Nickel(II) complexes of di- and tri-substituted thiourea mono- and di-anions

Article abstract of DOI:10.1016/j.ica.2010.12.011

Reaction of nickel(II) acetate, 1,2-bis(diphenylphosphino)ethane (dppe), and a di- or tri-substituted thiourea R¹NHC(S)R²R ³ (R³ = H or alkyl) with trimethylamine in hot methanol gave cationic nickel(II) complex

Full text of DOI:10.1016/j.ica.2010.12.011

Inorganica Chimica Acta 368 (2011) 1–5
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Inorganica Chimica Acta
journal homepage: www.elsevier.com/locate/ica
Nickel(II) complexes of di- and tri-substituted thiourea mono- and di-anions
b
Ho Ying Yuen a, William Henderson a, , Allen G. Oliver
⇑
a Department of Chemistry, University of Waikato, Private Bag 3105, Hamilton, New Zealand
b Molecular Structure Facility, Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556, USA
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 13 July 2010
Accepted 4 December 2010
Available online 16 December 2010
Reaction of nickel(II) acetate, 1,2-bis(diphenylphosphino)ethane (dppe), and a di- or tri-substituted thio-
urea R1NHC(S)R2R3 (R3 = H or alkyl) with trimethylamine in hot methanol gave cationic nickel(II) com-
plexes containing N,S-chelateÀd thiourea monoanion ligands [Ni{SC(NR2R3)NR1}(dppe)]+, which canÀbe
readily isolated as their BPh4 salts. The X-ray crystal structure of [Ni{SC(NMe2)NPh}(dppe)]+BPh4 is
reported.
Keywords:
Ó 2010 Elsevier B.V. All rights reserved.
Nickel complexes
Thiourea complexes
Sulfur donor ligands
Crystal structure
1. Introduction
2. Results and discussion
Thioureas are versatile ligands capable of binding to a wide
range of metal ions in various coordination modes [1]. Depending
on the actual thiourea ligand, they are capable of binding in either
a monodentate or bidentate chelating fashion, in a range of proton-
ation states as neutral ligands, or mono- or di-anions. Thiourea
monoanion complexes of a range of transition metals including
chromium [2], rhodium [3–5], ruthenium [3,6,7], technetium [8],
rhenium [9,10], gold [11], nickel [12,13], palladium [14] and plat-
inum [15,16] have been reported in the literature. The ligands bind
predominantly in an N,S-chelating mode giving four-membered
rings. There have also been many studies on ligands of the general
type R2NC(S)NHC(O)Ph, which often bind as monoanions, giving
six-membered rings through sulfur and oxygen [17].
In this contribution we report on some new nickel(II) com-
plexes containing thiourea monoanion ligands in conjunction with
the bidentate phosphine dppe [1,2-bis(diphenylphosphino)eth-
ane]. Examination of the literature reveals that such complexes
have not been described previously though some phosphine nick-
el(II) complexes of 2,4,6-trimercaptotriazine, which contain four-
membered Ni–S–C(NR)–NR rings have been described [18]. In con-
trast, bis(thiourea monoanion) complexes of the type [NiL2] [12,13]
and nickel complexes of heterocyclic thiones [19–21] are well doc-
umented in the literature.
Reaction of nickel(II) acetate with one equivalent of 1,2-
bis(diphenylphosphino)ethane (dppe) in warm methanol, followed
by addition of a tri-substituted thiourea R1NHC(S)R2R3 and Me3N
base resulted in the formation of orange solutions which were
shown by positive ion electrospray ionisation mass spectrometry
(ESI
MS)
to
contain
solely
the
thiourea
cations
[Ni{SC(NR2R3)NR1}(dppe)]+. Excellent agreement was observed be-
tween the observed and calculated isotope patterns, including
masses of the base peak (58Ni isotopomer). The cations can easily
be isolated by addition of an excess of NaBPh4 to the hot reaction
mixtures, giving orange tetraphenylborate salts 1. Although the
yields of the products are moderate (typically around 60% isolated
yield based on nickel(II) acetate) they are obtained in a high state
of purity, as shown by excellent elemental microanalytical data on
the as-isolated products. Attempts at preparing analogous com-
plexes using triphenylphosphine in place of dppe were unsuccess-
ful. The range of complexes synthesised is summarised in
Scheme 1.
