Reactivity of hemilabile pyridyl- and methyl-substituted pyrimidylselenolates with [MCl2(dppf)] (M?=?Pd, pt; dppf?=?bis(diphenylphisphino)ferrocene)

Article abstract of DOI:10.1016/j.ica.2018.03.034

The bis(diphenylphisphino)ferrocene (dppf) derived palladium analogue of [PdCl₂(dppf)] on reaction with the sodium salt of pyridyl/pyrimidyl selenolate yielded mononuclear cis configured complex [Pd(SeAr)₂(dppf)] (Ar = C₅H

Full text of DOI:10.1016/j.ica.2018.03.034

Accepted Manuscript
Research paper
Reactivity of hemilabile pyridyl- and methyl-substituted pyrimidylselenolates
with [MCl (dppf)] (M = Pd, Pt; dppf = bis(diphenylphisphino)ferrocene)
2
Rohit Singh Chauhan, David B. Cordes, Alexandra M.Z. Slawin, Seema Yadav,
Chandrakanta Dash
PII:
S0020-1693(18)30176-2
https://doi.org/10.1016/j.ica.2018.03.034
ICA 18179
DOI:
Reference:
To appear in:
Inorganica Chimica Acta
Received Date:
Revised Date:
Accepted Date:
31 January 2018
20 March 2018
21 March 2018
Please cite this article as: R.S. Chauhan, D.B. Cordes, A.M.Z. Slawin, S. Yadav, C. Dash, Reactivity of hemilabile
pyridyl- and methyl-substituted pyrimidylselenolates with [MCl (dppf)] (M
=
Pd, Pt; dppf
=
2
bis(diphenylphisphino)ferrocene), Inorganica Chimica Acta (2018), doi: https://doi.org/10.1016/j.ica.2018.03.034
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Reactivity of hemilabile pyridyl- and methyl-substituted pyrimidylselenolates
with [MCl (dppf)] (M = Pd, Pt; dppf = bis(diphenylphisphino)ferrocene)
2
a
b
b
c
Rohit Singh Chauhan* , David B. Cordes , Alexandra M. Z. Slawin , Seema Yadav ,
c
Chandrakanta Dash
a
Department of Chemistry, K. J. Somaiya College of Science and Commerce, Mumbai- 400 078,
Email: rohit.chuhan@somaiya.edu
b
EastCHEM School of Chemistry, University of St Andrews, St Andrews, Fife KY16 9ST
Email: amzs@st-andrews.ac.uk
c
Department of Chemistry, Central University of Rajasthan, Ajmer-305817, Rajasthan,
Email: ckdash@curaj.ac.in
Abstract:
The bis(diphenylphisphino)ferrocene (dppf) derived palladium analogue of [PdCl (dppf)]
2
on reaction with the sodium salt of pyridyl/pyrimidyl selenolate yielded mononuclear cis
configured complex [Pd(SeAr) (dppf)] (Ar = C H N, C H(4,6-Me) N ), as did the platinum
2
5
4
4
2
2
precursor [PtCl (dppf)] with methyl substituted pyrimidyl salt giving [Pt{SeC H(4,6-
2
4
Me) N } (dppf)]. In contrast, the reaction of platinum precursor with the sodium salt of
2
2 2
2
+
pyridylselenolate gave two different complexes [Pt (μ-SeC H N) (dppf) ]
and
2
5
4
2
2
[
Pt(Cl)(SeC H N)(dppf)] depending in the reaction solvent. These complexes were characterized
5
4
1
31
by elemental analysis and NMR ( H, P) spectroscopy. The molecular structure of
[
Pt{SeC H(4,6-Me) N } (dppf)] was established by single crystal X-ray diffraction analysis.
4
2
2 2
Keywords: Selenolate, NMR, X-ray, dppf.
1

