-BIAN)]2 [X
= Cl (7), I (8)], in which Ar = 4-iPrC6H4 (a), 4-MeOC6H4 (b), 4-
NO2C6H4 (c), 2-iPrC6H4 (d), 2,4,6-Me3C6H2 (e) and 2,6-iPr2C6H3
(f) in the cycloaddition reaction of phenylacetylene and benzyl az-
ide.
Catalytic Studies
Complexes 1–9 were tested for cycloaddition reactions
of alkynes and azides (CuAAC) using phenylacetylene and
benzyl azide, which are typical reagents of these classes of
compounds, respectively. The results are summarised in
Table 2 and schematically depicted in Figure 5. As can be
seen from this data, all the complexes except 3a are active
catalysts for this cycloaddition reaction. Among them, com-
plexes 1a–d exhibit the highest catalytic activities (26.9–
45.7 h–1, entries 1–4, Table 2).
The molecular features of complexes, namely, the type of
ancillary ligands EPh3 and the aryl substituents of Ar-
BIAN, present substantial effects on the catalytic activities.
The PPh3-coordinated complexes, including the cationic 1
and the neutral 5 and 6, exhibit relatively high catalytic ac-
tivities, which could be ascribed to increased stabilities of
the copper(I) active species when coordinated by PPh3, ow-
ing to a strong electron-donating ability of the latter ligand.
Additionally, cationic complexes 1 are much more active
than the neutral 5 and 6 towards cycloaddition reactions,
which indicates that the noticeable dissociation equilibrium
of PPh3 in cationic 1 might favour the cycloaddition reac-
tion compared with the relatively less labile neutral 5 and
6. The dimer complexes 7 and 8, not containing PPh3 or
AsPh3 ancillary ligands, present the lowest catalytic activi-
ties, which demonstrate that these ancillary ligands, in par-
ticular PPh3, play key roles in stabilising the catalytic transi-
tion states, ensuring higher catalytic activities in the cyclo-
addition reactions. The AsPh3-coordinated complexes 4 and
9 show much lower catalytic activities than the correspond-
ing PPh3-coordinated complexes 1 and 5 (or 6), which can
also be ascribed to a higher stabilisation of the transition
states (active species) involving PPh3 in relation to those
containing AsPh3. The dppe-coordinated cationic complex
2a gives a moderate catalytic activity, expectedly owing to
a considerable degree of hemilability of this ligand, whereas
complex 3a coordinated by dppf is inactive towards the cy-
cloaddition reaction, very likely owing to a higher coordi-
nation rigidity and, consequently, to a lack of lability of
this diphosphane. By comparing the catalytic activities of
complexes bearing the same ancillary ligands shown in
Table 2 and Figure 5, one can find out that, in general, elec-
tron-donating aryl substituents of Ar-BIAN give rise to rel-
atively higher catalytic activities. For instance, complexes
1a, 1b and 1d, bearing electron-donating 4-iPr, 4-MeO and
2-iPr aryl substituents, respectively, cause higher catalytic
activities than 1c bearing the electron-withdrawing 4-NO2
Table 2. Catalytic activities (TOF) of complexes 1–9 in the cycload-
dition reaction of phenylacetylene and benzyl azide.[a,b]
Entry Catalyst Yield TOF
[%]
Entry Catalyst Yield TOF
[%]
1
2
3
4
5
6
7
8
1a
1b
1c
1d
2a
3a
4a
4b
4c
4d
5a
5b
5c
5d
5e
6a
6b
71.2[c] 35.6[c]
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
6c
6d
6e
7a
7b
7c
7d
7e
7f
8a
8b
8c
8d
8e
8f
9.3
16.7
31.6
1.2
2.1
4.8
1.0
4.9
2.4
12.8
1.8
3.0
2.4
17.8
4.2
2.8
4.7
8.4
15.8
0.6
1.1
2.4
0.5
2.5
1.2
6.4
0.9
1.5
1.2
8.9
2.1
1.4
82.0
53.8
91.3
16.2
0
41.0
26.9
45.7
8.1
0
13.0
13.2
6.8
6.5
6.6
3.4
9
10
11
12
13
14
15
16
17
10.4
44.5
51.4
26.6
30.1
77.2
34.0
8.5
5.2
22.3
25.7
13.3
15.1
38.6
17.0
4.3
9a
[a] General reaction conditions: phenylacetylene (1.0 mmol), benzyl
azide (1.0 mmol), [Cu] = 0.002 m (1.0 mol-%), THF (5 mL), T =
50 °C, t = 2.0 h. TOF = turnover frequency. [b] For all reactions,
besides the reaction product, the remaining species observed after
2 h are only starting materials and catalyst. [c] Ref.[22]
Eur. J. Inorg. Chem. 2013, 1404–1417
1410
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

www.eurjic.org
FULL PAPER
Table 3. Syntheses of 1,4-disubstituted 1,2,3-triazoles catalyzed by group. Similar trends can also be observed for the neutral
complexes 1d and 5e.[a,b]
complexes 5 and 6.
The most active complexes [Cu(2-iPrC6H4-BIAN)-
(PPh3)2]BF4 (1d) and [CuCl(2,4,6-Me3C6H2-BIAN)(PPh3)]
(5e) were selected to test the reaction scope. The results are
given in Table 3. These two complexes behave efficiently in
a varied scope of substrates including diverse functionalised
alkynes and azides, such as 2-ethynylaniline, 3-azidopropan-
1-ol and ethyl 2-azidoacetate, and the complexes show good
tolerance towards various functional groups such as hy-
droxy, amine and ester groups. The substrates do not exhi-
bit significant effects on the catalytic activities, except for
3-azidopropan-1-ol, which leads to considerably higher ac-
tivities when reacted with both phenylacetylene and 2-eth-
ynylaniline (entries 7, 8, 19 and 20, Table 3).
It is worth mentioning that all reactions listed in Tables 2
and 3 are highly selective because, besides the correspond-
ing single reaction product, the remaining species observed
after 2.0 h of reaction are only starting materials and cata-
lyst.
Conclusion
A series of new cationic or neutral aryl-BIAN copper(I)
complexes 1–9 containing ancillary ligands PPh3 or AsPh3
was synthesised, characterised and tested as catalysts for
cycloaddition reactions of alkynes and azides. All the com-
plexes adopt distorted-tetrahedral geometries around the
copper(I) centres, characteristic of four-coordinate cop-
per(I) complexes. The well-defined single-site homogeneous
nature of these complexes allowed us to investigate the ef-
fects of ligands, including the aryl substituents of Ar-BIAN
and ancillary ligands, on the molecular structures of com-
plexes and on catalytic activities. The results show that the
formation of cationic complexes [Cu(Ar-BIAN)L2]BF4 1–4
is dominated by the electronic nature of L neutral donor
ligands of the type EPh3 (E = P or As). The PPh3 and
AsPh3 ligands, with relatively stronger electron-donating
abilities, led to stable cationic complexes 1 and 4, whereas
SbPh3 failed in the attempt to synthesise stable analogues.
This conclusion can also be extended to the neutral com-
plexes [CuX(Ar-BIAN)(EPh3)] 5–7. Ligand PPh3, with
stronger electron-donating ability, results in the formation
of complexes 5 and 6 coordinated by PPh3, whereas ligand
SbPh3 and sometimes AsPh3, with relatively weaker elec-
tron-donating abilities, fail to coordinate to CuI, thereby
forming the dimer complexes [{CuX(Ar-BIAN)}2] 7 and 8,
regardless of the nature of the halogen atoms (Cl or I,
respectively). Different from the ancillary ligands EPh3, the
Ar-BIAN ligand steric effects seem to be a key factor in
determining the formation of complexes, whereas the elec-
tronic nature of these bidentate ligands exhibit minor influ-
ences. All complexes 1–9 except the cationic dppf derivative
3a are active catalysts for cycloaddition reactions, of which
[a] General reaction conditions: alkyne (1.0 mmol), azide
complexes 1a–d exhibit the highest catalytic activities (26.9–
(1.0 mmol), catalyst (1.0 mol-%), THF (5 mL); T = 50 °C; t = 2.0 h.
45.7 h–1). Ancillary ligands EPh3 and aryl substituents of
[b] For all reactions, besides the reaction product, the remaining
species observed after 2 h are only starting materials and catalyst.
Ar-BIAN exhibit substantial effects on the catalytic activi-
Eur. J. Inorg. Chem. 2013, 1404–1417
1411
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

www.eurjic.org
FULL PAPER
(t, J = 7.8 Hz, 2 H, AnH), 7.47 [t, J = 7.4 Hz, 6 H, p-P(C6H5)3],
7.23 [t, J = 7.7 Hz, 12 H, m-P(C6H5)3], 7.19 (d, J = 7.5 Hz, 2 H,
AnH), 7.02 [br., 12 H, o-P(C6H5)3], 6.62 (d, J = 7.2 Hz, 4 H, o-
C6H4) ppm. 13C{1H} NMR (75 MHz, CD2Cl2): δ = 164.3 (C=N),
152.3 (C=N–C), 146.4, 144.5, 133.0, 131.6, 131.0, 130.8, 129.3,
129.0, 126.0, 125.7, 125.0, 121.2 (aromatic CH and other quater-
nary carbon atoms) ppm. C60H44BCuF4N4O4P2 (1097.33): calcd.