In a related fashion the one-pot reaction of nickel(II) acetate,
dppe, a sym-disubstituted thiourea RNHC(S)NHR (R = Ph or n-Bu)
and trimethylamine likewise gave orange solutions from which
the monocations can be isolated as orange solids 2 by precipitation
with excess NaBPh4. In this case, the addition of the large BPh4À an-
ion promotes the precipitation of the cationic complex containing a
mono-deprotonated thiourea ligand, as opposed to the neutral
complex containing a thiourea dianion.
An alternative route to one of the complexes (1e) utilised the
reaction of the known, green nickel(II) bis(thiourea monoanion)
complex [Ni{SC(N(CH2CH2)2O)NPh}2] 3 [12] with dppe in methanol
⇑
Corresponding author. Fax: +64 7 838 4219.
E-mail address: w.henderson@waikato.ac.nz (W. Henderson).
0020-1693/$ - see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2010.12.011

2
H.Y. Yuen et al. / Inorganica Chimica Acta 368 (2011) 1–5
+
Ph2
P
S
R2
R3
-
Ni
C
N
BPh4
N
P
Ph2
R1
Complex
R1
R2,R3
1a
1b
1c
1d
1e
1f
1g
1h
1i
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Me, Me
Cy, Cy
(CH2)4
(CH2)5
(CH2CH2)2O
(CH2CH2)2S
CH2Ph, (R)-CHMePh
Me, Me
p-C6H4NO2
p-C6H4NO2
(CH2CH2)2O
2a
2b
Ph
n-Bu
Ph, H
n-Bu, H
Fig. 1. Structure of the cation of [Ni{SC(NMe2)NPh}(dppe)]BPh4 1a showing the
atom numbering scheme. Thermal displacement ellipsoids are depicted at 50%
probability and hydrogen atoms are omitted for clarity.
Scheme 1. The range of new nickel(II)–phosphine–thiourea complexes reported in
this work.
which gave an orange solution from which [Ni{SC(N(CH2-
CH2)2O)NPh}(dppe)]BPh4 1e was isolated by addition of excess
NaBPh4.
3.09]. The thiourea ligand binds strongly as a bidentate ligand in
these complexes and addition of an additional donor ligand does
not effect conversion to a monodentate thiourea ligand. Thus, an
NMR experiment investigating the reaction between complex 1e
and 1 molar equivalent of PPh3 in CDCl3 showed peaks attributable
only to the starting materials.
Ph
The IR spectra of the complexes (where recorded) show a strong
absorption in the range 1503–1562 cmÀ1 due to the C@N group.
Additionally, the nitrophenyl derivative 1i shows a strong absorp-
N
S
O
N
C
Ni
C
N
O
tion for the NO2 group in the expected region at 1329(s) cmÀ1
.
S
N
In order to characterise the mode of binding of the thiourea li-
gand to nickel, an X-ray structure determination on [Ni{SC(N-
Me2)NPh}(dppe)]BPh4 1a was carried out. The structure of the
cation is shown in Fig. 1, together with the atom numbering
scheme, whilst Table 1 gives selected bond lengths and angles.