1
.
Introduction
The ferrocenylphosphine ligand has been extensively used as an efficient auxiliary ligand
mainly due to its rich coordination chemistry without tormenting the intrinsic property of derived
complex [1-3]. This inherent characteristic makes it an efficient materials and catalyst for the
alkene hydroformylation, alkoxycarbonylation and heck coupling reactions [1, 4]. Even though
ferrocenyl phosphine ligand was reported more than three decades ago but its chemical reactivity
and application were not been unearthed until recently [1, 5-7].
The reaction of [MCl (dppf)] (M = Pd, Pt) with Na S has afforded a binuclear product
2
2
[
M (μ-S) (dppf) ] which transformed to [Pt (μ-S)(μ-SCH Cl)(dppf) ] and terminal thio alkyl
2 2 2 2 2 2
complex [Pt(SCH Cl) (dppf)] in chlorinated solvents [8]. The latter mononuclear product has
2
2
also been reported by an oxidative reaction between [Pt(dppf) ] and bis(chloromethyl)disulfide
2
[
9-11]. The sulfurized dppf on reaction with [PdCl (PhCN) ] yielded a mononuclear complex of
2 2
composition [PdCl (L)] (L = Fe(C H P(S)Ph )(C H PPh )) [4]. However the reaction of other
2
5
4
2
5
4
2
chelating phosphine precursors [M(P∩P) ] (M= Pd, Pt; P∩P = dppe, dppp) with Ar E (Ar =
2
2 2
C H N, C H N ; E = Se, Te) yielded a mononuclear compound [M(EAr) (P∩P)] as well as the
5
4
5
3
2
2
binuclear product [M (μ-TeAr) (P∩P) ] (M = Pd, Pt; P∩P = dppe; Ar = C H N) [12-14] which
2
2
2
5
4
decomposes to high nuclearity complex along with unidentified product in chlorinated solvents
15-17]. The facile transformation of bridging chalcogenolates to terminal one is predominantly
[
due to high nucleophilicity of the complex which makes them highly susceptible towards attack
on chlorinated solvent [8, 16, 18, 19].
In this report, we describe the synthesis and characterization of various ferrocenyl
phosphine based palladium and platinum(II) selenolate complexes derived from pyridyl and
methyl substituted pyrimidyl selenolate ligand and studies their reactivity in chlorinated solvent.
2

2
.
Experimental:
All manipulations were carried out under a nitrogen atmosphere by using
standard Schlenk technique. Solvents used in the reactions were degassed with
nitrogen and distilled using standard procedures. The precursor complex
[
PtCl (PhCN) ] [20] and the ligands (SeC H N) , [21] and {SeC H(4,6-Me) N } [17] were
2 2 5 4 2 4 2 2 2
prepared by literature methods. The metal precursors PdCl , and dppf were procured from Strem
2
1
31
1
chemicals. The H, and P{ H}NMR spectra were recorded on a Bruker Avance-II
spectrometer operating at 500, 202.40 MHz, respectively and referenced for the solvent peak of
1
31
chloroform at δ 7.26 for H and externally to 85% H PO (0.00 ppm) for P NMR. Elemental
3
4
analyses were carried out on a Thermo Fischer Flash EA1112 CHNS analyzer.
Pt{SeC H(4,6-Me) N } (dppf)].0.5C H (1a) were collected at 173K on using a Rigaku
[
4
2
2 2
6
6
FR-XUltrahigh Brilliance Microfocus RA generator/confocal optics and XtaLAB P200
diffractometer, Mo-K radiation (λ = 0.71075 Å). Intensity data were collected using ω steps
α
accumulating area detector images spanning at least a hemisphere of reciprocal space. All data
were corrected for Lorentz polarization effects. A multi-scan absorption correction was applied
by using Crystal Clear [22]. The structures were solved by heavy-atom Patterson methods [23],
2
expanded using Fourier techniques and least-squares refinement [23] was on F using data
converged with unweighted and weighted agreement factors. The non-hydrogen atoms were
refined anisotropically and riding a model was used for hydrogen atoms. Molecular structures
were drawn using ORTEP [24]. Crystallographic and structural determination data are listed in
Table 1.
3