C 65.67, H 4.04, N 5.11; found C 65.65, H 4.04, N 5.14.
ties. In general, the PPh3-coordinated complexes (e.g., 1, 5
and 6) exhibit relatively high catalytic activities, whereas di-
mer complexes 7 and 8 containing no ancillary ligands pres-
ent the lowest catalytic activities. Additionally, the Ar-
BIAN ligands containing electron-donating aryl substitu-
ents give rise to higher catalytic activities. These complexes
behave efficiently in a wide scope of substrates.
1
Data for 1d: Yield 91%. H NMR (300 MHz, CD2Cl2): δ = 8.24–
8.20 [2 d (superimposed), J = 8.1 Hz (syn isomer), J = 8.3 Hz (anti
isomer), 2 H, AnH], 7.61–7.53 (m, 4 H, AnH, C6H4), 7.49–7.36 [m,
8 H, C6H4, p-As(C6H5)3], 7.14 [br., 14 H, AnH, m-As(C6H5)3],
6.91–6.74 [m, 14 H, C6H4, o-As(C6H5)3], 6.12 [d, J = 7.8 Hz (syn
isomer), 0.20 H, C6H4], 5.76 [d, J = 7.8 Hz (anti isomer), 1.80 H,
C6H4], 3.38 [septet, J = 6.7 Hz (anti isomer), 1.80 H, CH(CH3)2],
3.17 [septet, J = 6.7 Hz (syn isomer), 0.20 H, CH(CH3)2], 0.96–0.89
[2 d (superimposed), J = 6.8 Hz (syn isomer), J = 6.7 Hz (anti iso-
mer), 6 H, CH(CH3)2], 0.56–0.50 [2 d (superimposed), J = 6.7 Hz
(anti isomer), J = 6.8 Hz (syn isomer), 6 H, CH(CH3)2] ppm.
13C{1H} NMR (75 MHz, CD2Cl2): δ = 165.7 (syn isomer, C=N),
165.5 (anti isomer, C=N), 146.3 (anti isomer, C=N–C), 146.2 (syn
isomer, C=N–C), 143.5, 143.3, 140.7, 139.0, 133.4, 131.6, 131.5,
131.3, 130.6, 129.1, 128.6, 128.2, 127.7, 127.4, 127.2, 127.1, 126.7,
126.6, 126.4, 126.0, 125.5, 121.5, 120.2 (aromatic CH and other
quaternary carbon atoms), 29.6 [anti isomer, CH(CH3)2], 28.7 [syn
isomer, CH(CH3)2], 25.7 [anti isomer, CH(CH3)2], 24.8 [syn isomer,
CH(CH3)2], 21.8 [syn isomer, CH(CH3)2], 19.7 [anti isomer,
CH(CH3)2] ppm. C66H58BCuF4N2P2 (1091.49): calcd. C 72.63, H
5.36, N 2.57; found C 72.64, H 5.55, N 2.63.
Experimental Section
General: All manipulations dealing with air- or moisture-sensitive
materials were carried out under an inert atmosphere using a dual
vacuum/nitrogen line and standard Schlenk techniques. Unless
otherwise stated, all reagents were purchased from commercial sup-
pliers and used as received. All solvents were used under an inert
atmosphere and purified prior to use. Dichloromethane and aceto-
nitrile were purified over calcium hydride and phosphorus pentox-
ide, respectively, and distilled prior to use. Deuterated solvents
([D1]chloroform, [D2]dichloromethane and [D5]pyridine) were
dried by storage over 4 Å molecular sieves and degassed by the
freeze–pump–thaw method. Ligands Ar-BIAN [Ar = 4-iPrC6H4
(a), 4-MeOC6H4 (b), 4-NO2C6H4 (c), 2-iPrC6H4 (d), 2,4,6-
Me3C6H2 (e), 2,6-iPr2C6H3 (f)][36] and the complexes [Cu(EPh3)4]-
[21k]
BF4 (E = P, As, Sb),[37] [Cu(CH3CN)4]BF4
and [Cu(4-iPrC6H4-
BIAN)(PPh3)2]BF4 (1a)[22] were prepared according to the litera-
ture.
Elemental analyses were obtained from the elemental analysis ser-
vice of Instituto Superior Técnico (IST) on a Fisons Instrument
Mod EA-1108.
Data for 4a: Yield 51%. 1H NMR (300 MHz, CD2Cl2): δ = 8.22
(d, J = 8.2 Hz, 2 H, AnH), 7.60 (t, J = 7.6 Hz, 2 H, AnH), 7.43–
7.33 [m, 8 H, AnH, p-As(C6H5)3], 7.18–7.12 [m, 16 H, m-C6H4, m-
As(C6H5)3], 6.98 [d, J = 7.4 Hz, 12 H, o-As(C6H5)3], 6.68 (d, J =
7.7 Hz, 4 H, o-C6H4), 3.01 [septet, J = 6.8 Hz, 2 H, CH(CH3)2],
1.36 [d, J = 6.8 Hz, 12 H, CH(CH3)2] ppm. 13C{1H} NMR
(75 MHz, CD2Cl2): δ = 163.2 (C=N), 149.4 (C=N–C), 144.8, 144.2,
134.1, 133.2, 131.9, 131.7, 130.4, 129.5, 128.8, 128.1, 126.3, 125.4,
121.0 (aromatic CH and other quaternary carbon atoms), 34.2
[CH(CH3)2], 24.2 [CH(CH3)2] ppm. C66H58As2BCuF4N2 (1179.39):
calcd. C 67.21, H 4.96, N 2.38; found C 67.17, H 4.94, N 2.39.
NMR spectra were recorded on Bruker Avance III 300 (1H,
300.130 MHz; 13C, 75.4753 MHz; 31P, 121.495) or Bruker Avance
III 400 (1H, 400.132 MHz; 13C, 100.623 MHz; 31P, 161.923 MHz)
spectrometers. Spectra were referenced internally using the residual
protio solvent resonance relative to tetramethylsilane (δ = 0). Mul-
tiplicities were abbreviated as follows: singlet (s), broad (br), doub-
let (d), triplet (t), and multiplet (m). For air- and moisture-sensitive
compounds, NMR spectroscopy solutions were prepared in a
glovebox.
Syntheses of Copper(I) Complex Salts [Cu(Ar-BIAN)(EPh3)2]BF4 [E
= P (1), As (4)]: A typical synthetic procedure is described as fol-
lows: the desired amount of [Cu(PPh3)4]BF4 or [Cu(AsPh3)4]BF4
(0.5 mmol) and the ligand Ar-BIAN (0.5 mmol) were mixed in a
100 mL Schlenk tube. CH2Cl2 (30 mL) was added and the mixture
was stirred for 4 h at room temperature. After removal of solvent
under vacuum, red crystalline solids were isolated, washed with
Et2O (3ϫ 50 mL) and dried under vacuum.
Data for 4b: Yield 85%. 1H NMR (300 MHz, CD2Cl2): δ = 8.25
(d, J = 7.8 Hz, 2 H, AnH), 7.65 (t, J = 7.2 Hz, 2 H, AnH), 7.57
(d, J = 6.9 Hz, 2 H, AnH), 7.41 [t, J = 7.5 Hz, 6 H, p-As(C6H5)3],
7.20 [t, J = 7.5 Hz, 12 H, m-As(C6H5)3], 7.01 [d, J = 8.1 Hz, 12 H,
o-As(C6H5)3], 6.81 (AB, J = 9.0 Hz, 4 H, m-C6H4), 6.73 (AB, J =
9.0 Hz, 4 H, o-C6H4), 3.92 (s, 6 H, CH3O) ppm. 13C{1H} NMR
(75 MHz, CD2Cl2): δ = 162.6 (C=N), 159.4 (C=N–C), 143.7, 139.8,
133.6, 132.9, 131.5, 131.4, 130.1, 129.3, 128.4, 126.1, 124.8, 122.5,
114.9 (aromatic CH and other quaternary carbon atoms), 55.7
(CH3O) ppm. C62H50As2BCuF4N2O2 (1155.28): calcd. C 64.46, H
4.36, N 2.42; found C 64.44, H 4.41, N 2.34.
Data for 1b: Yield 86%. 1H NMR (300 MHz, CD2Cl2): δ = 8.23
(d, J = 8.4 Hz, 2 H, AnH) (An = acenaphthenic backbone), 7.62
(t, J = 7.8 Hz, 2 H, AnH), 7.48 (d, J = 8.7 Hz, 2 H, AnH), 7.42 [t,
J = 7.5 Hz, 6 H, p-P(C6H5)3], 7.18 [t, J = 7.4 Hz, 12 H, m-P-
(C6H5)3], 6.96 [br., 12 H, o-P(C6H5)3], 6.77 (AB pattern, J = 8.1 Hz,
4 H, m-C6H4), 6.46 (AB pattern, J = 8.1 Hz, 4 H, o-C6H4), 3.92 (s,
6 H, CH3O) ppm. 13C{1H} NMR (75 MHz, CD2Cl2): δ = 162.6
(C=N), 159.2 (C=N–C), 140.0, 133.3, 133.2, 133.1, 131.5, 131.4,
131.3, 130.4, 128.9, 128.3, 126.3, 124.7, 122.4, 114.8 (aromatic CH
and other quaternary carbon atoms), 55.7 (CH3O) ppm.
C62H50BCuF4N2O2P2 (1067.38): calcd. C 69.77, H 4.72, N 2.62;
found C 69.64, H 4.73, N 2.64.
