Diverse coordination behaviour of phosphorus(V)-functionalised 6-chloroaminobenzothiazole anions at various metal centres

Article abstract of DOI:10.1002/ejic.201100960

Aminobenzothiazole-functionalised phosphane 1 and its corresponding phosphorus(V) analogues 2-4 were synthesised in high yields. New 1D polymeric salts K[ClC₆H₃NC(S)NP(E)Ph₂]_∞ (E = O 5; E = S 6) were shown, by u

Full text of DOI:10.1002/ejic.201100960

FULL PAPER
DOI: 10.1002/ejic.201100960
Diverse Coordination Behaviour of Phosphorus(V)-Functionalised
6-Chloroaminobenzothiazole Anions at Various Metal Centres
Simon J. Coles,[a] Sophie H. Dale,[b] Mark R. J. Elsegood,[b] Kirsty G. Gaw,[b]
Thomas Gelbrich,[a] Michael B. Hursthouse,[a] Mark E. Light,[a] Thomas A. Noble,[b] and
Martin B. Smith*[b]
Keywords: Benzothiazole / Chalcogenides / Phosphanes / Potassium / Structure elucidation
Aminobenzothiazole-functionalised phosphane 1 and its cor-
responding phosphorus(V) analogues 2–4 were synthesised
in high yields. New 1D polymeric salts K[ClC6H3NC(S)NP-
(E)Ph2]ϱ (E = O 5; E = S 6) were shown, by using single-
crystal X-ray diffraction, to exhibit unique potassium metal
ion coordination through either κ3-N2O tridentate (E = O) or
κ2-N2 bridging (E = S) modes. In contrast, κ2-NE chelation (E
= S, Se) was observed upon complexation to a range of metal
fragments including {Ir(η5-Cp*)Cl} (E = S 8; E = Se 9), {Rh(η5-
Cp*)Cl} (E = S 10; E = Se 11), {Ru(η6-p-MeC6H4iPr)Cl} (E =
S 12), {Ru(η6-C6Me6)Cl} (E = S 13) and {Pt(PMe2Ph)Cl} (E =
S 14). All new compounds were characterised by a combina-
tion of multinuclear NMR, FTIR and microanalysis. Seven
compounds were structurally characterised by using single-
crystal X-ray crystallography.
Introduction
Chelating anionic ligands, such as the ubiquitous acac
anion (acac = acetylacetonato), have attracted considerable
interest over the years for their importance in many diverse
aspects of coordination chemistry. Aside from acac, many
other bidentate anionic ligands bearing group 15 or 16 do-
nor atoms have been widely documented. Scheme 1 illus-
trates a selection of popular recent examples including: amid-
inate (I),[1] guanidinate (II),[2] β-diketiminate (nacnac–)
(III),[3] bis(phosphinimino)methanide (IV)[4] and imidodi-
phosphinate (V)[5] ligands (R and RЈ denote various alkyl/
silyl/aryl groups; E = O, S, Se, Te). In these examples, the
principal bonding motifs observed are either κ2-NN- or κ2-
EE-chelation. Considerable recent interest in sulfur and se-
lenium analogues of V strides from observations that these
complexes are suitable single-source precursors for binary
metal sulfide[5c] or selenide[5d] thin semiconducting films.
As part of continuing studies in our group investigating
neutral and singly/doubly deprotonated functionalised terti-
ary phosphanes,[6] we report here the facile synthesis and
structural characterisation of two unusual potassium salts
of an anionic, benzothiazole-modified amino(phosphane)
oxide and sulfide.[7] We show, depending on the group 16
Scheme 1.
donor atom (O or S), two distinct coordination modes uti-
lising a combination of both nitrogen and/or O donor
centres. Furthermore, classical κ2-NE-chelation (E = S, Se)
was achieved upon facile complexation to a range of late
transition metal fragments including {M(η5-Cp*)Cl} (M =
Ir, Rh; Cp* = pentamethylcyclopentadienyl), {Ru(η6-p-Me-
C6H4iPr)Cl}, {Ru(η6-C6Me6)Cl} and {Pt(PMe2Ph)Cl}. All
new compounds reported here were characterised by a com-
bination of spectroscopic and crystallographic techniques.
Results and Discussion
Reaction of commercially available 6-chloroaminobenzo-
thiazole with Ph2PCl and NEt3, in diethyl ether, gave, after
work-up, amino(phosphane) 1 in excellent (95%) yield.[8]
Under standard conditions,[7b] oxidation with either aque-
ous H2O2 (30% w/w), elemental S8 or grey Se afforded the
corresponding phosphorus(V) compounds 2–4 in approxi-
mately 90% yield. The molecular structure of phosphane
oxide 2 was determined (Figure 1) and shows a tautomeric
[a] EPSRC National Crystallography Service, School of Chemistry,
University of Southampton,
Highfield, Southampton SO17 1BJ, U.K.
[b] Department of Chemistry, Loughborough University,
Loughborough, Leics LE11 3TU, U.K.
Fax: +44-1509-223925
E-mail: m.b.smith@lboro.ac.uk
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.201100960.