2
2
.1
Synthesis of complexes
.1.1 Preparation of [Pd{2-Se-C H(4,6-Me) N } (dppf)] (1a):
4
2
2 2
3
To a benzene-methanolic solution (10 cm ) of NaSeC H(4,6-Me) N [freshly prepared
4
2
2
3
from 45 mg, 0.12 mmol of (SeC H(4,6-Me) N ) , methanol (5cm ) and NaBH (10 mg, 0.26
4
2
2 2
4
3
mmol)] a solution (10 cm ) of [PdCl (dppf)] (98 mg, 0.12 mmol) was added in the same
2
solvents with stirring, which continued for 4 hours at room temperature. The wine red solution
3
was concentrated to 5 cm under reduced pressure. A reddish brown precipitate was formed
which was washed thoroughly with hexane and diethyl ether. The residue was recrystallized
from dichloromethane and few drops of hexane to afford reddish brown powder. (yield: 54 mg,
4
8%; m.p.:151 °C). Anal. Calcd for C H FeN P PdSe : C, 53.49; H, 4.10; N, 5.42%. Found:
46 42 4 2 2
1
C, 53.88; H, 3.94; N, 5.39%. UV-Vis: 270 nm (br), 405 nm (sh). H NMR (CDCl ) δ : 1.25 (s,
3
6
7
H, Me), 1.74 (s, 6H, Me), 4.31 (br, 4H, C H ), 4.69 (br, 4H, C H ), 6.86 (d, 4.8Hz, 2H, Ph),
5 4 5 4
.49 -7.56 (m, 8H, Ph), 7.60-7.64 (td, 2.6Hz, 4H, Ph), 7.66-7.72 (m, 6H, Ph), 7.80 (d, 4.8Hz, 2H,
31
1
C H(4,6-Me) N ); P{ H}NMR (CDCl ) δ : 28.6 ppm.
4
2
2
3
2
.1.2 Preparation of [Pd(SeC H N) (dppf)] (1b):
5 4 2
Prepared in a similar manner to complex 1a using [PdCl (dppf)] (65 mg, 0.08 mmol) and
2
(
SeC H N) (25 mg, 0.08 mmol) as the ligand precursor and recrystallized from
5 4 2
dichloromethane-hexane to give a brown powder. (yield 67 mg, 92%; m.p.:110 °C). Anal. Calcd.
for C H N P FePdSe : C, 54.21; H, 3.72; N, 2.87%. Found: C, 54.61; H, 3.67; N, 2.47%. UV-
4
4
36
2
2
2
1
Vis (λmax) : 278 nm (sh), 328 nm (br) . H NMR (CDCl ) δ : 4.26 (t, 1.5 Hz, 4H, C H ), 4.70 (t,
3
5
4
1
.8 Hz, 4H, C H ), 6.41 (d, 3.2 Hz, 2H, C H N), 7.34-7.41 (m, 8H, Ph), 7.58-7.64 (m, 4H, Ph),
5 4 5 4
4