Data for 4c: Yield 91%. 1H NMR (400 MHz, CD2Cl2): δ = 8.37
(d, J = 8.0 Hz, 2 H, AnH), 8.15 (d, J = 8.8 Hz, 4 H, m-C6H4), 7.70
(t, J = 8.0 Hz, 2 H, AnH), 7.45–7.42 [m, 8 H, AnH, p-As(C6H5)3],
7.23–7.20 [m, 12 H, m-As(C6H5)3], 7.05–7.03 [m, 12 H, o-As-
(C6H5)3], 6.84 (d, J = 8.8 Hz, 4 H, o-C6H4) ppm. 13C{1H} NMR
(100 MHz, CD2Cl2): δ = 164.5 (C=N), 152.0 (C=N–C), 146.5,
144.8, 133.3, 133.1, 132.9, 131.5, 130.4, 129.5, 129.0, 126.0, 125.8,
124.9, 121.3 (aromatic CH and other quaternary carbon atoms)
ppm. C60H44As2BCuF4N4O4 (1185.22): calcd. C 60.80, H 3.74, N
4.73; found C 60.97, H 3.72, N 4.65.
Data for 1c: Yield 87%. 1H NMR (300 MHz, CD2Cl2): δ = 8.38
(d, J = 8.4 Hz, 2 H, AnH), 8.14 (d, J = 7.2 Hz, 4 H, m-C6H4), 7.70
Eur. J. Inorg. Chem. 2013, 1404–1417
1412
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

www.eurjic.org
FULL PAPER
1
Data for 4d: Yield 70%. H NMR (400 MHz, CD2Cl2): δ = 8.29– follows: the desired amount of CuCl or CuI (0.5 mmol), PPh3
8.25 [2 d (superimposed), J = 6.8 Hz (syn isomer), J = 8.4 Hz (anti (0.5 mmol) and the ligand Ar-BIAN (0.5 mmol) were mixed in a
isomer), 2 H, AnH], 7.62–7.57 (m, 4 H, AnH, C6H4), 7.45–7.39 [m,
100 mL Schlenk tube. CH3CN (30 mL) was added and the mixture
8 H, C6H4, p-As(C6H5)3], 7.18 [t, J = 7.6 Hz, 12 H, m-As(C6H5)3], was heated at reflux for 3 h. After removal of the solvent under
6.98 (d, J = 7.6 Hz, 2 H, AnH), 6.86–6.82 [m, 14 H, C6H4, o-
As(C6H5)3], 6.52 [d, J = 8.0 Hz (syn isomer), 0.20 H, C6H4], 6.09
[d, J = 8.0 Hz (anti isomer), 1.80 H, C6H4], 3.49 [septet, J = 6.8 Hz
(anti isomer), 1.80 H, CH(CH3)2], 3.30 [septet, J = 6.4 Hz (syn
isomer), 0.20 H, CH(CH3)2], 1.01–0.95 [2 d (superimposed), J =
6.8, (syn isomer), J = 6.8 Hz (anti isomer), 6 H, CH(CH3)2], 0.63–
0.58 [2 d (superimposed), J = 6.8 (anti isomer), J = 6.8 Hz (syn),
6 H, CH(CH3)2] ppm. 13C{1H} NMR (100 MHz, CD2Cl2): δ =
165.8 (syn isomer, C=N), 165.4 (anti isomer, C=N), 145.8 (anti iso-
mer, C=N–C), 145.5 (syn isomer, C=N–C), 143.9, 140.6, 139.1,
133.3, 133.2, 133.0, 132.7, 132.0, 131.8, 131.4, 130.2, 129.4, 128.7,
128.4, 128.0, 127.5, 127.4, 127.2, 126.6, 126.3, 126.1, 126.0, 125.6,
121.2, 120.2 (aromatic CH and other quaternary carbon atoms),
29.7 [anti isomer, CH(CH3)2], 29.2 [syn isomer, CH(CH3)2], 25.5
[anti isomer, CH(CH3)2], 24.7 [syn isomer, CH(CH3)2], 21.5 [syn
isomer, CH(CH3)2], 20.0 [anti isomer, CH(CH3)2] ppm.
C66H58As2BCuF4N2 (1179.39): calcd. C 67.21, H 4.96, N 2.38;
found C 67.10, H 4.93, N 2.27.
Syntheses of Copper(I) Complex Salts {Cu(4-iPrC6H4-BIAN)[κ2-
P,P-(PPh2)2R]}BF4 [R = CH2CH2 (2a), (π-C5H4)Fe(π-C5H4) (3a)]:
A suspension of [Cu(NCMe)4]BF4 (0.72 mmol) and the ligand [1,2-
bis(diphenylphosphanyl)ethane (dppe) or 1,1Ј-bis(diphenylphos-
phanyl)ferrocene (dppf)] (0.72 mmol) in CH2Cl2 (30 mL) was
stirred for 2 h at room temperature, and was then treated with an
orange solution of 4-iPrC6H4-BIAN (0.72 mmol) in CH2Cl2
(20 mL). The mixture turned quickly to red, and was left stirring
for another 2 h. After filtration, the solution was concentrated un-
der vacuum and double-layered with pentane and left under argon
at room temperature to crystallise. Red crystalline solids were iso-
lated by filtration, washed with pentane (2ϫ 10 mL) and dried un-
der vacuum.
vacuum, dark crystalline solids were isolated, washed with Et2O
(3ϫ 50 mL) and dried under vacuum.
Data for 5a: Yield 81%. 1H NMR (400 MHz, CD2Cl2): δ = 8.09
(d, J = 8.0 Hz, 2 H, AnH), 7.48 (t, J = 7.8 Hz, 2 H, AnH), 7.40
(d, J = 7.2 Hz, 2 H, AnH), 7.34–7.28 [m, 17 H, C6H4, P(C6H5)3],
7.23–7.19 [m, 6 H, P(C6H5)3], 3.03 [septet, J = 6.8 Hz, 2 H,
CH(CH3)2], 1.38 [d, J = 7.2 Hz, 12 H, CH(CH3)2] ppm. 13C{1H}
NMR (100 MHz, CD2Cl2): δ = 160.1 (C=N), 147.2 (C=N–C),
145.8, 142.4, 133.9, 133.7, 133.6, 133.5, 131.1, 129.9, 129.3, 128.3,
128.2, 127.9, 127.5, 127.2, 123.8, 120.7 (aromatic CH and other
quaternary carbon atoms), 33.9 [CH(CH3)2], 23.9 [CH(CH3)2]
ppm. 31P{1H} NMR (162 MHz, CD2Cl2):
δ = –3.32 ppm.
C48H43ClCuN2P (777.85): calcd. C 74.12, H 5.57, N 3.60; found C
73.66, H 5.48, N 3.63.
Data for 5b: Yield 72%. 1H NMR (300 MHz, CD2Cl2): δ = 8.14
(d, J = 8.1 Hz, 2 H, AnH), 7.42–7.40 (br., 8 H, AnH, m-C6H4),
7.33–7.23 [m, 15 H, P(C6H5)3], 6.97 (d, J = 8.1 Hz, 4 H, o-C6H4),
3.91 (s, 6 H, CH3O) ppm. 13C{1H} NMR (75 MHz, CD2Cl2): δ =
159.8 (C=N), 158.4 (C=N–C), 142.1, 141.1, 134.0, 133.7, 133.6,
133.5, 131.1, 130.1, 129.3, 128.3, 128.2, 127.8, 127.3, 123.4, 122.6,
114.3 (aromatic CH and other quaternary carbon atoms), 55.5
(CH3O) ppm. 31P{1H} NMR (121 MHz, CD2Cl2): δ = –3.20 ppm.
C44H35ClCuN2O2P (753.75): calcd. C 70.11, H 4.68, N 3.72; found
C 70.09, H 4.24, N 3.63.
Data for 5c: Yield 81%. 1H NMR (300 MHz, CD2Cl2): δ = 8.29
(d, J = 8.1 Hz, 4 H, m-C6H4), 8.18 (d, J = 8.4 Hz, 2 H, AnH), 7.56
(t, J = 7.8 Hz, 2 H, AnH), 7.47 (d, J = 6.6 Hz, 4 H, o-C6H4), 7.38–
7.21 [m, 17 H, AnH, P(C6H5)3] ppm. 13C{1H} NMR (75 MHz,
CD2Cl2): δ = 161.2 (C=N), 153.5 (C=N–C), 145.8, 143.0, 133.6,
133.4, 133.1, 132.7, 131.3, 131.1, 129.8, 128.6, 128.5, 128.4, 126.4,
125.3, 124.7, 121.1 (aromatic CH and other quaternary carbon
atoms) ppm. 31P{1H} NMR (121 MHz, CD2Cl2): δ = –1.59 ppm.
C42H29ClCuN4O4P (783.69): calcd. C 64.37, H 3.73, N 7.15; found
C 64.68, H 3.52, N 6.65.
1
Data for 2a: Yield 81%. H NMR (400 MHz, CDCl3): δ = 8.12 (d,
J = 8.2 Hz, 2 H, AnH), 7.58 (dd, J = 8.2, 7.8 Hz, 2 H, AnH), 7.46–
7.43 [m, 4 H, P(C6H5)2], 7.31–7.27 [m, 18 H, AnH, P(C6H5)2], 7.19
(d, J = 8.4 Hz, 4 H, m-C6H4), 6.83 (d, J = 8.2 Hz, 4 H, o-C6H4),
3.05 [septet, J = 6.8 Hz, 2 H, CH(CH3)2], 2.38 (t, J = 6 Hz, 4 H,
CH2) 1.39 [d, J = 6.8 Hz, 12 H, CH(CH3)2] ppm. 13C{1H} NMR
(100 MHz, CD2Cl2): δ = 163.4 (C=N), 148.5 (C=N–C), 145.3,
132.6, 132.5, 132.4, 132.2, 132.0, 131.9, 131.7, 130.7, 129.2, 129.1,
128.4, 127.9, 126.4, 125.7, 124.8, 120.7 (aromatic CH and other
quaternary carbon atoms), 33.8 [CH(CH3)2], 25.5 (CH2), 24.1
[CH(CH3)2] ppm. 31P{1H} NMR (162 MHz, CDCl3): δ = –0.43
ppm. C56H52BCuF4N2P2 (965.34): calcd. C 69.68, H 5.43, N 2.90;
found C 69.32, H 5.67, N 2.83.