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859

M. B. Smith et al.
FULL PAPER
arrangement with the NH hydrogen on the endocyclic N(2)
atom. The P(1)–N(1) [1.636(2) Å], N(1)–C(1) [1.293(3) Å]
and C(1)–N(2) [1.353(3) Å] bond lengths provide evidence
of delocalisation in the P(1)–N(1)–C(1)–N(2) backbone.[7b]
Intermolecular N–H···O H-bonding links molecules of 2
into a 1D polymeric chain [N(2)···O(1A) 2.696(3) Å; N(2)–
H(2)···O(1A) 153(3)°].
Figure 1. Ellipsoid plot of 2. Thermal ellipsoids are drawn at the
50% probability level. All hydrogen atoms except those on N(2),
N(2A) and N(2B) are omitted for clarity. Selected bond lengths [Å]
and angles [°]: P(1)–O(1) 1.4935(18), P(1)–N(1) 1.636(2), N(1)–C(1)
1.293(3), C(1)–N(2) 1.353(3), C(1)–S(1) 1.790(2); O(1)–P(1)–N(1)
117.09(10), P(1)–N(1)–C(1) 125.01(18), N(1)–C(1)–N(2) 122.6(2),
N(1)–C(1)–S(1) 128.10(19). Symmetry operator: A = x + 1/2, –y +
1/2, –z + 1.
Scheme 2. Synthesis of compounds 1–14.
N(1)–C(1)–N(2) bond angle of 129.9(3)° (with respect to
sulfide 6, vide infra) was observed.[10] These metric param-
Metallation of 2–4 was smoothly achieved, at ambient eters suggest some degree of delocalisation within the O(1)–
temperature, with tBuOK in MeOH to generate potassium P(1)–N(1)–C(1)–N(2) skeletal backbone. The coordination
salts 5–7. Cleavage of the chloride bridge[9] of [MCl(μ- environment around K(1) is completed by a further K(1)–
Cl)(η5-Cp*)]2 (M = Ir, Rh), [RuCl(μ-Cl)(η6-p-MeC6H4- N(1) bond [2.820(2) Å] from an adjacent dimeric unit and
iPr)]2, [RuCl(μ-Cl)(η6-C6Me6)]2 or [PtCl(μ-Cl)(PMe2Ph)]2 additional K···π contacts [K(1)···C(14) 3.447(3) Å; K(1)···
with 2 equiv. of 6 or 7 (preformed or generated directly C(19Ј) 3.274(4) Å; K(1)···C(19) 3.339(3) Å]. Further inter-
from 3 or 4/tBuOK) gave the neutral mononuclear metal molecular contacts are present within the second unique
complexes Ir(η5-Cp*)Cl(6/7) (E = S 8; E = Se 9), Rh(η5- dimeric unit and comprise K···C [3.392(4) Å] and K···S
Cp*)Cl(6/7) (E = S 10; E = Se 11), Ru(η6-p-MeC6H4iPr)- [3.6260(11) Å]. These are significantly shorter than the
Cl(6) (12), Ru(η6-p-C6Me6)Cl(6) (13) and Pt(PMe2Ph)Cl(6) van der Waals radii for K/C (ca. 4.5 Å) and K/S (ca. 4.5 Å)
(14) in good yields (Scheme 2).
atoms.[11]
In contrast to 5, different structural ligating features are
The molecular structures of potassium salts 5 and 6 were
successfully determined by using X-ray crystallography clearly evident for the solvated sulfide analogue 6. Each po-
(Figures 2 and 3). For oxide 5, the asymmetric unit com- tassium is sevenfold coordinated by four nitrogen atoms of
prises two potassium cations, two anionic ligands and half a the deprotonated 6-chloroaminobenzothiazole ligands and
chloroform molecule of crystallisation, the latter disordered three MeOH molecules. Moreover, the unsaturated/terminal
over an inversion centre. The unsaturated nitrogen and oxy- amido N atoms of both anionic ligands bridge between two
gen atoms of the anionic ligand bridge two potassium symmetry-equivalent K metal ions. The resulting dimer is
centres, which leads to a centrosymmetric dimer comprising centrosymmetric and has a K2N4 unit at its centre. Imposed
two K2N2O2 units. In contrast, the second N atom brid- by symmetry, each four-membered K2N2 ring is exactly
ges[7b] to an adjacent potassium ion within a second dinu- planar. The rings exhibit K–N bond lengths of 2.865(2) and
clear unit. The K(1)–N(2ЈA)/K(1)–N(2Ј) bond lengths are 2.920(2) Å, with additional longer K–N distances of
3.057(3)/3.103(3) Å with K(1)–O(1ЈA)/K(1)–O(1Ј) bond 3.138(2) and 3.054(2) Å.[12] The two K2N2 rings form a di-
lengths of 2.623(2)/2.871(2) Å; both are in the normal ex- hedral angle of 58.83(5)°. Within the anionic ligand the
pected range. Within the 6-chloroaminobenzothiazole N(1)–C(7) and N(2)–C(7) bond lengths are 1.322(3) and
anion, the P(1)–O(1), P(1)–N(1), N(1)–C(1), C(1)–N(2), 1.334(3) Å, respectively, indicative of delocalisation within
C(1)–S(1) bond lengths are 1.494(2), 1.621(2), 1.341(4), the N–C–N backbone. The P(1)–N(2), P(1)–S(2) and S(1)–
1.310(4), 1.782(3) Å, respectively, and a more pronounced C(7) distances are 1.627(2), 1.9847(9) and 1.799(2) Å,
860
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Phosphorus(V)-Functionalised 6-Chloroaminobenzothiazole Anions
units, respectively. The coordination polyhedron about po-
tassium is a capped trigonal prism in which the four nitro-
gen substituents are exactly planar. There are also two
intermolecular O–H···S hydrogen bonds, which presumably
assist in stabilisation of the unusual 1D chain [O(1)···S(2)
3.247(2) Å; O(1)–H(1)···S(2) 169(3)° and O(2)···S(2)
3.263(2) Å; O(2)–H(2)···S(2) 154(2)°; see Figure 3 and Sup-
porting Information].