The Ni has adopted a four-coordinate, distorted square-planar
geometry and is coordinated by two phosphorus atoms of the dppe
ligand and the nitrogen and sulfur of the thiourea ligand. The an-
gles about the Ni reflect this distorted environment (see Table 1),
Ph
3
The complexes 1 and 2 are soluble in chlorinated hydrocarbon
solvents, but generally only sparingly soluble in methanol and eth-
anol, and insoluble in water; the exception is the cyclohexyl (Cy)
complex 1b, which is moderately soluble in methanol, accounting
for the lower isolated yield of this complex, even when some water
was added to aid precipitation.
and can be quantified by the s4 parameter of Houser and co-work-
ers [23] which gives a s4 value of 0.184 for 1a; on this scale a reg-
ular square-planar geometry has a s4 parameter of 0.00 whilst a
tetrahedron has 1.00. The Ni–P(1) bond trans to the sulfur of the
thiourea ligand [2.1716(7) Å] is slightly longer than the other Ni–
P distance [2.1523(7) Å, trans to nitrogen], reflecting the higher
trans-influence [24] of the sulfur donor compared to the nitrogen
donor.
The complexes have 31P{1H} NMR spectra consistent with their
structures; for all complexes two doublets (due to 2J(PP) coupling
between the two inequivalent phosphines) were observed, with
chemical shifts indicative of a five-membered dppe-Ni ring [22].
By comparison with analogous triphenylphosphine platinum(II)
thiourea monoanion complexes, where the 195Pt isotope provides
additional information on ligand arrangements, the more down-
field resonance is assigned as the PPh2 group trans to the sulfur do-
nor [16]. The 1H NMR spectra show the expected features; it is
noteworthy that there is an upfield shift for the ligand protons
on coordination, as exemplified by complex 1e. Here, the morpho-
line protons shift (with the greatest shift for the CH2N protons)
from the ligand PhNHC(S)N(CH2CH2)2O [CH2O d 3.80 (m) and
CH2N d 3.72 (m)] to the complex 1e [CH2O d 3.40 and CH2N d
Although there appear to be few relevant structures in the liter-
ature to provide suitable comparisons with 1a, the bis(thiourea
monoanion) complex [Ni{SC(N(CH2CH2)2O)NPh}2]
3 has been
structurally characterised. [12] In this complex the Ni–S bond dis-
tance [2.211(2) Å] is slightly longer than in 1a [2.2079(7) Å], pre-
sumably as a result of two mutually trans, high trans-influence
sulfur donors. However the Ni–N bond distance of 1a
[1.936(2) Å] is considerably longer than that in 3 [1.888(7) Å], be-

H.Y. Yuen et al. / Inorganica Chimica Acta 368 (2011) 1–5
3
Table 1
Selected bond lengths (Å) and angles (°) for [Ni{SC(NMe2)NPh}(dppe)]BPh4 1a.
Ni(1)–N(1)
Ni(1)–S(1)
N(1)–C(1)
N(2)–C(3)
P(1)–C(18)
P(2)–C(24)
N(1)–Ni(1)–P(2)
P(2)–Ni(1)–P(1)
P(2)–Ni(1)–S(1)
C(1)–S(1)–Ni(1)
C(1)–N(1)–Ni(1)
C(1)–N(2)–C(3)
C(3)–N(2)–C(2)
N(1)–C(1)–S(1)
N(1)–C(1)–Ni(1)
1.936(2)
2.2079(7)
1.327(3)
1.462(4)
1.813(3)
1.811(3)
168.69(6)
86.38(3)
95.66(3)
77.38(8)
98.43(16)
120.9(2)
115.6(2)
109.05(18)
49.92(12)
Ni(1)–P(2)
2.1523(7)
2.502(2)
1.428(3)
1.472(4)
1.814(2)
1.819(2)
104.47(6)
74.67(6)
165.37(3)
123.8(2)
131.86(16)
123.1(2)
128.8(2)
122.1(2)
176.15(18)
Ni(1)–P(1)
S(1)–C(1)
N(2)–C(1)
C(10)–C(11)
P(1)–C(10)
P(2)–C(11)
2.1716(7)
1.755(3)
1.332(3)
1.531(3)
1.835(2)
1.834(2)
Ni(1)ÁÁÁC(1)
N(1)–C(4)
N(2)–C(2)
P(1)–C(12)
P(2)–C(30)
N(1)–Ni(1)–P(1)
N(1)–Ni(1)–S(1)
P(1)–Ni(1)–S(1)
C(1)–N(1)–C(4)
C(4)–N(1)–Ni(1)
C(1)–N(2)–C(2)
N(1)–C(1)–N(2)
N(2)–C(1)–S(1)
N(2)–C(1)–Ni(1)
cause of lengthening by the high trans-influence phosphine ligand,
compared to the mutually trans N donors in 3. The sulfur in 1a is
also in a slightly constrained geometry with an Ni–S–C angle of
77.39(8)° [compared to a corresponding angle of 76.49° in 3],
whilst the ligand has a bite angle N(1)–Ni(1)–S(1) of 74.67(6)°,
identical to that in 3. There is a long transannular contact of
2.503(2) Å from Ni to C(1); this is within Van der Waals contact,
but is unlikely to be a bonding interaction.