Data for 5d: Yield 85%. 1H NMR (300 MHz, CD2Cl2): δ = 8.05 (d,
J = 8.4 Hz, 2 H, AnH), 7.49–7.25 [m, 25 H, AnH, C6H4, P(C6H5)3],
6.87 (d, J = 6.9 Hz, 2 H, AnH), 3.96 [br., isomer, 0.80 H, CH-
(CH3)2], 3.37 [br., isomer, 1.20 H, CH(CH3)2], 0.92–0.59 [m, 12
H, CH(CH3)2] ppm. 13C{1H} NMR (75 MHz, CD2Cl2): δ = 162.2
(C=N), 146.7 (C=N–C), 142.4, 133.9, 133.7, 131.1, 129.8, 129.6,
128.5, 128.3, 128.2, 127.8, 126.6, 126.3, 124.3, 120.3 (aromatic CH
and other quaternary carbon atoms), 28.3 [CH(CH3)2], 24.5
[CH(CH3)2], 22.5 [CH(CH3)2] ppm. 31P{1H} NMR (121 MHz,
CD2Cl2): δ = –3.71 ppm. C48H43ClCuN2P (777.85): calcd. C 74.12,
H 5.57, N 3.60; found C 74.01, H 5.74, N 3.39.
1
Data for 3a: Yield 91%. H NMR (400 MHz, CDCl3): δ = 8.21 (d,
J = 8.3 Hz, 2 H, AnH), 7.59 (dd, J = 8.0, 7.5 Hz, 2 H, AnH), 7.41
[dd, J = 7.5, 7.1 Hz, 4 H, P(C6H5)2], 7.28–7.16 [m, 22 H, AnH,
P(C6H5)2, m-C6H4], 6.54 (d, J = 8.4 Hz, 4 H, o-C6H4), 4.39 (s, 4
H, C5H4), 3.98 (s, 4 H, C5H4), 3.06 [septet, J = 6.9 Hz, 2 H,
CH(CH3)2], 1.4 [d, J = 6.9 Hz, 12 H, CH(CH3)2] ppm. 13C{1H}
NMR (100 MHz, CD2Cl2): δ = 163.0 (C=N), 148.6 (C=N–C),
145.6, 133.4, 133.3, 133.2, 133.1, 132.9, 131.7, 131.4, 130.6, 129.0,
128.9, 128.8, 128.6, 128.1, 126.1, 125.1, 120.5 (aromatic CH and
other quaternary carbon atoms), 73.9 (C5H4), 71.9 (C5H4) 33.9
[CH(CH3)2], 24.2 [CH(CH3)2] ppm. 31P{1H} NMR (162 MHz,
CDCl3): δ = –10.92 ppm. C64H56BCuF4FeN2P2·0.5CH2Cl2: calcd.
C 66.57, H 4.94, N 2.41; found C 66.50, H 5.08, N 2.43.
Data for 5e: Yield 77%. 1H NMR (400 MHz, CD2Cl2): δ = 8.06
(d, J = 8.4 Hz, 2 H, AnH), 7.50 (t, J = 7.8 Hz, 2 H, AnH), 7.44 (t,
J = 9.0 Hz, 6 H, m-C6H5), 7.36 (t, J = 7.4 Hz, 3 H, p-C6H5), 7.25
(t, J = 7.0 Hz, 6 H, o-C6H5), 7.00 (br., 4 H, C6H2), 6.90 (d, J =
7.2 Hz, 2 H, AnH), 2.44 (s, 6 H, p-CH3), 2.00 (br., 12 H, o-CH3)
ppm. 13C{1H} NMR (100 MHz, CD2Cl2): δ = 162.3 (C=N), 144.4
(C=N–C), 141.5, 134.8, 134.0, 133.9, 133.6, 131.0, 129.8, 129.4,
129.3, 128.6, 128.5, 128.3, 128.2, 123.2 (aromatic CH and other
quaternary carbon atoms), 20.7 (p-CH3), 18.1 (o-CH3) ppm.
31P{1H} NMR (162 MHz, CD2Cl2):
δ
=
–2.23 ppm.
Syntheses of Neutral Copper(I) Complexes [CuX(Ar-BIAN)(PPh3)]
[X = Cl (5), I (6)]: A typical synthetic procedure is described as
C48H43ClCuN2P (777.85): calcd. C 74.12, H 5.57, N 3.60; found C
73.90, H 5.51, N 3.65.
Eur. J. Inorg. Chem. 2013, 1404–1417
1413
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

www.eurjic.org
FULL PAPER
Data for 6a: Yield 89%. 1H NMR (400 MHz, CD2Cl2): δ = 8.09
(d, J = 8.0 Hz, 2 H, AnH), 7.48 (t, J = 7.2 Hz, 2 H, AnH), 7.36–
7.21 [m, 25 H, AnH, C6H4, P(C6H5)3], 3.03 [septet, J = 6.8 Hz, 2
7.39 (m, 12 H, AnH, C6H4), 7.18 (d, J = 8.1 Hz, 8 H, C6H4), 3.08
[septet, J = 6.9 Hz, 4 H, CH(CH3)2], 1.40 [d, J = 6.9 Hz, 24 H,
CH(CH3)2] ppm. 13C{1H} NMR (75 MHz, CD2Cl2): δ = 163.2
H, CH(CH3)2], 1.39 [d, J = 7.2 Hz, 12 H, CH(CH3)2] ppm. 13C{1H} (C=N), 148.8 (C=N–C), 145.0, 142.4, 131.2, 131.0, 128.5, 127.9,
NMR (100 MHz, CD2Cl2): δ = 160.3 (C=N), 147.3 (C=N–C), 126.6, 124.4, 120.9 (aromatic CH and other quaternary carbon
145.7, 142.6, 133.8, 133.6, 131.1, 129.9, 129.4, 128.3, 128.2, 128.0,
127.4, 127.2, 123.9, 120.9 (aromatic CH and other quaternary
carbon atoms), 33.8 [CH(CH3)2], 23.9 [CH(CH3)2] ppm. 31P{1H}
atoms), 33.9 [CH(CH3)2], 23.8 [CH(CH3)2] ppm. C60H58Cl2Cu2N4
(1033.14): calcd. C 69.89, H 5.47, N 5.43; found C 69.74, H 5.59,
N 5.42.
NMR (162 MHz, CD2Cl2):
(869.31): calcd. C 66.32, H 4.99, N 3.22; found C 65.99, H 4.82, N
3.15.
δ = –2.95 ppm. C48H43CuIN2P
Data for 7b: Yield 63%. 1H NMR (400 MHz, CD2Cl2): δ = 8.15
(d, J = 7.6 Hz, 4 H, AnH), 7.58 (t, J = 7.6 Hz, 4 H, AnH), 7.54
(d, J = 6.8 Hz, 4 H, AnH), 7.23 (AB, J = 8.4 Hz, 8 H, m-C6H4),
7.06 (AB, J = 8.4 Hz, 8 H, o-C6H4), 3.93 (s, 12 H, CH3O) ppm.
13C{1H} NMR (100 MHz, CD2Cl2): δ = 162.7 (C=N), 159.1
(C=N–C), 142.2, 140.4, 131.3, 130.7, 128.3, 127.0, 124.1, 122.5,
114.9 (aromatic CH and other quaternary carbon atoms), 55.7
(CH3O) ppm. C52H40Cl2Cu2N4O4 (982.91): calcd. C 63.54, H 4.10,
Data for 6b: Yield 76%. 1H NMR (300 MHz, CD2Cl2): δ = 8.07
(d, J = 8.0 Hz, 2 H, AnH), 7.52 (t, J = 7.6 Hz, 2 H, AnH), 7.47
(d, J = 7.2 Hz, 2 H, AnH), 7.35–7.25 [m, 19 H, m-C6H4,
P(C6H5)3], 6.94 (d, J = 8.3 Hz, 4 H, o-C6H4), 3.90 (s, 6 H, CH3O)
ppm. 13C{1H} NMR (75 MHz, CD2Cl2): δ = 160.2 (C=N), 158.4
(C=N–C), 142.6, 141.1, 133.8, 133.6, 131.2, 129.8, 129.5, 128.4, N 5.70; found C 63.29, H 4.02, N 5.70.
128.3, 127.9, 127.6, 123.7, 122.6, 114.4 (aromatic CH and other
Data for 7c: Yield 76%. 1H NMR (300 MHz, C5D5N): δ = 8.22
quaternary carbon atoms), 55.5 (CH3O) ppm. 31P{1H} NMR
(121 MHz, CD2Cl2): δ = –2.91 ppm. C44H35CuIN2O2P (845.20):
calcd. C 62.53, H 4.17, N 3.31; found C 62.66, H 4.00, N 3.20.
(br., 8 H, m-C6H4), 7.92 (d, J = 7.5 Hz, 4 H, AnH), 7.41 (br., 4 H,
AnH), 7.26 (br., 8 H, o-C6H4), 6.94 (br., 4 H, AnH) ppm. 13C{1H}
NMR (75 MHz, C5D5N): δ = 161.6 (C=N), 158.6 (C=N–C), 145.8,
143.1, 132.6, 132.1, 131.3, 129.4, 129.2, 127.1, 125.4, 119.9 (aro-
matic CH and other quaternary carbon atoms) ppm.