7
.68-7.73(m, 10H, o-Ph+ C H N) 7.80 (d, 4.5 Hz, 2H, C H N), 8.2(d, 4.8 Hz, 2H, C H N);
5 4 5 4 5 4
3
1
1
P{ H}NMR (CDCl ) δ : 28.3 ppm.
3
2
.1.3 Preparation of [Pt{2-Se-C H(4,6-Me) N } (dppf)] (2a):
4 2 2 2
Prepared in a similar manner to complex 1a, using [PtCl (dppf)] (99 mg, 0.12 mmol) and
2
Na{2-Se-C H(4,6-Me) N } [freshly prepared from {2-Se-C H(4,6-Me) N } (45 mg, 0.12 mmol)
4
2
2
4
2
2 2
in benzene and NaBH (10 mg, 0.26 mmol) in methanol]and recrystallized from benzene-acetone
4
to afford yellow cryatals in 72% yield (80 mg), m.p.: 176 °C (dec.). Anal. Calcd for
C H FeN P PtSe : C, 49.26; H, 3.77; N, 4.99%. Found: C, 49.68; H, 3.52; N, 4.74%. UV-Vis
46
42
4
2
2
1
(
λmax) : 348 nm (br), 435 nm (sh). H NMR (CDCl ) δ : 1.26 (s, 6H, Me), 1.74 (s, 6H,Me), 4.19
3
(
br, 4H, C H ), 4.38 (br, 4H, C H ), 7.28-7.35 (m, 4H, Ph), 7.38-7.48 (m, 8H, Ph), 7.67 (d,
5
4
5
4
3
1
1
1
4
.5Hz, 2H, C HN ), 7.82-7.87 (m, 8H, Ph) ; P{ H}NMR (CDCl ) δ : 12.6 [ J(Pt-P) = 3183 Hz]
5 2 3
ppm.
2
.1.4 Preparation of [Pt (μ-SeC H N) (dppf) ]Cl (3):
2 5 4 2 2 2
3
To a benzene solution (15 cm ) of [PtCl (dppf)] (110 mg, 0.14 mmol), a methanolic
2
3
solution (8 cm ) of Na(SeC H N) [freshly prepared from (C H N) Se (42 mg, 0.14 mmol) and
5
4
5
4
2
2
NaBH (11 mg, 0.29 mmol)] was added and the mixture was stirred for 4 hours. The solvents
4
were evaporated under vacuum and the residue was extracted with benzene and passed through
celite. The ensuing solution on slow evaporation afforded a yellow powder (Yield 54 mg, 43%)
m.p.: 118°C (dec.). Anal. Calcd. for C H N Cl P Fe Pt Se : C, 55.47; H, 3.82; N, 1.66%.
7
8
64
2
2
4
2
2
2
1
Found: C, 55.78; H, 4.14; N, 1.88%. UV-Vis (λmax) : 435 nm (br), 509 nm (br). H NMR
(
CD OH) δ: 4.32 (br, 4H, C H ), 4.67 (br, 4H, C H ), 6.38 (d, 2.8 Hz, 2H, C H N), 7.32-7.42 (m,
3 5 4 5 4 5 4
8
H, Ph), 7.56-7.66 (m, 4H, Ph+C H N), 7.81-7.88 (m, 8H, Ph+C H N), 8.48 (d, 5.0Hz, 2H,
5 4 5 4
5