The C-S bond distance of 1a, 1.755(3) Å, is shorter than that ex-
pected for a C–S single bond (e.g. of a thioether, around 1.82 Å [25])
but longer than a C@S double bond (around 1.71 Å in Me2NC(S)NH2
[26]). Comparison of the C–S and C–N bond distances in the cores
of the thiourea ligands of 1a and 3 reveals that in 1a the C–S bond
is longer than in 3 [1.7357(3) Å] and the exocyclic C–N bond is con-
siderably shorter than in 3 [1.332(3) vs. 1.3397(2) Å]. These indi-
cate that in 1a the ligand has more C–S single bond character. Of
the five N–C bonds in 1a, C(1)–N(1) [1.327(3) Å] and C(1)–N(2)
[1.332(3) Å] are the shortest, and their similarity reflects delocali-
sation within the ligand, whose bonding is best represented by the
structure in Scheme 1. C(4)–N(1), to the sp2 hybridised carbon of
the phenyl ring is the next longest at 1.428(3) Å, with C(3)–N(2)
[1.462(4)] and C(2)–N(2) [1.472(4)] being the longest (single)
bonds to the two methyl groups, as expected.
The four-membered Ni(1)–S(1)–C(1)–N(1) is planar, but the
NMe2 group [defined by C(3), N(2) and C(2)] of the thiourea ligand
is twisted by 14.91° from the plane of the four-membered ring
[producing a C(2)–N(2)–C(1)–N(1) torsion angle of 17.07°]. The
same distortion is observed in 3, with an angle of 14.84° between
the corresponding planes. As a result of slight pyramidalisation of
the ring nitrogen N(1) in 1a [the sum of the bond angles around
N(1) is 354.09°, compared to 360° for a planar nitrogen] the at-
tached carbon C(4) of the phenyl ring is bent out of the plane of
the four-membered ring. The phenyl ring is also inclined at an an-
gle of 72.19° to the least squares plane of the four-membered ring.
These distortions presumably minimise steric interactions be-
tween the phenyl ring and the NMe2 group.
scribed previously [16]. The thioureas precipitated in high yields,
and were isolated by filtration, washed with diethyl ether and used
without further purification.
ESI mass spectra were recorded on a Bruker MicrOTOF instru-
ment, which was calibrated using a solution of sodium formate.
Samples of isolated products were prepared for analysis by disso-
lution in a few drops of dichloromethane followed by dilution with
methanol and centrifugation. Assignment of ions was assisted by
comparison of experimental and theoretical isotope patterns, the
latter calculated using an internet-based programme [27]. NMR
spectra were recorded in CDCl3 solution (unless otherwise stated)
on a Bruker AC300P instrument. Elemental analyses were carried
out by the Campbell Microanalytical Laboratory, University of
Otago, Dunedin, New Zealand. IR spectra were recorded as KBr
disks on a Perkin–Elmer Spectrum 100 FT-IR spectrometer.
3.1. Synthesis of [Ni{SC(NR2R3)NR1}(dppe)]BPh4 from tri-substituted
thioureas – general method
A mixture of Ni(OAc)2Á4H2O (100 mg, 0.402 mmol) and dppe
(160 mg, 0.402 mmol) in methanol (30 mL) was stirred and gently
warmed for 5 min, to give a yellow solution. The thiourea (1 mol
equivalent) was added, producing an orange solution. Aqueous tri-
methylamine (1 mL) was then added, and the mixture briefly
warmed to around 60 °C. The resulting orange to red-orange solu-
tion was then gravity filtered to remove a small quantity of insol-
uble material. Solid NaBPh4 (250 mg, 0.731 mmol) was added to
the rewarmed filtrate, producing a precipitate of the product,
which was allowed to cool to room temperature. In some cases,
some water was added at this point to assist precipitation. The
product was filtered, washed, and dried under vacuum.
Using the general method, the following complexes were
prepared:
3.1.1. [Ni{SC(NMe2)NPh}(dppe)]BPh4 1a
PhNHC(S)NMe2 (73 mg) gave an orange solid that was washed
with cold methanol (5 mL) to give 248 mg (65%) of product. Anal.
Calc. for C59H55BN2NiP2S: C, 74.13; H, 5.80; N, 2.93. Found: C,
73.98; H, 5.92; N, 2.86%. ESI MS m/z 635.130 (calcd. 635.134),
[1aÀBPh4]+. 1H NMR, d 7.59–6.30 (m, Ph), 2.60 (s, CH3), 1.88–1.51
(m, CH2, dppe). 31P{1H} NMR, d 62.0 [d, 2J(PP) 48, P trans S], 57.3
3. Experimental
Nickel(II) acetate tetrahydrate (BDH), sodium tetraphenylborate
(BDH) and aqueous trimethylamine (BDH, 25–30% w/v), 1,3-di-n-
butylthiourea, 1,3-diphenylthiourea (thiocarbanilide, BDH) and
1,2-bis(diphenylphosphino)ethane (dppe, Aldrich) were used as
[d, 2J(PP) 48, P trans N]. IR mmax 1562(s) cmÀ1
.
supplied.
The
thioureas
PhNHC(S)NMe2,
PhNHC(S)NCy2,
3.1.2. [Ni{SC(NCy2)NPh}(dppe)]BPh4 1b
PhNHC(S)N(CH2)4, PhNHC(S)N(CH2)5, PhNHC(S)N(CH2Ph)((R)-
CHMePh), PhNHC(S)N(CH2CH2)2O, PhNHC(S)N(CH2CH2)2S, p-
O2NC6H4NHC(S)NMe2 and p-O2NC6H4NHC(S)N(CH2CH2)2O were
prepared by the standard method, by addition of the appropriate
amine to PhNCS or p-NO2C6H4NCS (Aldrich) in diethyl ether, as de-
PhNHC(S)NCy2 (129 mg), with addition of water (5 mL) to the
cooled reaction mixture, gave a red-orange solid that was washed
with methanol–water (1:1, 10 mL) to give 198 mg (45%) of prod-
uct. Anal. Calc. for C61H71BN2NiP2S: C, 75.88; H, 6.56; N, 2.57.
Found: C, 75.83; H, 6.61; N, 2.52%. ESI MS m/z 771.309 (calcd.

4
H.Y. Yuen et al. / Inorganica Chimica Acta 368 (2011) 1–5
771.260), [1bÀBPh4]+. 31P{1H} NMR, d 60.7 [d, 2J(PP) 44, P trans S]
3.2. Alternative synthesis of complex 1e
and 55.0 [d, 2J(PP) 44, P trans N]. IR mmax 1503(s) cmÀ1
.