Data for 6c: Yield 85%. 1H NMR (300 MHz, CD2Cl2): δ = 8.27
(d, J = 9.0 Hz, 4 H, m-C6H4), 8.19 (d, J = 8.4 Hz, 2 H, AnH), 7.56
(t, J = 7.5 Hz, 2 H, AnH), 7.45–7.24 [m, 19 H, o-C6H4, P(C6H5)3], C48H28Cl2Cu2N8O8 (1042.80): calcd. C 55.29, H 2.71, N 10.75;
7.19 (d, J = 7.2 Hz, 2 H, AnH) ppm. 13C{1H} NMR (75 MHz,
CD2Cl2): δ = 161.1 (C=N), 153.3 (C=N–C), 145.9, 143.2, 133.6,
133.4, 132.9, 132.4, 131.3, 131.2, 129.9, 128.6, 128.5, 126.4, 125.3,
124.7, 121.5 (aromatic CH and other quaternary carbon atoms)
δ = –1.58 ppm.
C42H29CuIN4O4P (875.14): calcd. C 57.64, H 3.34, N 6.40; found
C 57.38, H 3.16, N 6.57.
found C 55.14, H 2.57, N 10.64.
Data for 7d: Yield 57%. 1H NMR (300 MHz, CD2Cl2): δ = 8.07
(d, J = 7.7 Hz, 4 H, AnH), 7.49–7.30 (m, 14 H, AnH, C6H4), 6.83–
6.74 (m, 6 H, AnH, C6H4), 6.21 (d, J = 7.6 Hz, 4 H, C6H4), 3.55
[septet, J = 6.5 Hz, 4 H, CH(CH3)2], 1.35 [d, J = 6.4 Hz, 12 H,
CH(CH3)2], 1.08 [d, J = 6.4 Hz, 12 H, CH(CH3)2] ppm. 13C{1H}
NMR (75 MHz, CD2Cl2): δ = 164.6 (C=N), 145.4 (C=N–C), 142.8,
ppm. 31P{1H} NMR (121 MHz, CD2Cl2):
Data for 6d: Yield 80%. 1H NMR (400 MHz, CD2Cl2): δ = 8.06 (d, 140.7, 131.3, 128.9, 128.2, 128.0, 127.1, 126.6, 125.2, 120.6 (aro-
J = 8.2 Hz, 2 H, AnH), 7.50–7.25 [m, 23 H, AnH, C6H4, P(C6H5)3], matic CH and other quaternary carbon atoms), 29.1 [CH(CH3)2],
6.82 (d, J = 7.2 Hz, isomer, 3.30 H, AnH, C6H4), 6.35 (br., isomer,
0.70 H, C6H4), 4.12 [br., isomer, 0.70 H, CH(CH3)2], 3.25 [br., iso-
25.2 [CH(CH3)2], 23.2 [CH(CH3)2] ppm. C60H56Cl2Cu2N4
(1031.13): calcd. C 69.89, H 5.47, N 5.43; found C 69.99, H 5.17,
mer, 1.30 H, CH(CH3)2], 1.38–0.55 [m, 12 H, CH(CH3)2] ppm. N 5.00.
13C{1H} NMR (100 MHz, CD2Cl2): δ = 162.4 (C=N), 146.6
Data for 7e: Yield 89%. 1H NMR (400 MHz, CD2Cl2): δ = 8.14
(C=N–C), 142.6, 140.3, 138.7, 134.1, 133.9, 133.6, 133.2, 131.1,
130.0, 129.6, 128.4, 128.3, 127.8, 126.8, 126.4, 124.6, 124.4, 123.3,
119.2, 116.6 (aromatic CH and other quaternary carbon atoms),
28.6 [CH(CH3)2], 24.8 [CH(CH3)2], 24.5 [CH(CH3)2], 23.7
[CH(CH3)2], 21.4 [CH(CH3)2] ppm. 31P{1H} NMR (162 MHz,
CD2Cl2): δ = –2.03 ppm. C48H43CuIN2P (869.31): calcd. C 66.32,
H 4.99, N 3.22; found C 66.32, H 5.20, N 3.05.
(d, J = 8.0 Hz, 4 H, AnH), 7.51 (t, J = 8.0 Hz, 4 H, AnH), 6.96 (s,
8 H, C6H2), 6.78 (d, J = 7.6 Hz, 4 H, AnH), 2.48 (s, 12 H, p-CH3),
1.84 (s, 24 H, o-CH3) ppm. 13C{1H} NMR (100 MHz, CD2Cl2): δ
= 165.1 (C=N), 143.0 (C=N–C), 141.9, 136.5, 131.1, 130.9, 129.7,
129.0, 127.8, 127.2, 124.0 (aromatic CH and other quaternary car-
bon atoms), 20.7 (p-CH3), 17.2 (o-CH3) ppm. C60H56Cl2Cu2N4
(1031.13): calcd. C 69.89, H 5.47, N 5.43; found C 69.89, H 5.62,
N 5.30.
Data for 6e: Yield 83%. 1H NMR (300 MHz, CD2Cl2): δ = 8.07
(d, J = 8.4 Hz, 2 H, AnH), 7.50 (t, J = 8.0 Hz, 2 H, AnH), 7.46–
7.35 [m, 9 H, P(C6H5)3], 7.26 [t, J = 7.5 Hz, 6 H, P(C6H5)3], 7.01
(br., 4 H, C6H2), 6.90 (d, J = 7.2 Hz, 2 H, AnH), 2.45 (s, 6 H, p-
CH3), 2.15 (br., 12 H, o-CH3) ppm. 13C{1H} NMR (75 MHz,
CD2Cl2): δ = 162.6 (C=N), 144.1 (C=N–C), 141.8, 135.1, 134.3,
134.1, 133.6, 133.2, 131.0, 130.0, 129.5, 129.3, 128.7, 128.5, 128.3,
128.1, 127.4, 123.3 (aromatic CH and other quaternary carbon
atoms), 20.7 (p-CH3), 19.0 (o-CH3) ppm. 31P{1H} NMR
(121 MHz, CD2Cl2): δ = –0.39 ppm. C48H43CuIN2P (869.31):
calcd. C 66.32, H 4.99, N 3.22; found C 66.38, H 4.93, N 3.22.
Data for 7f: Yield 40%. 1H NMR (400 MHz, CD2Cl2): δ = 8.16 (d,
J = 8.0 Hz, 4 H, AnH), 7.56 (t, J = 8.0 Hz, 4 H, AnH), 7.49–7.42
(m, 12 H, C6H3), 6.90 (d, J = 7.2 Hz, 4 H, AnH), 3.11 [septet, J =
6.8 Hz, 8 H, CH(CH3)2], 1.40 [d, J = 6.8 Hz, 24 H, CH(CH3)2],
1.10 [d, J = 6.8 Hz, 24 H, CH(CH3)2] ppm. 13C{1H} NMR
(100 MHz, CD2Cl2): δ = 165.2 (C=N), 143.5 (C=N–C), 142.1,
137.3, 131.25, 131.21, 128.8, 127.1, 126.7, 124.7, 124.2 (aromatic
CH and other quaternary carbon atoms), 29.1 [CH(CH3)2], 23.4
[CH(CH3)2], 22.6 [CH(CH3)2] ppm. C72H80Cl2Cu2N4 (1199.45):
calcd. C 72.10, H 6.72, N 4.67; found C 71.90, H 7.01, N 4.58.
Syntheses of Dimeric Copper(I) Complexes [{Cu(Ar-BIAN)X}2] [X
= Cl (7), I (8)]: The procedure is the same as those used for synthe-
ses of complexes 5 and 6, except that AsPh3 (0.5 mmol) or SbPh3
(0.5 mmol) were used in place of PPh3.
Data for 8a: Yield 92%. 1H NMR (400 MHz, CD2Cl2): δ = 8.08
(d, J = 8.4 Hz, 4 H, AnH), 7.53 (t, J = 8.4 Hz, 4 H, AnH), 7.43–
7.38 (m, 20 H, AnH, C6H4), 3.10 [septet, J = 6.8 Hz, 4 H, CH-
(CH3)2], 1.44 [d, J = 6.8 Hz, 24 H, CH(CH3)2] ppm. 13C{1H} NMR
(100 MHz, CD2Cl2): δ = 161.8 (C=N), 147.9 (C=N–C), 145.4,
131.3, 130.4, 128.0, 127.4, 127.3, 124.1 (aromatic CH and other
Date for 7a: Yield 87%. 1H NMR (300 MHz, CD2Cl2): δ = 8.18
(d, J = 8.1 Hz, 4 H, AnH), 7.58 (t, J = 8.1 Hz, 4 H, AnH), 7.44–
Eur. J. Inorg. Chem. 2013, 1404–1417
1414
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

www.eurjic.org
FULL PAPER
quaternary carbon atoms), 33.9 [CH(CH3)2], 23.8 [CH(CH3)2]
ppm. C60H56Cu2I2N4 (1214.03): calcd. C 59.36, H 4.65, N 4.62;
found C 59.16, H 4.80, N 4.43.
(821.80): calcd. C 70.15, H 5.27, N 3.41; found C 70.00, H 5.18, N
3.41.