The molecular structures of 8 (Supporting Information),
9 and 11 (Figures 4 and 5) are isostructural (Tables 1 and
2) and each reveals a classic piano-stool arrangement com-
prising an η5-Cp*, a chelating κ2-N/Se-[ClC6H3NC(S)-
NP(E)Ph2]– (E = S, Se) anion and a chloride ligand around
Figure 2. Ellipsoid plot of 5 showing the coordination environment
around each potassium metal centre. Thermal ellipsoids are drawn
at the 30% probability level. All C–H hydrogen atoms and phenyl
groups on phosphorus are omitted for clarity. Selected bond
lengths [Å] and angles [°]: K(1)–N(1) 2.820(2), K(1)–N(2ЈA)
3.057(3), K(1)–N(2Ј) 3.103(3), K(1)–O(1ЈA) 2.623(2), K(1)–O(1Ј)
2.871(2), P(1)–O(1) 1.494(2), P(1)–N(1) 1.621(2), N(1)–C(1)
1.341(4), C(1)–N(2) 1.310(4), C(1)–S(1) 1.782(3); O(1)–P(1)–N(1)
120.34(13), P(1)–N(1)–C(1) 119.6(2), N(1)–C(1)–N(2) 129.9(3).
Symmetry operators: –x + 2, –y, –z + 1; –x + 2, –y, –z + 2; x, y, z
+ 1.
Figure 4. Ellipsoid plot of 9. Thermal ellipsoids are drawn at the
50% probability level. All hydrogen atoms are removed for clarity.
Selected bond lengths [Å] and angles [°]: Ir(1)–Se(1) 2.5102(4),
Ir(1)–N(1) 2.128(3), Ir(1)–Cl(2) 2.4161(9), Ir(1)–Cav 2.166(4),
Se(1)–P(1) 2.1591(10), P(1)–N(2) 1.610(3), N(2)–C(17) 1.324(4),
N(1)–C(17) 1.335(4); Cl(2)–Ir(1)–N(1) 91.24(8), Cl(2)–Ir(1)–Se(1)
82.14(2), N(1)–Ir(1)–Se(1) 88.93(7), Ir(1)–Se(1)–P(1) 97.57(3),
Se(1)–P(1)–N(2) 117.07(12), P(1)–N(2)–C(17) 125.9(3), N(1)–
C(17)–N(2) 130.9(3), Ir(1)–N(1)–C(17) 122.6(2).
Figure 3. Ellipsoid plot of 6 showing part of the 1D chain and
the coordination environment around K(1). Thermal ellipsoids are
drawn at the 50% probability level. All C–H hydrogen atoms except
those on O(1), O(1A) and O(2) are omitted for clarity. Selected
bond lengths [Å] and angles [°]: K(1)–N(1) 2.920(2), K(1)–N(2)
3.138(2), K(1)–N(1A) 2.865(2), K(1)–N(2A) 3.054(2), K(1)–O(1)
2.829(2), K(1)–O(2) 2.6882(19), K(1)–O(1A) 2.779(2), N(1)–C(7)
1.322(3), N(2)–C(7) 1.334(3), S(1)–C(7) 1.799(2), N(2)–P(1)
1.627(2), P(1)–S(2) 1.9851(9); N(1)–K(1)–N(2) 44.93(5), K(1)–
N(2)–C(7) 81.41(13), N(1)–C(7)–N(2) 122.1(2), C(7)–N(1)–K(1)
90.68(14), P(1)–N(2)–C(7) 123.61(18), K(1)–N(2)–P(1) 125.08(10),
N(2)–P(1)–S(2) 117.84(7). Symmetry operators: –x, –y, –z – 1; –x
+ 1, –y, –z – 1; 1 + x, y, z.
respectively.[10,13] The potassium ion is additionally coordi-
nated by two bridging [K–O 2.779(2) and 2.829(2) Å] and
one nonbridging MeOH [K–O 2.6882(19) Å] solvent mole-
cules.[14] As a result, the dimeric units are connected
through K2O2 rings to give 1D chains that extend parallel
to the crystallographic a axis. The plane of the K2O2 core
forms dihedral angles of 59.70(8) and 68.26(8)° with adja-
cent K2N2 rings. Furthermore, the K···K separations are
Figure 5. Ellipsoid plot of 11. Thermal ellipsoids are drawn at the
50% probability level. All hydrogen atoms are removed for clarity.