The dark green complex [Ni{SC(N(CH2CH2)2O)NPh}2] 3 (pre-
pared by a minor modification of the literature procedure [12])
(400 mg, 0.799 mmol) and dppe (319 mg, 0.801 mmol) were stir-
red in methanol (25 mL) resulting in the rapid formation of a
red-orange solution, with a small quantity of insoluble white mate-
rial. After stirring for 1 h the solution was filtered, and NaBPh4
(250 mg, 0.731 mmol) added to the filtrate, giving an orange pre-
cipitate. The product was filtered, washed with cold methanol
(5 mL) and dried to give 409 mg (51%) of 1e, which had an identical
31P{1H} NMR spectrum to the material prepared in a one-pot reac-
tion from Ni(OAc)2Á4H2O.
3.1.3. [Ni{SC(N(CH2)4)NPh}(dppe)]BPh4 1c
PhNHC(S)N(CH2)4 (84 mg) gave an orange solid that was
washed with cold methanol (5 mL) to give 246 mg (62%) of prod-
uct. Anal. Calc. for C61H57BN2NiP2S: C, 74.61; H, 5.86; N, 2.85.
Found: C, 74.65; H, 6.03; N, 2.82%. ESI MS m/z 661.162 (calcd.
661.150), [1cÀBPh4]+. 1H NMR, d 7.70–6.33 (m, Ph), 3.50 (s, br,
CH2), 2.45 (s, br, CH2), 1.87–1.53 (m, CH2, dppe). 31P{1H} NMR, d
61.9 [d, 2J(PP) 48, P trans S] and 58.1 [d, 2J(PP) 48, P trans N]. IR mmax
1538(s) cmÀ1
.
3.1.4. [Ni{SC(N(CH2)5)NPh}(dppe)]BPh4 1d
PhNHC(S)N(CH2)5 (90 mg), with addition of water (2 mL) to the
cooled reaction mixture, gave an orange solid that was washed
with cold methanol (5 mL) to give 256 mg (64%) of product. Anal.
Calc. for C62H59BN2NiP2S: C, 74.77; H, 5.98; N, 2.81. Found: C,
74.92; H, 6.08; N, 2.75%. ESI MS m/z 675.161 (calcd. 675.166),
[1dÀBPh4]+. 31P{1H} NMR, d 61.8 [d, 2J(PP) 47, P trans S] and 56.8
3.3. Synthesis of [Ni{SC(NHR2)NR1}(dppe)]BPh4 from disubstituted
thioureas R1NHC(S)NHR2
The following complexes were synthesised using an analogous
procedure for the synthesis of the tri-substituted thiourea
complexes:
[d, 2J(PP) 47, P trans N]. IR mmax 1548(s) cmÀ1
.
3.1.5. [Ni{SC(N(CH2CH2)2O)NPh}(dppe)]BPh4 1e
3.3.1. [Ni{SC(NHPh)NPh}(dppe)]BPh4 2a
PhNHC(S)N(CH2CH2)2O (89 mg) gave a light orange solid that
was washed with cold methanol (5 mL) to give 234 mg (58%) of
product. Anal. Calc. for C61H57BN2NiOP2S: C, 73.42; H, 5.76; N,
2.81. Found: C, 73.20; H, 5.72; N, 2.74%. ESI MS m/z 677.149 (calcd.
677.145), [1eÀBPh4]+. 1H NMR, d 7.65–6.32 (m, Ph), 3.40 (s, CH2O),
3.09 (s, CH2N) 1.83–1.56 (m, CH2, dppe). 31P{1H} NMR, d 62.3 [d,
2J(PP) 48, P trans S], 57.6 [d, 2J(PP) 49, P trans N]. IR mmax 1550(s)
PhNHC(S)NHPh (93 mg) gave an orange microcrystalline solid
that was washed with cold methanol (5 mL) to give 181 mg
(45%) of product. Anal. Calc. for C63H55BN2NiP2S: C, 75.37; H,
5.53; N, 2.79. Found: C, 75.33; H, 5.51; N, 2.69%. ESI MS m/z
683.143 (calcd. 683.134), [2aÀBPh4]+. 1H NMR, d 7.67–6.42 (m,
Ph), 1.87–1.50 (m, CH2, dppe). 31P{1H} NMR, d 62.2 [d, 2J(PP) 50,
P trans S], 59.7 [d, 2J(PP) 50, P trans N]. IR mmax 1552(s) cmÀ1
.
cmÀ1
.
3.1.6. [Ni{SC(N(CH2CH2)2S)NPh}(dppe)]BPh4 1f
3.3.2. [Ni{SC(NHBu)NBu}(dppe)]BPh4 2b
PhNHC(S)N(CH2CH2)2S (98 mg) gave a yellow-orange solid that
was washed with cold methanol (5 mL) to give 295 mg (72%) of
product. Anal. Calc. for C61H57BN2NiP2S2: C, 72.26; H, 5.67; N,
2.76. Found: C, 72.08; H, 5.75; N, 2.71%. ESI MS m/z 693.136 (calcd.
693.122), [1fÀBPh4]+. 1H NMR, d 7.60–6.32 (m, Ph), 3.37 (s, CH2S),
3.50 (s, CH2N), 1.79–1.53 (m, CH2, dppe). 31P{1H} NMR, d 62.1 [d,
2J(PP) 48, P trans S] and 54.3 [d, 2J(PP) 48, P trans N]. IR mmax
BuNHC(S)NHBu (78 mg) gave an orange microcrystalline pre-
cipitate that was washed with cold methanol (5 mL) and dried to
give 245 mg (63%) of product. Anal. Calc. for C59H63BN2NiP2S: C,
73.51; H, 6.59; N, 2.91. Found: C, 73.55; H, 6.66; N, 2.83%. ESI MS
m/z 643.190 (calcd. 643.197). 31P{1H} NMR, d 61.2 [d, 2J(PP) 49, P
trans S], 58.2 [d, 2J(PP) 49, P trans N].
1547(s) cmÀ1
.
3.4. X-ray structure determination of [Ni{SC(NMe2)NPh}(dppe)]BPh4
3.1.7. [Ni{SC(N(CH2Ph)((R)-CHMePh)NPh}(dppe)]BPh4 1g
1a
PhNHC(S)N(CH2Ph)((R)–CHMePh) (141 mg) gave an orange so-
lid that was washed with cold methanol (5 mL) and then metha-
nol–water (1:1, 5 mL) to give 269 mg (60%) of product. Anal. Calc.
for C72H65BN2NiP2S: C, 77.07; H, 5.84; N, 2.50. Found: C, 77.22;
H, 5.88; N, 2.47%. ESI MS m/z 801.212 (calcd. 801.213). 31P{1H}
NMR, d 62.3 [d, 2J(PP) 47, P trans S] and 57.4 [d, 2J(PP) 47, P trans N].
The complex crystallises as red block-like crystals by vapour
diffusion of diethyl ether into a dichloromethane solution at room
temperature.
An arbitrary sphere of data was collected on a crystal having
approximate dimensions of 0.36 Â 0.25 Â 0.11 mm, on a Bruker
APEX-II diffractometer using a combination of
x- and u-scans of
3.1.8. [Ni{SC(NMe2)NC6H4NO2}(dppe)]BPh4 1h
0.3° [28]. Data were corrected for absorption and polarisation ef-
fects and analysed for space group determination. The structure
was solved by direct methods and expanded routinely [29]. The
model was refined by full-matrix least-squares analysis of F2
against all reflections. All non-hydrogen atoms were refined with
anisotropic thermal displacement parameters. Unless otherwise
noted, hydrogen atoms were included in calculated positions.
Thermal parameters for the hydrogens were tied to the isotropic
thermal parameter of the atom to which they are bonded (1.5Â
for methyl, 1.2Â for all others).
p-NO2C6H4NHC(S)NMe2 (92 mg) gave a light orange solid that
was washed with cold methanol (5 mL) to give 215 mg (53%) of
product. Anal. Calc. for C59H54BN3NiO2P2S: C, 70.80; H, 5.44; N,
4.20. Found: C, 70.93; H, 5.48; N, 4.18%. ESI MS m/z 680.117 (calcd.
680.119). 31P{1H} NMR, d 63.1 [d, 2J(PP) 48, P trans S] and 57.1 [d,
2J(PP) 48, P trans N].
3.1.9. [Ni{SC(N(CH2CH2)2O)NC6H4NO2}(dppe)]BPh4 1i
p-NO2C6H4NHC(S)N(CH2CH2)2O (108 mg) gave an orange solid
that was washed with cold methanol (5 mL) to give 249 mg
(59%) of product. Anal. Calc. for C61H56BN3NiO3P2S: C, 70.25; H,
5.42; N, 4.03. Found: C, 70.06; H, 5.44; N, 4.02%. ESI MS m/z
722.150 (calcd. 722.130), [1iÀBPh4]+. 31P{1H} NMR (d6-DMSO), d
68.4 [d, 2J(PP) 40, P trans S], 62.2 [d, 2J(PP) 40, P trans N]. IR mmax
There are two molecules of the Ni cation and associated BPh4
anion and one molecule of diethyl ether of crystallisation in the
ꢀ
unit cell of the primitive triclinic space group P1. The diethyl ether
of crystallisation is located on the inversion centre at [0.5, 1, 0]. It is
disordered over two sites with the methylene carbon split between
two positions.
1533(s) and 1329(s) cmÀ1
.

H.Y. Yuen et al. / Inorganica Chimica Acta 368 (2011) 1–5
5
[3] W. Henderson, B.K. Nicholson, M.B. Dinger, R.L. Bennett, Inorg. Chim. Acta 338
(2002) 210.
[4] P. Piraino, G. Bruno, G. Tresoldi, G. Faraone, G. Bombieri, J. Chem. Soc., Dalton
Trans. (1983) 2391.
3.5. Crystal data for C61H60BN2NiO0.50P2S
Mr = 992.63; triclinic; space group P1; a = 13.4272(3) Å;
ꢀ
[5] W.P. Bosman, A.W. Gal, Cryst. Struct. Commun. 5 (1976) 703.
[6] L.A. Hoferkamp, G. Rheinwald, H. Stockli-Evans, G. Süss-Fink, Organometallics
15 (1996) 704.
[7] S.D. Robinson, A. Sahajpal, J.W. Steed, Inorg. Chim. Acta 306 (2000) 205.
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30 (1991) 4638.
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(1996) 4227.
[10] M. Lipowska, L. Hansen, A. Taylor Jr., L.G. Marzilli, Inorg. Chem. 35 (1996) 4484.
[11] W. Henderson, B.K. Nicholson, E.R.T. Tiekink, Inorg. Chim. Acta 359 (2006) 204.
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Bas 99 (1980) 314.
b = 14.3573(4) Å;
b = 83.9350(10)°;
T = 100(2) K; k(Mo
c = 15.1669(4) Å;
a
= 65.0730(10)°;
c
= 72.0430(10)°; V = 2521.32(11) Å3; Z = 2;
Ka
) = 0.71073 Å;
l
(Mo
K
a
) = 0.533 mmÀ1
;
Dcalc = 1.307 g cmÀ3; 37922 reflections collected; 10321 unique
(Rint = 0.0342); giving R1 = 0.0447, wR2 = 0.1081 for 8592 data with
[I > 2r(I)] and R1 = 0.0571, wR2 = 0.1151 for all 10321 data. Resid-
ual electron density (e ÅÀ3) max/min: 0.987/À1.061.
Acknowledgements
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We thank the Universities of Waikato and Notre Dame for
financial support of this work. WH thanks Ching Chan and Julia
Lin for recording the NMR spectra, and Ryland Fortney-Zirker for
recording mass spectra.
Appendix A. Supplementary material
CCDC 783826 contains the supplementary crystallographic 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. Supplementary data associated with this article
can be found, in the online version, at doi:10.1016/
j.ica.2010.12.011.
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