X-ray Diffraction: Crystallographic and experimental details of
crystal structure determinations are given in Table S1 of Support-
ing Information. In each case, a specimen crystal was selected un-
der an inert atmosphere, covered with polyfluoroether and
mounted on the end of a nylon loop. All crystal data were collected
at 150 K in a Bruker AXS-KAPPA APEX II diffractometer
equipped with an Oxford Cryosystems open-flow nitrogen cryostat,
using graphite-monochromated Mo-Kα radiation (λ = 0.71073 Å).
Cell parameters were retrieved by using Bruker SMART[38] soft-
ware and refined by using Bruker SAINT[39] on all observed reflec-
tions. Absorption corrections were applied using SADABS.[40]
Structure solution and refinement were performed using direct
methods with the programs SIR92,[41] SIR97,[42] SIR2004[43] and
SHELXL,[44] all included in the package of programs WINGX-
Version 1.70.01.[45] Crystal structures were refined to convergence,
even though some of the crystals were of poorer quality, such as
compounds 3a, 4d, 5a and 8e that presented high Rint (0.1167,
0.1078, 0.1414 and 0.1231, respectively), and relatively low ratio of
observed/unique reflections. Some of the crystals showed the pres-
ence of disordered solvent molecules, the PLATON/SQUEEZE[46]
routine being applied whenever a good disorder model was imposs-
ible to attain (1b, 1c, 1d, 3a, 4a, 5c, 8a, 8e and 9a). When analysing
the diffraction data of compound 8e, a low value of |E2 – 1| = 0.728
pointed to the presence of racemic twinning. The TWIN law used
was –1 0 0 0 –1 0 0 0 –1, and the BASF component was refined to
0.30. Non-hydrogen atoms were refined with anisotropic thermal
parameters. All hydrogen atoms were inserted in idealised positions
Data for 8b: Yield 80%. 1H NMR (300 MHz, C5D5N): δ = 7.87 (d,
J = 6.5 Hz, 4 H, AnH), 7.57 (d, J = 8.7 Hz, 8 H, m-C6H4), 7.32–
7.28 (m, 8 H, AnH), 6.97 (d, J = 8.8 Hz, 8 H, o-C6H4), 3.59 (s, 12
H, CH3O) ppm. 13C{1H} NMR (75 MHz, C5D5N): δ = 161.8
(C=N), 159.6 (C=N–C), 144.6, 143.1, 132.9, 131.0, 130.0, 129.5,
124.9, 123.4, 116.6 (aromatic CH and other quaternary carbon
atoms), 56.7 (CH3O) ppm. C52H40Cu2I2N4O4 (1165.81): calcd. C
53.57, H 3.46, N 4.81; found C 53.64, H 3.28, N 4.81.
Data for 8c: Yield 70%. 1H NMR (300 MHz, C5D5N): δ = 8.24
(br., 8 H, m-C6H4), 7.95 (d, J = 8.1 Hz, 4 H, AnH), 7.43 (br., 4 H,
AnH), 7.32 (br., 8 H, o-C6H4), 6.96 (br., 4 H, AnH) ppm. 13C{1H}
NMR (75 MHz, C5D5N): δ = 161.7 (C=N), 158.5 (C=N–C), 145.9,
143.3, 132.6, 131.3, 129.5, 129.1, 127.1, 125.4, 120.0 (aromatic CH
and other quaternary carbon atoms) ppm. C48H28Cu2I2N8O8
(1225.70): calcd. C 47.04, H 2.30, N 9.14; found C 47.13, H 2.21,
N 9.16.
Data for 8d: Yield 61% 1H NMR (300 MHz, CD2Cl2): δ = 7.95 (d,
J = 7.8 Hz, 4 H, AnH), 7.43–7.13 (m, 20 H, AnH, C6H4), 6.75 (d,
J = 6.6 Hz, 4 H, C6H4), 3.46–3.34 [m, 4 H, CH(CH3)2], 0.89 [d, J
= 5.7 Hz, 24 H, CH(CH3)2] ppm. 13C{1H} NMR (75 MHz,
CD2Cl2): δ = 162.5 (C=N), 145.4 (C=N–C), 142.6, 140.1, 138.1,
131.3, 130.1, 128.5, 128.0, 126.6, 124.6, 121.2 (aromatic CH and
other quaternary carbon atoms), 28.5 [CH(CH3)2], 24.5 [CH-
(CH3)2] ppm. C60H56Cu2I2N4 (1214.03): calcd. C 59.36, H 4.65, N
4.62; found C 58.81, H 4.64, N 4.25.
Data for 8e: Yield 74%. 1H NMR (400 MHz, CD2Cl2): δ = 8.00 and allowed to refine riding in the parent C atoms, with C–H dis-
(d, J = 8.4 Hz, 4 H, AnH), 7.46 (t, J = 7.8 Hz, 4 H, AnH), 7.00 (s, tances of 0.95, 0.98 and 1.00 Å for aromatic, methyl and methine
8 H, C6H2), 6.75 (d, J = 6.8 Hz, 4 H, AnH), 2.49 (s, 12 H, p-CH3), H atoms, respectively, and with Uiso(H) = 1.2Ueq(C). Graphic pres-
2.19 (s, 24 H, o-CH3) ppm. 13C{1H} NMR (100 MHz, CD2Cl2): δ entations were prepared with ORTEP-III.[47] CCDC-896177 (for
= 161.9 (C=N), 144.0 (C=N–C), 141.5, 134.3, 130.9, 129.6, 129.3, 1b), -896178 (for 1c), -896179 (for 1d), -896180 (for 3a), -896181
128.6, 128.4, 127.2, 123.1 (aromatic CH and other quaternary car-
bon atoms), 20.8 (p-CH3), 18.8 (o-CH3) ppm. C60H56Cu2I2N4
(1214.03): calcd. C 59.36, H 4.65, N 4.62; found C 59.15, H 4.67,
N 4.57.
(for 4a), -896182 (for 4d), -896183 (for 5a), -896184 (for 5b),
-896185 (for 5c), -896186 (for 6a), -896187 (for 6b), -896188 (for
6e), -896189 (for 7f), -896190 (for 8a), -896191 (for 8e), -896192
(for 8f) and -896193 (for 9a) contain the supplementary crystallo-
graphic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
Data for 8f: Yield 47%. 1H NMR (300 MHz, CD2Cl2): δ = 8.09 (d,
J = 8.1 Hz, 4 H, AnH), 7.50 (t, J = 7.8 Hz, 4 H, AnH), 7.42–7.40
(br., 12 H, C6H3), 6.73 (br., 4 H, AnH), 3.25 [septet, J = 6.0 Hz, 8
H, CH(CH3)2], 1.31 [d, J = 6.6 Hz, 24 H, CH(CH3)2], 0.97 [d, J =
5.7 Hz, 24 H, CH(CH3)2] ppm. 13C{1H} NMR (75 MHz, CD2Cl2):
δ = 164.4 (C=N), 143.8 (C=N–C), 142.2, 137.8, 131.1, 130.7, 128.5,
127.4, 126.4, 124.8, 124.2 (aromatic CH and other quaternary car-
bon atoms), 28.9 [CH(CH3)2], 24.3 [CH(CH3)2], 23.4 [CH(CH3)2]
ppm. C72H80Cu2I2N4 (1382.35): calcd. C 62.56, H 5.83, N 4.05;
found C 62.44, H 5.95, N 4.08.
General Procedure for the CuAAC Reaction: In a typical experi-
ment, azide (1.0 mmol), alkyne (1.0 mmol) and copper(I) complex
(1.0 mol-%) were weighed in the glovebox, and mixed in a 15 mL
vial. THF (5 mL) was added and the resulting mixture was stirred
for 2 h at 50 °C under a nitrogen atmosphere. An aliquot of the
final crude mixture was evaporated to dryness and characterised
1
by H NMR spectroscopy in CDCl3. The yield was calculated by
1H NMR spectroscopy, by integration of specific resonances char-
acteristic of the reagents and product, using the copper(I) complex
resonances as internal standards. The triazole products 10–19 were
identified by their 1H NMR spectra, which were consistent with
the data reported in the corresponding literature. In the case of the
new triazoles 20 and 21, the solvent and the remaining reagents
were removed under vacuum. The residue was washed with n-hex-
ane and recrystallised from methanol.
Synthesis of Neutral Copper(I) Complex [CuCl(4-iPrBIAN)(AsPh3)]
(9a): The procedure is the same as those used for syntheses of com-
plexes 5 and 6, except that AsPh3 (0.5 mmol) was used in place of
PPh3. In this particular case, in which the equimolar amounts of
4-iPrC6H4-BIAN, AsPh3 and CuCl (1.0 equiv.) were present, com-
plex 9a was exclusively isolated in good yield, and not as the dimer
complex 7a (see above).
1
Data for 9a: Yield 76%. H NMR (400 MHz, CDCl3): δ = 8.05 (d,
J = 8.0 Hz, 2 H, AnH), 7.50 (t, J = 7.8 Hz, 2 H, AnH), 7.44 (d, J
Data for 20: 1H NMR (300 MHz, CDCl3): δ = 7.80 (s, 1 H,
= 7.2 Hz, 2 H, AnH), 7.32–7.20 [m, 23 H, C6H4, As(C6H5)3] ppm. C=CHN3), 7.35 (d, J = 7.5 Hz, 1 H, o-C6H4), 7.13 (t, J = 7.2 Hz,
13C{1H} NMR (100 MHz, CDCl3): δ = 161.5 (C=N), 147.7 (C=N–
C), 145.4, 142.4, 137.2, 133.5, 131.2, 130.2, 128.7, 128.6, 128.2,
127.4, 124.1, 121.0 (aromatic CH and other quaternary carbon
1 H, p-C6H4), 6.75 (t, J = 8.7 Hz, 2 H, m-C6H4), 5.48 (br., 2 H,
NH2), 4.58 (t, J = 6.6 Hz, 2 H, CH2), 3.68 (t, J = 5.4 Hz, 2 H,
CH2), 2.18 (m, 2 H, CH2), 1.91 (br., 1 H, OH) ppm. 13C{1H} NMR
atoms), 33.8 [CH(CH3)2], 24.1 [CH(CH3)2] ppm. C48H43AsClCuN2 (75 MHz, CDCl3): δ = 145.2 (C-NH2 and C=CHN3), 129.2 (C6H4),
Eur. J. Inorg. Chem. 2013, 1404–1417
1415
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

www.eurjic.org
FULL PAPER
3193; b) T. R. Chan, R. Hilgraf, K. B. Sharpless, V. V. Fokin,
Org. Lett. 2004, 6, 2853–2855.