Selected bond lengths [Å] and angles [°]: Rh(1)–Se(1) 2.5110(7),
Rh(1)–N(1) 2.132(5), Rh(1)–Cl(1) 2.4217(16), Rh(1)–Cav 2.167(6),
Se(1)–P(1) 2.1584(17), P(1)–N(2) 1.606(5), N(2)–C(17) 1.332(8),
N(1)–C(17) 1.338(7); Cl(1)–Rh(1)–N(1) 93.40(13), Cl(1)–Rh(1)–
Se(1) 83.26(4), N(1)–Rh(1)–Se(1) 89.69(12), Rh(1)–Se(1)–P(1)
97.30(5), Se(1)–P(1)–N(2) 117.9(2), P(1)–N(2)–C(17) 126.1(4),
3.6938(10) and 4.2659(11) Å within the K2N2 and K2O2 N(1)–C(17)–N(2) 129.8(5), Rh(1)–N(1)–C(17) 123.4(4).
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M. B. Smith et al.
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the metal centre. Extensive delocalisation within the M(1)– tially coplanar to within approximately Ϯ0.04 Å and N(2)
E(1)–P(1)–N(2)–C(17)–N(1) (M = Ir, Rh) six-membered and Ir(1) lie in the range 0.244–0.256 and 1.121–1.250 Å,
ring is evident, as indicated by the appropriate differences respectively, to the same side of this plane.
in bond lengths. Hence the P–Se bond lengths [2.1591(10) Å
The molecular structure of 14 (Figure 6) confirms the κ2-
for 9; 2.1584(17) Å for 11] are intermediate between those N/S-bidentate behaviour of the [ClC6H3NC(S)NP(S)Ph2]–
expected for P–Se single and P=Se double bonds, which is anion around the square-planar PtII centre with PMe2Ph/
supportive of regular charge delocalisation across the Cl– present as auxiliary ligands. Of the two possible geomet-
SePCN2 framework.[15] The six-membered metallacyclic ric isomers that could be anticipated, the X-ray structure of
ring in 8, 9 and 11 adopts an asymmetric boat conforma- 14 reveals that the N(1) donor centre is trans to P(2). The
tion in which atoms N(1), C(17), P(1) and E(1) are essen- Pt(1)–P(2), Pt(1)–S(1), Pt(1)–N(1) and Pt(1)–Cl(1) bond
Table 1. Crystallographic data for 2, 5, 6 and 8.
Compound
2
5
6
8
Empirical formula
Formula weight
Crystal system
Space group
a [Å]
b [Å]
c [Å]
C19H14ClN2OPS
384.80
orthorhombic
P212121
10.6308(2)
12.0146(4)
13.7050(4)
2(C38H26Cl2K2N4O2P2S2)·CHCl3 C21H21ClKN2O2PS2 C29H28Cl2IrN2PS2
1810.98
triclinic
P1
503.04
762.72
triclinic
P1
monoclinic
P21/n
¯
¯
13.1740(2)
13.2239(2)
13.6498(2)
107.8897(10)
113.0629(8)
91.7783(8)
2050.76(5)
1
7.7261(2)
12.8359(3)
13.0946(4)
68.9510(10)
80.0470(10)
77.472(2)
1176.66(5)
2
7.9797(16)
16.183(3)
21.534(4)
α [°]
β [°]
γ [°]
90.41(3)
Volume [Å3]
Z
1750.47(8)
4
2780.7(9)
4
T [K]
120(2)
1.460
0.438
block, colourless
0.18ϫ0.10ϫ0.08
3.39–27.54
4013
0.0767
0.0406, 0.0845
150(2)
1.466
0.679
plate, colourless
0.17ϫ0.17ϫ0.10
3.10–25.25
7398
0.0433
0.0491, 0.1372
150(2)
1.420
0.605
block, colourless
0.10ϫ0.07ϫ0.05
2.95–25.25
4250
0.0479
0.0394, 0.0978
150(2)
1.822
5.224
needle, yellow
0.32ϫ0.04ϫ0.04
2.99–27.49
6368
0.0523
0.0303, 0.0650
Density (calcd.) [Mg/m3]
Absorption coeff. [mm–1]
Crystal habit, colour
Crystal size [mm3]
θ Range [°]
Independent reflections
Rint
Final R, Rw[a]
[a] R = Σ||Fo| – |Fc||/Σ|Fo| for “observed” reflections having F2Ͼ 2σ (F2). Rw = [Σw(Fo – Fc ) /Σw(Fo2)2]1/2 for all data.
2
2 2
Table 2. Crystallographic data for 9, 11 and 14.
Compound
9
11
14
Empirical formula
Formula weight
Crystal system
Space group
a [Å]
b [Å]
c [Å]
C29H28Cl2IrN2PSSe
809.62
monoclinic
P21/n
8.00540(10)
16.2441(3)
21.5752(5)
C29H28Cl2N2PRhSSe
720.33
monoclinic
P21/n
7.9701(3)
16.3122(8)
21.5858(13)
C27H24Cl2N2P2PtS2·0.91OEt2·0.09CH2Cl2
843.62
monoclinic
P21/n
9.7390(19)
15.142(3)
23.176(5)
α [°]
β [°]
90.4909(7)
90.811(2)
97.93(3)
γ [°]
Volume [Å3]
Z
2805.55(9)
4
2806.1(2)
4
3385.0(12)
4
T [K]
150(2)
1.917
6.401
block, orange
0.15ϫ0.10ϫ0.08
3.00–26.00
5498
0.0398
0.0263, 0.0554
120(2)
1.705
2.251
plate, orange
0.12ϫ0.08ϫ0.01
2.99–25.33
5083
0.129
0.0530, 0.1067
150(2)
1.655
4.561
block, colourless
0.15ϫ0.15ϫ0.10
2.98–27.46
7582
0.0471
0.0360, 0.0826
Density (calcd.) [Mg/m3]
Absorption coeff. [mm–1]
Crystal habit, colour
Crystal size [mm3]
θ Range [°]
Independent reflections
Rint
Final R, Rw[a]
[a] R = Σ||Fo| – |Fc||/Σ|Fo| for “observed” reflections having F2Ͼ 2σ (F2). Rw = [Σw(Fo – Fc ) /Σw(Fo2)2]1/2 for all data.
2
2 2
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Phosphorus(V)-Functionalised 6-Chloroaminobenzothiazole Anions
lysers) were performed by the Loughborough University Analytical
Services within the Department of Chemistry. The mass spectra for
1, 2, 4 and 12–14 were analysed (JEOL SX102 instrument) by fast
atom bombardment (FAB) in a positive ionisation mode by using
a 3-nitrobenzyl alcohol (NOBA) matrix. Compounds 3, 5, 6, 8 and
9 were analysed (Thermofisher LTQ Orbitrap XL) by nano-electro-
spray (nano-ESI) in a positive ionisation mode with CH2Cl2/
CH3OH as solvent and NH4[OAc].
lengths are broadly as anticipated, and the S(1)–P(1)–N(2)–
C(1)–N(1) distances are similar to those found in 8 (Sup-
porting Information).
Compound 1: To a stirred solution of 6-chloroaminobenzothiazole
(4.181 g, 22.64 mmol) and NEt3 (2.507 g, 24.78 mmol) in diethyl
ether (50 mL) at 0 °C was added dropwise a solution of Ph2PCl
(4.948 g, 22.43 mmol) over 30 min. The resulting white suspension
was stirred for 18 h and concentrated to dryness, and degassed dis-
tilled water (50 mL) was added. Solid 1 was collected by suction
filtration, washed with distilled water (50 mL), n-hexane (50 mL),
absolute ethanol (2ϫ30 mL) and dried in vacuo. Yield: 7.986 g
1
(95%). 31P{1H} NMR (CDCl3): δ = 42.5 ppm. H NMR: δ = 7.50
(s, arom. H), 7.41–7.29 (m, arom. H), 7.20 (s, arom. H), 7.08 (s,
arom. H) ppm. FTIR: ν = 3113 (NH), 1594 (CN), 924 (PN) cm–1.
˜
Figure 6. Ellipsoid plot of 14. Thermal ellipsoids are drawn at the
50% probability level. All hydrogen atoms are removed for clarity.
Selected bond lengths [Å] and angles [°]: Pt(1)–S(1) 2.3177(11),
Pt(1)–N(1) 2.107(3), Pt(1)–Cl(1) 2.3076(11), Pt(1)–P(2) 2.2336(11),
S(1)–P(1) 2.0251(17), P(1)–N(2) 1.599(4), N(2)–C(1) 1.335(5),
C(1)–N(1) 1.338(5); Cl(1)–Pt(1)–N(1) 90.07(9), Cl(1)–Pt(1)–S(1)
177.78(4), N(1)–Pt(1)–S(1) 89.82(9), Pt(1)–S(1)–P(1) 89.84(5), S(1)–
P(1)–N(2) 116.94(15), P(1)–N(2)–C(1) 125.3(3), N(2)–C(1)–N(1)
129.1(4), Pt(1)–N(1)–C(1) 121.6(3).
FAB-MS: m/z = 369 [M]+. C19H14ClN2PS (368.8): calcd. C 61.88,
H 3.83, N 7.60; found C 61.52, H 3.80, N 7.54.
Compound 2: To a stirred solution of 1 (0.192 g, 0.517 mmol) in thf
(10 mL) was added aqueous H2O2 (30% w/w, 0.1 mL, 0.88 mmol).
The solution was stirred for approximately 1 h, the volume was
reduced to approximately 5 mL, and diethyl ether (30 mL) was
added. The solid was collected by suction filtration, washed with
diethyl ether (5 mL) and dried in vacuo. Yield: 0.193 g (97%).
31P{1H} NMR (CDCl3): δ = 26.5 ppm. 1H NMR: δ = 7.82–7.77
(m, arom. H), 7.47–7.30 (arom. H), 7.14 (dd, J = 8.6, J = 2 Hz,
arom. H), 7.04 (d, J = 8.6 Hz, arom. H) ppm. FTIR: ν = 3076
˜
Conclusions
(NH), 1631 (CN), 1163 (PO), 957 (PN) cm–1. FAB-MS: m/z = 385
[M]+. C19H14ClN2OPS (384.8): calcd. C 59.30, H 3.67, N 7.28;
found C 59.25, H 3.63, N 7.12.
We observed three distinct ligating modes for a deriv-
atised benzothiazole anion at a potassium or late transition
metal centre based on IrIII, RhIII, RuII or PtII. Further stud-
ies are underway and will be reported in due course.
Compound 3: The solids 1 (1.000 g, 2.696 mmol) and S8 (0.086 g,
2.682 mmol) were stirred in thf (20 mL) for 4 h. The solvent was
concentrated in vacuo to approximately 1–2 mL, and addition of
diethyl ether (30 mL) resulted in a pale yellow solid 3. The product
was collected by suction filtration, washed with diethyl ether
(5 mL) and dried in vacuo. Yield: 1.028 g (95%). 31P{1H} NMR
(CDCl3): δ = 49.5 ppm. 1H NMR: δ = 8.01–7.87 (m, arom. H),
7.41–7.33 (arom. H), 7.17 (dd, J = 8.6, J = 2 Hz, arom. H), 7.01
Experimental Section
Materials: The syntheses of compounds 1–4 were conducted under
a nitrogen atmosphere whilst all other reactions were carried out
under aerobic conditions. Dichloromethane was previously distilled
from CaH2, diethyl ether from sodium/benzophenone, thf and hex-
anes from sodium. The chlorido-bridged dimers [IrCl(μ-Cl)(η5-
(d, J = 8.6 Hz, arom. H) ppm. FTIR: ν = 3181 (NH), 1624 (CN),
˜
948 (PN), 626 (PS) cm–1. FAB-MS: m/z
=
401 [M]+.
C19H14ClN2PS2 (400.9): calcd. C 56.93, H 3.52, N 6.99; found C
56.92, H 3.61, N 6.84.
Cp*)]2,[16]
[RhCl(μ-Cl)(η5-Cp*)]2,[16]
[RuCl(μ-Cl)(η6-p-Me-
and [PtCl(μ-Cl)-
C6H4iPr)]2,[17] [RuCl(μ-Cl)(η6-C6Me6)]2
[18]
Compound 4: The solids 1 (0.165 g, 0.445 mmol) and grey Se
(0.036 g, 0.456 mmol) were stirred in thf (20 mL) for 4 h. Unreacted
Se was removed by filtration through a Celite pad. The solvent was
concentrated in vacuo to approximately 1–2 mL, and addition of
diethyl ether (30 mL) resulted in a colourless solid 4. The product
was collected by suction filtration, washed with diethyl ether
(5 mL) and dried in vacuo. Yield: 0.175 g (88%). 31P{1H} NMR
[19]
(PMe2Ph)]2
were synthesised according to published methods.
All other solvents and chemicals were obtained from commercial
suppliers. With the exception of Ph2PCl, which was distilled under
high vacuum prior to use, all other solvents and chemicals were
used without any further purification.
Instrumentation: Fourier transform infrared (FTIR) spectra were
recorded within pressed KBr pellets by using either a Perkin–Elmer
system 2000 (over the range 4000–400 cm–1) or Spectrum 100S
(over the range 4000–250 cm–1) Fourier-transform spectrometer. 1H
NMR and 31P{1H} NMR spectra were recorded with a JEOL
FX90Q, Bruker AC250 FT, Bruker FX 400 or Bruker DPX-400
FT spectrometer with chemical shifts (δ) reported relative to either
external tetramethylsilane (TMS) or 85% H3PO4. Coupling con-
stants (J) were recorded in Hertz. All NMR spectra were recorded
in CDCl3 unless otherwise stated. Elemental analyses (Perkin–
Elmer 2400 or Exeter Analytical Inc. CE-440 CHN Elemental Ana-
1
[CDCl3/(CD3)2SO]: δ = 43.9 (1JPSe = 726 Hz) ppm. H NMR: δ =
7.92–7.87 (m, arom. H), 7.37–7.35 (arom. H), 7.18 (dd, J = 8.5, J
= 2 Hz, arom. H), 7.02 (d, J = 8.5 Hz, arom. H) ppm. FTIR: ν =
˜
3070 (NH), 1619 (CN), 948 (PN), 586 (PSe) cm–1. FAB-MS: m/z =
449 [M]+. C19H14ClN2PSSe (447.8): calcd. C 50.96, H 3.15, N 6.26;
found C 51.11, H 2.94, N, 6.12.
Potassium Salts 5–7: An illustrative example is given here for the
synthesis of compound 5. To
a suspension of 2 (0.100 g,
0.260 mmol) in MeOH (10 mL) was added tBuOK (0.029 g,
0.258 mmol). The solution was stirred for 18 h and concentrated to
Eur. J. Inorg. Chem. 2012, 859–865
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
863

M. B. Smith et al.
FULL PAPER
1
dryness to afford the moisture-sensitive solid 5. Yield: 0.087 g
(65%). Selected data for 5: 31P{1H} NMR (CD3OD): δ = 23.8 ppm.
(CDCl3): δ = 27.3 ppm. H NMR: δ = 8.29 (d, J = 8.8 Hz, arom.
H), 8.11 (m, arom. H), 7.63 (m, arom. H), 7.44 (m, arom. H), 7.29
(d, J = 2.3 Hz, arom. H), 7.14 (m, arom. H), 1.76 (s, CH3) ppm.
1H NMR (CD OD): δ = 7.91–7.07 (arom. H) ppm. FTIR: ν =
˜
3
1220 (PO), 965 (PN) cm–1. FAB-MS: m/z = 385 [M – K + 2H]+. FTIR: ν = 1486 (CN), 602 (PS) cm–1. FAB-MS: m/z = 698 [M]+.
˜
C19H13ClKN2OPS·0.5CHCl3 (482.6): calcd. C 48.53, H 2.83, N C31H31Cl2N2PRuS2 (698.7): calcd. C 53.29, H 4.48, N 4.01; found
5.81; found C 49.17, H 2.70, N 5.47. The sulfide analogue 6 was
C 53.17, H 4.33, N 3.83. Selected data for 14: 31P{1H} NMR
(CDCl3): δ = –20.3 (1JPPt = 3385 Hz), 27.1 (2JPPt = 138 Hz) ppm.
prepared in 67% yield. Selected data for 6: 31P{1H} NMR
1
(CD3OD): δ = 47.4 ppm. H NMR: δ = 8.05–7.02 (arom. H) ppm. 1H NMR: δ = 7.94 (d, J = 8.8 Hz, arom. H), 7.83 (m, arom. H),
FTIR: ν = 962 (PN), 610 (PS) cm–1. FAB-MS: m/z = 401 [M –
7.49–7.27 (m, arom. H), 7.14 (dd, J = 8.8, J = 2.2 Hz, arom. H),
˜
K(CH3OH)2]+. C19H13ClKN2PS2·2H2O (475.0): calcd. C 48.04, H
3.61, N 5.90; found C 47.49, H 3.50, N 5.48. The selenide analogue
7 was similarly prepared in quantitative yield from 4. Selected data
for 7: 31P{1H} NMR [(CD3)2SO]: δ = 33.3 (1JPSe = 697 Hz) ppm.
1H NMR: δ = 7.95–7.05 (arom. H) ppm. C19H13ClKN2PSSe·4H2O
(557.9): calcd. C 40.90, H 3.80, N 5.02; found C 40.61, H 2.39, N
4.57.
1.49 (br. s, CH ) ppm. FTIR: ν = 1496 (CN), 597 (PS) cm–1. FAB-
˜
3
MS: m/z = 767 [M]+. C27H24Cl2N2P2PtS2 (768.6): calcd. C 42.19,
H 3.15, N 3.65; found C 42.58, H 3.57, N 3.40.
Single-Crystal X-ray Structure Determinations: Slow diffusion of
hexanes into a CDCl3 solution of 2 gave suitable crystals. Vapour
diffusion of Et2O into a CDCl3/MeCN solution of 5 gave suitable
crystals. Slow concentration of a MeOH solution of 6 gave suitable
crystals. X-ray quality crystals of 8, 9 and 11 were obtained upon
slow diffusion of petroleum ether (b.p. 60–80 °C) into a CDCl3
solution. Vapour diffusion of Et2O into a CDCl3 solution of 14
gave suitable crystals. Measurements for 2, 5, 6, 8, 9, 11 and 14
were obtained with a Nonius κ CCD area-detector diffractometer
mounted at the window of a rotating molybdenum anode, and Ω
scans were employed such that 95% of the unique data were re-
corded at least once. Data collection and processing were carried
out with the programs COLLECT[20] and DENZO,[21] and an em-
pirical absorption correction was applied with SORTAV.[22] The
structures were solved by direct methods or Patterson synthe-
sis[23,24] and refined by full-matrix least-squares[24] on F2. Non-
hydrogen atoms were refined anisotropically, and hydrogen atoms
were treated by using a riding model, except for OH in 6, for which
coordinates were freely refined. Disordered CH2Cl2 (9%) in 14 was
isotropically modelled. CCDC-223295 (for 14), -838885 (for 5),
-838886 (for 6), -838887 (for 9), -852752 (for 2), -852753 (for 8)
and -852754 (for 11) contain 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.
Complexes 8–14: An illustrative example is given here for the syn-
thesis of compound 9. To an orange suspension of [IrCl(μ-Cl)(η5-
Cp*)]2 (0.058 g, 0.073 mmol) in thf (10 mL) were added 4 (0.065 g,
0.145 mmol) and tBuOK (0.017 g, 0.151 mmol). The orange solu-
tion was stirred at room temp. for approximately 3 h and concen-
trated to dryness under reduced pressure. The residue was extracted
into CH2Cl2 (10 mL), filtered through a Celite plug and concen-
trated to approximately 1 mL. Addition of diethyl ether (20 mL)
afforded a yellow solid, which was collected by suction filtration
and dried in vacuo. Yield: 0.098 g (80%). Selected data for 9:
31P{1H} NMR (CDCl3): δ = 11.9 (1JPSe = 554 Hz) ppm. 1H NMR:
δ = 8.22 (d, J = 8.8 Hz, arom. H), 8.10 (m, arom. H), 7.66 (m,
arom. H), 7.45 (m, arom. H), 7.29 (d, J = 2.4 Hz, arom. H), 7.23
(m, arom. H), 7.13 (dd, J = 8.8, J = 2.1 Hz, arom. H), 1.30 (Cp*)
ppm. FTIR: ν = 1492 (CN), 577 (PSe) cm–1. FAB-MS: m/z = 775
˜
[M – Cl]+. C29H28Cl2IrN2PSSe (810.4): calcd. C 42.98, H 3.49, N
3.46; found C 42.72, H 3.47, N 3.41. In a similar manner, complex
8 was prepared in 78% yield. Selected data for 8: 31P{1H} NMR
(CDCl3): δ = 23.1 ppm. 1H NMR: δ = 8.13–8.08 (m, arom. H),
7.72 (m, arom. H), 7.46 (m, arom. H), 7.29–7.21 (m, arom. H), 7.12
(dd, J = 8.8, J = 2.4 Hz, arom. H), 1.30 (Cp*) ppm. FTIR: ν =
˜
1493 (CN), 601 (PS) cm–1. FAB-MS: m/z = 726 [M – Cl]+.
C29H28Cl2IrN2PS2 (763.5): calcd. C 45.62, H 3.70, N 3.67; found
C 45.45, H 3.47, N 3.45. Complexes 10–14 were prepared from the
isolated potassium salts 6 or 7 and the appropriate chlorido-
bridged dimer (isolated yields given in parentheses): 10 (77%), 11
(56%), 12 (84%), 13 (75%), 14 (60%). Selected data for 10: 31P{1H}
Supporting Information (see footnote on the first page of this arti-
cle): Additional X-ray figures for 5, 6 and 8.
Acknowledgments
We would like to thank the Engineering and Physical Sciences Re-
search Council (EPSRC) for a studentship (K. G. G.), Infineum
UK Ltd for financial support and Johnson Matthey plc for loan
of precious metal. The EPSRC mass spectrometry service at Swan-
sea is gratefully acknowledged.
1
NMR (CDCl3): δ = 27.8 ppm. H NMR: δ = 8.31 (d, J = 8.8 Hz,
arom. H), 8.12 (m, arom. H), 7.71 (m, arom. H), 7.45 (m, arom.
H), 7.30 (d, J = 2.2 Hz, arom. H), 7.14 (dd, J = 8.8, J = 2.2 Hz,
arom. H), 1.31 (Cp*) ppm. FTIR: ν = 1494 (CN), 601 (PS) cm–1.
˜
C29H28Cl2N2PRhS2 (673.5): calcd. C 51.71, H 4.20, N 4.16; found
C 51.43, H 4.17, N 3.94. Selected data for 11: 31P{1H} NMR
[1] For recent examples of amidinate chemistry, see: a) S. Collins,
Coord. Chem. Rev. 2011, 255, 118–138; b) E. F. Trunkely, A.
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2
1
(CDCl3): δ = 16.7 (1JPSe 564 Hz, JPRh 3.8 Hz) ppm. H NMR: δ
= 8.44 (d, J = 8.9 Hz, arom. H), 8.14 (m, arom. H), 7.65 (m, arom.
H), 7.46 (m, arom. H), 7.32 (d, J = 2.2 Hz, arom. H), 7.16 (dd, J
= 8.9, J = 2.2 Hz, arom. H), 1.32 (Cp*) ppm. FTIR: ν = 1487 (CN),
˜
576 (PSe) cm–1. C29H28Cl2N2PRhSSe (720.26): calcd. C 48.36, H [2] For recent examples of guanidinate chemistry, see: a) C. Jones,
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3.93, N 3.89; found C 48.10, H 3.76, N 3.86. Selected data for 12:
1
31P{1H} NMR (CDCl3): δ = 31.7 ppm. H NMR: δ = 8.34 (d, J =
8.9 Hz, arom. H), 8.28–7.21 (m, arom. H), 7.15 (dd, J = 8.9, J =
2.2 Hz, arom. H), 5.54 (d, J = 5.4 Hz, cym), 5.24 (d, J = 6.1 Hz,
cym), 5.13 (d, J = 5.4 Hz, cym), 4.44 (d, J = 5.8 Hz, cym), 2.77
(sept, CH), 2.10 (s, CH3), 1.50 (Cp*), 1.13 (virtual t, CH3) ppm.
[3] For recent examples of β-diketiminate (nacnac–) chemistry, see:
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˜
C29H27Cl2N2PRuS2 (670.7): calcd. C 51.93, H 4.07, N 4.18; found
C 52.11, H 4.25, N 3.76. Selected data for 13: 31P{1H} NMR
864
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Published Online: January 9, 2012
Eur. J. Inorg. Chem. 2012, 859–865
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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