31
1
1
C H N); P{ H}NMR (CD OH) δ : 12.3 [ J(Pt-P) = 3169Hz] ppm. On recording the NMR of
5
4
3
1
titled complex 3 in CDCl Solution; H NMR (CDCl ) δ: 4.14 (br, 4H, C H ), 4.32 (br, 4H,
3
3
5
4
C H ), 7.08-7.13 (m, 4H, Ph), 7.33-7.39 (m, 9H, Ph+C H N), 7.66-7.73 (m, 9H, Ph+C H N),
5
4
5
4
5
4
3
1
1
1
1
8
3
.48 (d, 4.1Hz, 1H, C H N); P{ H}NMR (CDCl ) δ : 9.9 [ J(Pt−P) = 3762Hz], 14.9 [ J(Pt−P) =
5
4
3
149Hz] ppm.
2
.1.5 Preparation of [Pt(Cl)(SeC H N)(dppf)] (4):
5 4
3
To a dichlormethane solution (15 cm ) of [PtCl (dppf)] (165 mg, 0.21 mmol ) a
2
3
methanolic solution (8 cm ) of Na(SeC H N) [freshly prepared from (C H N) Se (65 mg, 0.21
5
4
5
4
2
2
mmol) and NaBH (16 mg, 0.42 mmol)] was added and the mixture was stirred for 4 hour. The
4
solvents were reduced in vacuo and the residue was extracted with dichloromethane which on
slow evaporation afforded a yellow powder (Yield 139 mg, 73%) m.p. 161 °C (dec.). Anal.
Calcd. for C H NClP FePtSe: C, 49.73; H, 3.42; N, 1.49%. Found: C, 49.48; H, 3.59; N,
3
9
32
2
1
1
.58%. UV-Vis (λmax) : 277 nm (sh), 307 nm (br). H NMR (CDCl ) δ: 4.21 (br, 4H, C H ), 4.34
3 5 4
(
br, 4H, C H ), 7.11-7.16 (m, 4H, Ph), 7.31-7.36 (m, 9H, Ph+C H N), 7.68-7.73 (m, Ph+C H N),
5 4 5 4 5 4
3
1
1
1
1
8
=
3
.41 (d, 4.4Hz, 4H, C H N); P{ H}NMR (CDCl ) δ : 10.1 [ J(Pt−P) = 3766Hz], 14.6 [ J(Pt−P)
5 4 3
3143Hz] ppm.
.
Results and Discussion:
Treatment of [PdCl (dppf)] with two equivalents of sodium aryl selenolate NaSeAr (Ar =
2
C H N, C H(4,6-Me) N ) prepared by the reductive cleavage of the Se−Se bond of diselenide by
5
4
4
2
2
NaBH in methanol, afforded an orange mononuclear product of composition [Pd(SeAr) (dppf)]
4
2
31
(
Ar = C H(4,6-Me) N : 1a,C H N: 1b, scheme 1). The P NMR of both of the complexes
4 2 2 5 4
showed one resonance at ~28 ppm. It is noteworthy that an oxidative reaction of [Pd(dppe)2]
6

with dipyridyldiselenides resulted the similar mononuclear product [Pd{SeC H (3-R)N} (dppe)]
5
3
2
(R = H, Me) [16]. Similarly, reaction of platinum precursor with the sodium salt of methyl
substituted pyrimidylselenolate in a benzene-methanol mixture gave rise to a yellow powder of
composition [Pt{2-Se-C H(4,6-Me) N } (dppf)] (2a, Scheme 1). The observed coupling constant
4
2
2 2
3
183 Hz is in good agreement with reported value for the mononuclear complexes [17, 25, 26].
The molecular structures of [Pt{2-Se-C H(4,6-Me) N } (dppf)]. 0.5C H (1a) has been
4
2
2 2
6
6
established by X-ray diffraction (Figures 2). Selected interatomic parameters for 1a.0.5C H are
6
6
summarized in Tables 2. The complex 1a, adopts the expected distorted square planner geometry
around the platinum atom, defined by the coordination of two phosphorus and two selenium
atoms. The Pt−Se distances [2.4578(10) and 2.4595(11)Å] fall in the middle of the range of
reported Pt–Se distance for both complexes of the type [Pt(SeR) (dppf)] (Pt–Se range 2.453–
2
2
.477 Å) [27-30] and [Pt(SeAr) (P∩P)] (Pt–Se range 2.418–2.511 Å) [27, 31-34]. The Pt−P
2
distances [2.295(2) and 2.301(2)Å] are slighly longer than other reported Pt–P bonds for
compounds of the type values for [Pt(SeAr) (P∩P)] (2.238–2.274 Å) [31-34]; however, when
2
comparing against Pt(dppf) complexes with any selenolate ligands, [Pt(SeR) (dppf)], the Pt–Se
2
bond distances in 3a fall into the known range (2.279–2.306 Å) [27, 32-34]. The Se−Pt−Se angle
is acute [84.38(3)°] as a result of the bond angle imposed by the wide bite-angle of dppf [P–Pt–P
1
01.83(8)°]. These angles are similar to those found in [Pt(SeC≡C(CH ) Me) (dppf)]·C H (Se–
2 4 2 6 6
Pt–Se 85.08°, P–Pt–P 97.98°) [29].
The reaction of [PtCl (dppf)] with two equivalents of sodium 2-pyridylselenolate in a
2
benzene-methanol mixture yielded
a
binuclear product of composition [Pt (μ-
2
SeC H N) (dppf) ]Cl (3). In contrast, a similar reaction in a dichloromethane-methanol mixture
5
4
2
2
2
3
1
afforded exclusively a product of the type [Pt(Cl)(SeC H N)(dppf)] (4) (scheme 2). The P
5
4
7

1
NMR of complex 4 displayed two resonances at 14.6 and 10.1 ppm with J(Pt−P) values of 3143
and 3766Hz, respectively. These two resonances, with different Pt-P coupling constants arise,
due to the differing chemical environments of each phosphorus; one being trans to the
selenolate, the other trans to the chloride [15, 35]. In an attempt to substitute both the chloride,
the reaction has been performed between [PtCl (dppf)] and [Pb(SeC H N)] which also has
2
5
4
resulted similar composition of complex 4. It is noteworthy that similarly an oxidative addition
reaction of [Pd(PPh ) ] with dipyridyl ditellurides gave an expected oxidative addition product
3
4
[
Pd{2-TeC H (3-R)N} (PPh ) ] (R = H, Me) which on keeping in CDCl solution resulted
5 3 2 3 2 3
derivative [PdCl{2-Te(Cl) C H (3-Me)(PPh )] [16]. Even the reaction of [Pd Cl (μ-Cl )(PPh ) ]
2
5
3
3
2
2
2
3 2
with sodium salt of pyridyl tellurolate afforded complex [PdCl{2-TeC H (3-Me)(PPh )] [35].
5
3
3
2
+
The complex [Pt (μ-SeC H N) (dppf) ] (3) in CDCl solution also exhibited similarly two
2
5
4
2
2
3
phosphorus peaks corroborated with platinum satellites as discussed above for the complex 4
3
1
(
scheme 2). The P NMR of complex 3 in CD OH exhibited a single resonance at 12.6 ppm
3
1
with a J(Pt–P) coupling of 3169Hz, corresponding to a symmetrical phosphorus environment,
with a selenolate ligand trans to the phosphine ligand [15, 26, 35, 36]. In contrast, in CDCl3
solution, complex 3 exhibited two phosphorus peaks with almost identical chemical shifts and
coupling to platinum as seen for complex 4. This suggests, that in CDCl solution, the cationic
3
binuclear complex 3 converts to the mononuclear complex 4 (Scheme 2). The four membered
ring of {Pt Se } in complex 3 has been stabilized due to π bonding effect [8, 37]. The
2
2
chlorination of seleno bridge, has been anticipated due to perturbation of π cloud in presence of
electron-withdrawing group to weaken the Pt-Se bond and open up the four membered ring [38].
An ionic nature of complex 3 has also been monitored by molar conductivity measurement
2
+
where complex [Pt (μ-SeC H N) (dppf) ] (3) showed a non electrolyte nature in CHCl (1.8 μS
2
5
4
2
2
3
8

2
-1
2
-1
cm mole ) however, it is 1:2 electrolyte in methanol (133.2 μS cm mole ). This indicates the
existence of neutral species in dichloromethane, while in polar solvent like CH OH complex
3
adopts ionic structure. A similar reactivity pattern has been reported for the complex like [Pt (μ-
2
2
+
2+
S) (dppf) ]
[8], [Pt (μ-SeCH CH NMe ) (dppe) ]
[35, 36], and [Pt (μ−TeC H (3-
2 5 3
2
2
2
2
2
2 2
2
2
+
Me) (dppe) ]
(dppe=1,2-bis(diphenylphosphino)ethane) [15]. The rapid conversion of
2
2
binuclear complex to mononuclear compound is well documented in literatures [8, 15, 18, 19].
The possibilty of the formation of a mononuclear species is expected to be due to the strong trans
effect of phosphine ligand which weaken the bridging chalcogenolate linkage and results the
formation of the mononuclear mixed halide/chalcogenolates complexes.
All complexes are colored and show absorption bands in visible range of electronic
spectra. The bands are red-shifted with respect to the diselenide ligands. The highest occupied
molecular orbital (HOMO) is located on the selenolate ligands, whereas the lowest unoccupied
molecular orbital (LUMO) is probably delocalised over phosphine ligand [35].
4
.
Conclusion:
The substitution reaction of pyridyl/pyrimidyl selenolate with palladium and platinum(II)
metal precursors [MCl (dppf)] (M = Pd, Pt) afforded mono or binuclear products. The pyrimidyl
2
derived selenolate gave rise solely to mononuclear complexes with both platinum and palladium,
and the pyridylselenolate gave rise to equivalent complexes with palladium. In contrast, on
reaction with platinum, the pyridyl derived selenolate yielded either binuclear, [Pt (μ-
2
SeC H N) (dppf) ]Cl , or mononuclear [Pt(Cl)(SeC H N)(dppf)] products. The isolation of
5
4
2
2
2
5
4
these mononuclear [M(SeAr) (dppf)] (M = Pd, Pt; Ar = C H N, C H(2,6-Me)N ) and ionic
2
5
4
4
2
compounds depend upon substituent present on phenyl ring and solvent involved during the
course of reaction. The instant conversion of binuclear to mono-nuclear species is mainly
9

aroused due to nucleophilic attack of chlorinated solvent on selenolate bridged binuclear
complex.
Acknowledgement:
One of the authors (RSC) is grateful to DST for the financial support under the DST young
scientist scheme YSS/2014/000797. We thank to Drs. V. K. Jain and Vijay Joshi for
encouragement of this work and valuable suggestions for the preparation of this article.
Supporting Information
CCDC-Nos. 1574352-1574354 for [PdCl (dppf)].CH Cl , [PtCl (dppf)].0.5CH Cl and
2
2
2
2
2
2
[
Pt{2-Se-C H(4,6-Me) N } (dppf)].0.5C H ,
respectively contain
the
supplementary
4
2
2 2
6
6
crystallographic data for this paper. These data can be obtained free of charge at
www.ccdc.cam.ac.uk/conts/retrieving.html or from the Cambridge Crystallographic Data Center,
1
2 Union Road, Cambridge CB2 1EZ, UK [Fax: + 44-1223/336-033; E-mail:
deposit@ccdc.cam.ac.uk].
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1
)
S. W. Chien, T. S. A. Hor in Ferrocenes: Ligands, Materials and Biomolecules (Ed.: P.
Štěpnička), Wiley, Chichester, 2008, chapter 2, pp. 33–116; b) K.-S. Gan, T. S. A. Hor in
Ferrocenes: Homogeneous Catalysis, Organic Synthesis Materials Science (Eds.: A.
Togni, T. Hayashi), Wiley-VCH, Weinheim, 1995, chapter 1, pp. 3–104; c) G. Bandoli,
A. Dolmella, Coord. Chem. Rev. 209 (2000) 161–196.
1
0

2
)
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1
4

Table 1. Crystallographic and structural determination data for [Pt{2-Se-C H(4,6-
4
Me) N } (dppf)]. 0.5C H (1a)
2
2 2
6
6
Complex
1a
Chemical formula
Formula wt.
C H FeN P PtSe
2
49
45
4
2
1160.73
3
Crystal size (mm )
0.09 x 0.03 x 0.01
Triclinic
Crystal system
Space group
Unit cell dimensions
a (Å)
ꢀ
P
-1
11.3463(18)
15.7103(15)
15.896(2)
117.826(7)
101.96(2)
93.179(15)
2413.3(7)
1.597
b (Å)
c (Å)
α (°)
β (°)
γ (°)
3
Volume (Å )
-3
ρcacld , g cm
Z
2
-1
μ (mm )/F(000)
4.795/1138
-13≤h≤13
Limiting indices
-
18≤k≤18
17≤l≤19
-
θ for data collection(°)
1.864-25.388
29339
No of reflections collected
No of independent reflection (Rint)
8733 (0.0749)
8733/36/551
Data/restraints/parameters
Final R , wR indices (I˃2σI)
0.0487, 0.1081
0.0881, 0.1200
0.933
1
2
R , wR (all data)
1
2
2
Goodness of fit on F
1
5

Table 2: Selected bond lengths (Å) and angles (°) of [Pt{2-Se-C H(4,6-Me) N } (dppf)]
4
2
2 2
1
a·0.5C H6
6
Pt(1)-P(1)
2.301(2)
Pt(1)-P(2)
2.295(2)
Pt(1)-Se(1)
2.4595(11)
1.901(10)
101.83(8)
85.52(6)
Pt(1)-Se(2)
2.4578(10)
1.922(10)
84.38(3)
Se(1)-C(35)
Se(2)-C(43)
P(2)-Pt(1)-P(1)
P(1)-Pt(1)-Se(1)
P(1)-Pt(1)-Se(2)
Se(1)-Pt(1)-Se(2)
P(2)-Pt(1)-Se(2)
P(2)-Pt(1)-Se(1)
88.84(6)
167.23(6)
171.66(6)
1
6

Figure captions
Figure 1: ORTEP diagram of [Pt{2-Se-C H(4,6-Me) N } (dppf)].0.5C H (1a.0.5C H ) with
4
2
2 2
6
6
6
6
atomic numbering scheme. The ellipsoids were drawn at the 50% probability level.
Hydrogen atoms and solvent molecules are omitted for clarity.
1
7

Figure 1: ORTEP diagram of [Pt{2-Se-C H(4,6-Me) N } (dppf)].0.5C H (1a) with atomic
4
2
2 2
6
6
numbering scheme. The ellipsoids were drawn at the 50% probability level. Hydrogen atoms and
solvent molecules are omitted for clarity.
1
8

M
Pd
Pd
Pt
X
N
C
N
R
Me
H
1a
1b
2a
Me
Scheme 1
1
9

N
Ph Ph
Ph Ph
P
Pt
P
Se
Se
P
Pt
[
PtCl (dppf)]
Fe
Cl2
2
Fe
P
in benzene
Ph Ph
Ph Ph
N
(3)
Methanol
2
NaBH4
2
CDCl3
N
Se
N
SeNa
2
Ph Ph
[
PtCl (dppf)]
N
2
P
Pt
P
Se
Cl
Fe
in DCM
Ph Ph
(4)
Scheme 2
2
0

The bis(diphenylphisphino)ferrocene (dppf) derived palladium analogue of [PdCl (dppf)] on
2
reaction with the sodium salt of pyridyl/pyrimidyl selenolate yielded mononuclear cis configured
complex [Pd(SeAr) (dppf)] (Ar = C H N, C H(4,6-Me) N ), as did the platinum precursor
2
5
4
4
2
2
[
PtCl (dppf)] with methyl substituted pyrimidyl salt giving [Pt{SeC H(4,6-Me) N } (dppf)]. In
2 4 2 2 2
contrast, the reaction of platinum precursor with the sodium salt of pyridylselenolate gave two
2+
different complexes [Pt (μ-SeC H N) (dppf) ] and [Pt(Cl)(SeC H N)(dppf)] depending in the
2
5
4
2
2
5
4
reaction solvent.
2
1

Highlights

Studied the reaction of [PdCl (dppf)] with the sodium salt of pyridyl/pyrimidyl
2
selenolate.


Reaction of [PtCl (dppf)] with sodoim salt of pyridyl selenolate ligands.
2
Isolation of binuclear and mononuclear products depending upon the solvent.
2
2