127.8 (C6H4), 120.4 (C=CHN3), 117.5 (C6H4), 116.9 (C6H4), 99.5
(C6H4), 58.9 (CH2), 47.1 (CH2), 32.7 (CH2) ppm. C11H14N4
(202.26): calcd. C 60.53, H 6.47, N 25.67; found C 60.51, H 6.59,
N 25.53.
[8]
[9]
[10]
L. Liang, D. Astruc, Coord. Chem. Rev. 2011, 255, 2933–2945.
S. Díez-González, Catal. Sci. Technol. 2011, 1, 166–178.
N. Candelon, D. Lastécouéres, A. K. Diallo, J. R. Aranzaes, D.
Astruc, J.-M. Vincent, Chem. Commun. 2008, 741–743.
P. S. Donnelly, S. D. Zanatta, S. C. Zammit, J. M. White, S. J.
Williams, Chem. Commun. 2008, 2459–2461.
S. Özçubukçu, E. Ozkal, C. Jimeno, M. A. Pericàs, Org. Lett.
2009, 11, 4680–4683.
F. Li, T. S. A. Hor, Chem. Eur. J. 2009, 15, 10585–10592.
S.-Q. Bai, L. Koh, T. S. A. Hor, Inorg. Chem. 2009, 48, 1207–
1213.
I. Cano, M. C. Nicasio, P. J. Pérez, Org. Biomol. Chem. 2010,
8, 536–538.
J. García-Álvarez, J. Díez, J. Gimeno, Green Chem. 2010, 12,
2127–2130.
S. Lal, S. Díez-González, J. Org. Chem. 2011, 76, 2367–2373.
a) S. Díez-González, A. Correa, L. Cavallo, S. P. Nolan, Chem.
Eur. J. 2006, 12, 7558–7564; b) S. Díez-González, E. C. Escud-
ero-Adán, J. Benet-Buchholz, E. D. Stevens, A. M. Z. Slawin,
S. P. Nolan, Dalton Trans. 2010, 39, 7595–7606.
Data for 21: 1H NMR (300 MHz, CDCl3): δ = 7.87 (s, 1 H,
C=CHN3), 7.35 (d, J = 7.5 Hz, 1 H, o-C6H4), 7.11 (t, J = 7.5 Hz,
1 H, p-C6H4), 6.74 (t, J = 8.3 Hz, 2 H, m-C6H4), 5.44 (br., 2 H,
NH2), 5.16 (s, 2 H, CH2), 4.25 (q, 2 H, CH2), 1.28 (t, J = 7.2 Hz,
3 H, CH3) ppm. 13C{1H} NMR (75 MHz, CDCl3): δ = 166.3
(C=O), 148.8 (C=CHN3), 145.1 (C–NH2), 129.2 (p-C6H4), 127.9
(o-C6H4), 121.4 (C=CHN3), 117.4 (m-C6H4), 116.8 (m-C6H4), 113.5
(C6H4), 62.5 (CH2), 51.0 (CH2), 14.1 (CH3) ppm. C12H14N4O2
(246.27): calcd. C 58.53, H 5.73, N 22.75; found C 58.23, H 5.78,
N 22.70.
[11]
[12]
[13]
[14]
[15]
[16]
Supporting Information (see footnote on the first page of this arti-
cle): It contains crystal data and structure refinements for com-
plexes 1b–d, 3a, 4a, 4d, 5a–c, 6a, 6b, 6e, 7f, 8a, 8e, 8f and 9a (Table
S1) and ORTEP diagrams of complexes 1b–d, 4d, 5b, 5c, 6a, 6b, 6e,
7f, 8e, 8f and 9a (Figures S1–S13).
[17]
[18]
[19]
[20]
[21]
S. Díez-González, S. P. Nolan, Angew. Chem. 2008, 120, 9013;
Angew. Chem. Int. Ed. 2008, 47, 8881–8884.
P. Fabbrizzi, S. Cicchi, A. Brandi, E. Sperotto, G. van Koten,
Eur. J. Org. Chem. 2009, 5423–5430.
Acknowledgments
a) S. G. Correia, M. M. Marques, J. R. Ascenso, A. F. G. Rib-
eiro, P. T. Gomes, A. R. Dias, M. Blais, M. D. Rausch, J. C. W.
Chien, J. Polym. Sci., Part A 1999, 37, 2471–2480; b) H.-R.
Liu, S. I. Costa, P. T. Gomes, M. T. Duarte, R. Branquinho,
A. C. Fernandes, J. C. W. Chien, M. M. Marques, J. Or-
ganomet. Chem. 2005, 690, 1314–1323; c) J.-C. Yuan, L. C.
Silva, P. T. Gomes, P. Valerga, J. M. Campos, M. R. Ribeiro,
J. C. W. Chien, M. M. Marques, Polymer 2005, 46, 2122–2132;
d) V. Rosa, P. J. Gonzalez, T. Avilés, P. T. Gomes, R. Welter,
A. C. Rizzi, M. C. G. Passeggi, C. D. Brondino, Eur. J. Inorg.
Chem. 2006, 23, 4761–4769; e) V. Rosa, S. A. Carabineiro, T.
Avilés, P. T. Gomes, R. Welter, J. M. Campos, M. R. Ribeiro,
J. Organomet. Chem. 2008, 693, 769–775; f) L.-D. Li, C. S. B.
Gomes, P. T. Gomes, M. T. Duarte, Synth. Commun. 2008, 38,
4415–4425; g) L.-D. Li, C. S. B. Gomes, P. T. Gomes, M. T. Du-
arte, Z. Fan, Dalton Trans. 2011, 40, 3365–3380; h) L.-D. Li,
P. T. Gomes, M. A. N. D. A. Lemos, F. Lemos, Z. Fan, Macro-
mol. Chem. Phys. 2011, 212, 367–374; i) L.-D. Li, C. S. B.
Gomes, P. S. Lopes, P. T. Gomes, H. P. Diogo, J. R. Ascenso,
Eur. Polym. J. 2011, 47, 1636–1645; j) V. Rosa, T. Avilés, G.
Aullon, B. Covelo, C. Lodeiro, Inorg. Chem. 2008, 47, 7734–
7744; k) V. Rosa, C. I. M. Santos, R. Welter, G. Aullón, C.
Lodeiro, T. Avilés, Inorg. Chem. 2010, 49, 8699–8708; l) P.
Frémont, H. Clavier, V. Rosa, T. Avilés, P. Braunstein, Organo-
metallics 2011, 30, 2241–2251; m) C. Romain, V. Rosa, C. Flie-
del, F. Bier, F. Hild, R. Welter, S. Dagorne, T. Avilés, Dalton
Trans. 2012, 41, 3377–3379.
L. Li, P. S. Lopes, V. Rosa, C. A. Figueira, M. A. N. D. A.
Lemos, M. T. Duarte, T. Avilés, P. T. Gomes, Dalton Trans.
2012, 41, 5144–5154.
For other works about copper(I) complexes containing Ar-
BIAN and phosphanes, see: a) T. Kern, U. Monkowius, M.
Zabel, G. Knör, Eur. J. Inorg. Chem. 2010, 4148–4156; b) T.
Kern, U. Monkowius, M. Zabel, G. Knör, Inorg. Chim. Acta
2011, 374, 632–636.
a) P. Comba, C. Katsichtis, B. Nuber, H. Pritzkow, Eur. J. In-
org. Chem. 1999, 777–783; b) D. Saravanabharathi, P. Venugo-
palan, A. G. Samuelson, Polyhedron 2002, 21, 2433–2443; c) T.
McCormick, W.-L. Jia, S. Wang, Inorg. Chem. 2006, 45, 147–
155.
a) J. Díez, M. P. Gamasa, J. Gimeno, A. Aguirre, S. García-
Granda, J. Holubova, L. R. Falvello, Organometallics 1999, 18,
662–669; b) J. Díez, M. P. Gamasa, J. Gimeno, M. Lanfranchi,
A. Tiripicchio, J. Organomet. Chem. 2001, 637–639, 677–682;
We thank the Fundação para Ciência e Tecnologia (FCT) for fin-
ancial support (grant numbers PEst-OE/QUI/UI0100/2011-2012
and PEst-C/EQB/LA0006/2011; projects PTDC/QUI/65474/2006,
PTDC/EQU-EQU/110313/2009 and PTDC/QUI-QUI/099873/
2008, co-financed by Fundo Europeu de Desenvolvimento Re-
gional (FEDER)) and fellowships to L. L., C. A. F., C. S. B. G.,
V. R. and C. F. (grant numbers SFRH/BPD/30733/2006, SFRH/
BD/47730/2008, SFRH/BPD/64423/2009, SFRH/BPD/44262/2008
and SFRH/BPD/73253/2010, respectively).
[1] a) V. V. Rostovtsev, L. G. Green, V. V. Fokin, K. B. Sharpless,
Angew. Chem. 2002, 114, 2708–2711; Angew. Chem. Int. Ed.
2002, 41, 2596–2599; b) C. W. Tornøe, C. Christensen, M. Mel-
dal, J. Org. Chem. 2002, 67, 3057–3064; c) M. Meldal, C. W.
Tornøe, Chem. Rev. 2008, 108, 2952–3015.
[2] a) D. B. Ramachary, C. F. Barbas III, Chem. Eur. J. 2004, 10,
5323–5331; b) W. H. Binder, C. Kluger, Curr. Org. Chem. 2006,
10, 1791–1815; c) Y. Hua, A. H. Flood, Chem. Soc. Rev. 2010,
39, 1262–1271; d) J. E. Hein, V. V. Fokin, Chem. Soc. Rev. 2010,
39, 1302–1315; e) K. D. Hänni, D. A. Leigh, Chem. Soc. Rev.
2010, 39, 1240–1251.
[3] a) H. C. Kolb, K. B. Sharpless, Drug Discovery Today 2003, 8,
1128–1137; b) J. E. Moses, A. D. Moorhouse, Chem. Soc. Rev.
2007, 36, 1249–1262; c) Y. L. Angell, K. Burgess, Chem. Soc.
Rev. 2007, 36, 1674–1689; d) J.-F. Lutz, Z. Zarafshani, Adv.
Drug Delivery Rev. 2008, 60, 958–970; e) G. C. Tron, T. Pirali,
R. A. Billington, P. L. Canonico, G. Sorba, A. A. Genazzani,
Med. Res. Rev. 2008, 28, 278–308; f) J. M. Holub, K. Kirshen-
baum, Chem. Soc. Rev. 2010, 39, 1325–1337; g) A. H. El-
Sagheer, T. Brown, Chem. Soc. Rev. 2010, 39, 1388–1405.
[4] J.-F. Lutz, Angew. Chem. 2007, 119, 1036; Angew. Chem. Int.
Ed. 2007, 46, 1018–1025.
[5] a) F. Fazio, M. C. Bryan, O. Blixt, J. C. Paulson, C.-H. Wong,
J. Am. Chem. Soc. 2002, 124, 14397–14402; b) T. Jin, M. Yan,
Menggenbateer, T. Minato, M. Bao, Y. Yamamoto, Adv. Synth.
Catal. 2011, 353, 3095–3100; c) T. Jin, M. Yan, Y. Yamamoto,
ChemCatChem 2012, 4, 1217–1229.
[22]
[23]
[24]
[25]
[6] a) W. G. Lewis, F. G. Magallon, V. V. Fokin, M. G. Finn, J.
Am. Chem. Soc. 2004, 126, 9152–9153; b) J.-C. Meng, V. V.
Fokin, M. G. Finn, Tetrahedron Lett. 2005, 46, 4543–4546.
[7] a) Q. Wang, T. R. Chan, R. Hilgraf, V. V. Fokin, K. B.
Sharpless, M. G. Finn, J. Am. Chem. Soc. 2003, 125, 3192–
Eur. J. Inorg. Chem. 2013, 1404–1417
1416
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

www.eurjic.org
FULL PAPER
c) W.-Y. Yeh, Y.-C. Liu, S.-M. Peng, G.-H. Lee, Inorg. Chim.
Acta 2005, 358, 1987–1992; d) P. Braunstein, D. Bubrin, B.
Sarkar, Inorg. Chem. 2009, 48, 2534–2540.
[26] C. A. Tolman, Chem. Rev. 1977, 77, 313–348.
[27] L. R. Martin, F. W. B. Einstein, R. K. Pomeroy, Inorg. Chem.
1983, 22, 1959–1961.
[35]
a) S. P. Neo, Z.-Y. Zhou, T. C. W. Mak, T. S. A. Hor, J. Chem.
Soc. Dalton Trans. 1994, 3451–3457; b) N. Armaroli, G. Ac-
corsi, G. Bergamini, P. Ceroni, M. Holler, O. Moudam, C. Du-
hayon, B. Delavaux-Nicot, J.-F. Nierengarten, Inorg. Chim.
Acta 2007, 360, 1032–1042; c) M. G. Babashkina, D. A. Safin,
A. Klein, M. Bolte, Eur. J. Inorg. Chem. 2010, 4018–4026; d)
D. A. Safin, M. G. Babashkina, M. Bolte, A. Klein, Crys-
tEngComm 2011, 13, 568–576.
[28] G. Salas, J. A. Casares, P. Espinet, Dalton Trans. 2009, 8413–
8420.
[29] L. E. Manzer, C. A. Tolman, J. Am. Chem. Soc. 1975, 97, 1955–
1986.
[36]
[37]
R. van Asselt, C. J. Elsevier, W. J. J. Smeets, A. L. Spek, R. Be-
nedix, Recl. Trav. Chim. Pays-Bas 1994, 113, 88–98.
[30] L. S. Bonnington, R. K. Coll, E. J. Gray, J. I. Flett, W. Hender-
son, Inorg. Chim. Acta 1999, 290, 213–221.
[31] C. A. Tolman, W. C. Seidel, L. W. Gosser, J. Am. Chem. Soc.
1974, 96, 53–60.
a) A. Hetherington, W. Levason, M. D. Spicer, Polyhedron
1990, 9, 1609–1612; b) J. R. Black, W. Levason, M. D. Spicer,
M. Webster, J. Chem. Soc. Dalton Trans. 1993, 3129–9136.
SMART Software for the CCD Detector System, v. 5.625,
Bruker AXS Inc., Madison, WI, USA, 2001.
SAINT Software for the CCD Detector System, v. 7.03, Bruker
AXS Inc., Madison, WI, USA, 2004.
G. M. Sheldrick, SADABS, Program for Empirical Absorption
Correction, University of Göttingen, Germany, 1996.
[38]
[39]
[40]
[41]
[32] Note: the cone angles of dppe and dppf were calculated based
3
on Tolman’s cone angle equation:[26] θ = (2/3)
θi/2, θ = (2/
͚
i = 1
3)(90/2 + 145/2+ 145/2) = 126.7° for dppe, and θ = (2/
3)(108.84/2 + 145/2+ 145/2) = 132.9° for dppf. The angle P–
M–P for dppe (90°) is a typical value obtained from the litera-
ture,[24] whereas the angle for dppf (108.84°) was obtained from
the molecular structure of 3a.
A. Altomare, G. L. Cascarano, C. Giacovazzo, A. Guagliardi,
J. Appl. Crystallogr. 1993, 26, 343–350.
[33] a) T. Kräuter, B. Neumüller, Polyhedron 1996, 15, 2851–2857;
b) M. D. Fryzuk, M. D. Le Page, C. D. Montgomery, S. J.
Rettig, Inorg. Chem. Commun. 1999, 2, 378–380; c) S. H. Oak-
ley, D. B. Soria, M. P. Coles, P. B. Hitchcock, Dalton Trans.
2004, 537–546; d) T. S. Lobana, R. Sharma, A. Castiñeiras, G.
Hundal, R. J. Butcher, Inorg. Chim. Acta 2009, 362, 3547–3554;
e) T. S. Lobana, R. Sharma, A. Castiñeiras, R. J. Butcher, Z.
Anorg. Allg. Chem. 2010, 636, 2698–2703.
[34] a) M. R. Churchill, J. R. Missert, Inorg. Chem. 1981, 20, 619–
621; b) A. J. Blake, R. O. Gould, A. J. Holder, A. J. Lavery, M.
Schröder, Polyhedron 1990, 9, 2919–2924; c) M. Koman, M.
Mariassy, G. Ondrejovic, Acta Crystallogr. Sect. C 1991, 47,
1204–1206; d) S. Ye, W. Kaim, B. Sarkar, B. Schwederski, F.
Lissner, T. Schleid, C. Duboc-Toia, J. Fiedler, Inorg. Chem.
Commun. 2003, 6, 1196–1200; e) M. Sieger, C. Vogler, A. Klein,
A. Knöldler, M. Wanner, J. Fiedler, S. Zálisˇ, T. L. Snoeck, W.
Kaim, Inorg. Chem. 2005, 44, 4637–4643.
[42] A. Altomare, M. C. Burla, M. Camalli, G. L. Cascarano, C.
Giacovazzo, A. Guagliardi, A. G. G. Moliterni, G. Polidori, R.
Spagna, J. Appl. Crystallogr. 1999, 32, 115–119.
[43] M. C. Burla, R. Caliandro, M. Camalli, B. Carrozzini, G. L.
Cascarano, L. De Caro, C. Giacovazzo, G. Polidori, R.
Spagna, J. Appl. Crystallogr. 2005, 38, 381–388.
[44] G. M. Sheldrick, Shelxl-97, A Computer Program for Refine-
ment of Crystal Structure, University of Göttingen, Germany,
1997.
[45] L. J. Farrugia, J. Appl. Crystallogr. 1999, 32, 837–838.
[46] A. L. Spek, J. Appl. Crystallogr. 2003, 36, 7–13.
[47] M. N. Burnett, C. K. Johnson, ORTEP-III: Oak Ridge Ther-
mal Ellipsoid Plot Program for Crystal Structure Illustration,
Oak Ridge National Laboratory Report ORNL-6895, 1996.
Received: October 7, 2012
Published Online: January 14, 2013
Eur. J. Inorg. Chem. 2013, 1404–1417
1417
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim