Synthesis and characterization of heterobimetallic complexes with pyridyl selenolato ligands. Crystal structure of [{Pt(C5H4N)(SeC5H4N)(dppp)}ZnCl2]

Article abstract of DOI:10.1016/j.jorganchem.2016.12.013

Reactions of [Pt(SeC₅H₄N)₂(P∩P)] with M(OAc)₂.2H₂O/MX₂(P∩P = dppm, dppp; M = Zn, Cd, Hg, Cu; X = Cl) resulted various products depend upon the nature of the phosphine. In case of dppm, reac

Full text of DOI:10.1016/j.jorganchem.2016.12.013

Accepted Manuscript
Synthesis and characterization of heterobimetallic complexes with pyridyl selenolato
ligands. Crystal structure of [{Pt(C H N)(SeC H N)(dppp)}ZnCl ]
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Rohit Singh Chauhan, Neelam Shivran, Alexandra M.Z. Slawin, J. Derek Woollins
PII:
S0022-328X(16)30565-4
10.1016/j.jorganchem.2016.12.013
JOM 19736
DOI:
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 7 August 2016
Revised Date: 21 November 2016
Accepted Date: 13 December 2016
Please cite this article as: R.S. Chauhan, N. Shivran, A.M.Z. Slawin, J. Derek Woollins, Synthesis
and characterization of heterobimetallic complexes with pyridyl selenolato ligands. Crystal structure
of [{Pt(C H N)(SeC H N)(dppp)}ZnCl ], Journal of Organometallic Chemistry (2017), doi: 10.1016/
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j.jorganchem.2016.12.013.
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Graphic Abstract
Synthesis and characterization of heterobimetallic complexes with pyridyl
selenolato ligands. Crystal structure of [{Pt(C5H4N)(SeC5H4N)(dppp)}ZnCl2]
Rohit Singh Chauhan*a, Neelam Shivranb, Alexandra M. Z. Slawinc and J. Derek Woollinsc

ACCEPTED MANUSCRIPT
Synthesis and characterization of heterobimetallic complexes with pyridyl
selenolato ligands. Crystal structure of [{Pt(C5H4N)(SeC5H4N)(dppp)}ZnCl2]
Rohit Singh Chauhan*a, Neelam Shivranb, Alexandra M. Z. Slawinc and J. Derek Woollinsc
a Department of Chemistry, K. J. Somaiya College of Science and Commerce,
Mumbai- 400 078 (India),
Email: rohit.chuhan@somaiya.edu
b Department of Chemistry, Indian Institute of Science Education and Research,
Pune-411008 (India),
cEastCHEM School of Chemistry
University of St Andrews
St Andrews
Fife KY16 9ST
Email: amzs@st-andrews.ac.uk
Abstract
Reactions of [Pt(SeC5H4N)2(P∩P)] with M(OAc)2.2H2O/MX2 (P∩P = dppm, dppp; M =
Zn, Cd, Hg, Cu; X = Cl) resulted various products depend upon the nature of the phosphine. In
case of dppm, reaction between [Pt(SeC5H4N)2(dppm)] and M(OAc)2.2H2O/MX2 (M = Zn, Cd,
Hg) afforded an exchange product of composition [PtCl2(dppm)]. Similarly, the reaction with
‘dppp’ analog yielded an adduct [{Pt(SeC5H4N)2(dppp)}MX2] (M = Cd, Hg, Cu; X = Cl, OAc).
Whereas, reaction with Zn(OAc)2, on extraction with dichloromethane resulted the product with
the loss of one selenium atom of composition [{Pt(C5H4N)(SeC5H4N)(dppp)}ZnCl2]. These
complexes were characterized by elemental analyses and NMR (1H, 31P, 77Se, 195Pt)
spectroscopy. The molecular structure of [{Pt(C5H4N)(SeC5H4N)(dppp)}ZnCl2] was established
by single crystal X-ray diffraction analyses.
Keywords: Platinum, Selenolate, NMR, X-ray, Phosphines.
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1. Introduction
The nature of metallophilic bonding (i.e. attractive interaction between closed shell
transition metals) has been drawn considerable interest for quite some time. Due to rich
coordination reactivity and structural diversity [1-5], it finds proven application in the field of
material science [6-8] and design of luminescent compounds [9, 10]. There is the range of
strategies applied for the development of various metallophilic ligands, part of the attention has
been focused towards d8 metal complexes that have a variable chalcogen and metal atom in their
inner core. The easiest type of system consists of two chalcogen and two metal centers (M2S2).
In 1971, Ugo et. al. reported a powerful metallophilic binuclear complex [Pt2(µ-
S)2(PPh3)4] [11]. These metalloligands, [Pt2(µ-S)2(P-P)2] [P-P = 2PPh3, 2dppy, dppp, dppf,
2PMe2Ph, dppe] show powerful Lewis basicity towards d-and f- block elements[12-15].
Renewed interest in the development of metallophilic bonds through the metal chalcogen core,
has been shown by V. W.–W.Yam et. al. They have performed a reaction between [Pt2(µ-
E)2(dppy)4] (dppy = 2 diphenylphosphineopyridne) (E= S, Se) and [M2(dppm)], which yielded
polynuclear complexes [Pt2 (dppy)4(µ3-E)2M2(dppm)]2+ (M = Cu, Ag, Au) [15]. They have also
performed the same reaction with [M(CH3CN)4]+ (M = Cu, Ag) and isolated a tetranuclear d10
copper(I) and silver(I) clusters containing a µ4-sulfido moiety which all exhibits rich
photochemical and physical properties [16-18]. Thus, the Lewis basic core {Pt2(µ-E)2} ( E= S,
Se) can be combined with Lewis acidic metal complexes to give mixed-metal materials as well
as multinuclear homo-platinum complexes [15]. Despite growing interest in the Pt2S2 core as a
metallophilic ligand still the heavier analog like Pt2Se2, PtSe2 remain uncharted, even those
which have proven better nuclophilic behavior [19, 20] and luminescence property [21, 22].
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Thus fully characterized heterometallic complexes bridged with heavier chalcogen
ligands for example selenolato and tellurolato ligands are comparatively very few in number.
Therefore, in this work, we have described the synthesis and characterization of some new
heterometallic complexes derived from [Pt(SeC5H4N)2(P∩P)] (P∩P = dppm, dppp) (from
substitution reaction between [PtCl2(P∩P)] with two mole of sodium salt of pyridyl selenolate)
and M(OAc)2.2H2O (M = Zn, Cd, Hg, Cu). The result of the work is reported as here in.
2. Experimental
2.1 Materials and methods
The compounds [PtCl2(P∩P)] [P∩P = dppm (bis(diphenylphosphino)methane), dppe
dppp (1,3-bis(diphenylphosphino)propane)] [23] [Pt(SeC5H4N)2((P∩P)] (P∩P = dppm, dppp)
[24] and the ligands (SeC5H4N)2, [25] were prepared by literature methods. The metal
precursors MCl2 (M = Zn, Cd); [M(OAc)2].2H2O (M = Zn, Cd, Hg, Cu) were procured from
stern chemical. All reactions were carried out under a nitrogen atmosphere in dry and distilled
1
analytical grade solvents at room temperature. The H, 31P{1H},77Se{1H} and 195Pt{1H}NMR
spectra were recorded on a Bruker Avance-II spectrometer operating at 300, 121.49, 57.23 and
1
64.52 MHz, respectively. Chemical shifts are relative to internal chloroform (δ 7.26) for H,
external 85% H3PO4 for 31P, and external Me2Se for 77Se{1H} and Na2PtCl6 in D2O for 195Pt
NMR. Elemental analyses were carried out on a Thermo Fischer Flash EA1112 CHNS analyzer.
Intensity data for [{Pt(C5H4N)(SeC5H4N)(dppp)}ZnCl2] was measured on Bruker Apex-
II, CCD difractometer with MoKα radiation, and Mercury CCD were used. The structures were
solved by direct methods or charge flipping [26] and refinement [27] was on F2 using data that
had been corrected for absorption effects with an empirical procedure. Non-hydrogen atoms
were modeled with anisotropic displacement parameters, hydrogen atoms in their calculated
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positions. Molecular structures were drawn using ORTEP [28]. Crystallographic and structural
determination data are listed in Table 1.
2.2
Synthesis of complexes
2.2.1. [Pt(SeC5H4N)2(dppm)] (1)
To a dichloromethane suspension (10 cm3) of [PtCl2(dppm)] (531 mg, 0.81 mmole) was
added a methanol-benzene solution (15 cm3) of NaSeC5H4N [prepared from (SeC5H4N)2 (255
mg, 0.81 mmol) in benzene and NaBH4 (70 mg, 1.89 mmol) in methanol]. The mixture was
stirred for 6 h, after which a clear yellow solution was obtained. The latter was dried under
reduced pressure and thoroughly washed with diethyl ether followed by hexane. The residue was
extracted with dichloromethane through Florisil. Yellow crystalline powder was obtained. (Yield
569 mg, 78%). Anal. calcd. for C35H30N2P2PtSe2: C, 47.04; H, 3.38, N; 3.13%. Found: C, 46.93;
H, 3.34; N; 3.09%. 31P{1H} NMR (CDCl3) δ: –50.41 [(1J (Pt–P) = 2704 Hz)]. The
characerization data are consitent with literature value [24].
2.2.2. [PtCl2(dppm)] (1a)
(i)
To a benzene solution (10 cm3) of [Pt(SeC5H4N)2(dppm)] (150 mg, 0.17 mmol), a
methanolic solution (30 cm3) of Zn(OAc)2.2H2O (38 mg, 0.17 mmol) was added with stirring
which continued for 4 h at room temperature. The solvent was evaporated under vacuum and the
residue was extracted with dichloromethane and passed through cellite. The extractant on slow
evaporation afforded pale white powder of [PtCl2(dppm)] (yield 52 mg, 48% m.p. 330oC (dec.)).
1
Anal. calcd. for C25H22Cl2P2Pt: C, 46.17; H, 3.41%. Found: C, 45.98; H, 3.36%. H NMR
(CDCl3) δ: 4.35 (br, P-CH2), 7.32-7.68 (m, Ph); 31P{1H} NMR (CDCl3) δ: –64.2 [1J(Pt-P) = 3081
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Hz]. Similarly the reaction between [Pt(SeC5H4N)2(dppm)] (100 mg, 0.11 mmol) and ZnCl2 (17
mg, 0.12 mmol) in dichloromethane solution afforded white powder of 1 (yield 40 mg, 55%).
1
Anal. calcd. for C25H22Cl2P2Pt: C, 46.17; H, 3.41%. Found: C, 46.14; H, 3.46%. H NMR
(CDCl3) δ: 3.93 (m, P-CH2), 7.54–7.71 (m, Ph); 31P{1H} NMR (CDCl3) δ: –64.4 [1J(Pt-P) =
3087 Hz].
(ii)
Prepared similar to 1a (method i) by using Cd(OAc)2.2H2O (46 mg, 0.17 mmol) and
[Pt(SeC5H4N)2(dppm)] (150 mg, 0.17 mmol), after processing and recrystallization in
dichloromethane and hexane mixture, white powder of compound 1a (yield 60 mg, 55%) was
obtained. 1H NMR (CDCl3) δ: 4.31 (m, P-CH2), 7.43-7.67 (m, Ph ); 31P{1H} NMR (CDCl3) δ: –
64.4 [1J(Pt–P) = 3087 Hz]. Even the reaction between [Pt(SeC5H4N)2(dppm)] (85 mg, 0.10
mmol) and CdCl2 (19 mg, 0.10 mmol) also resulted the product 1a (yield 40 mg, 65%) as
mentioned above. The 1H NMR and 31P{1H} spectra were consistent with the sample prepared as
in (i).
(iii) Similarly to method (i) product 1a obtained by the reaction between Hg(OAc)2.2H2O (60
mg, 0.17 mmol) and [Pt(SeC5H4N)2(dppm)] (46 mg, 0.17 mmol) on recrystallization in
dichloromethane-hexane mixture. NMR spectra (1H and 31P) were consistent with compound 1a
(yield 64 mg, 59%).
2.2.3. [Pt(SeC5H4N)2(dppp)] (2)
Prepared similar way to 1 by using the [PtCl2(dppp)] (485 mg, 0.71 mmole) and
NaSeC5H4N [prepared from (SeC5H4N)2 (224 mg, 0.71 mmol) in benzene and NaBH4 (56 mg,
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1.45 mmol) in methanol] and recrystallized with dichloromethane-hexane to give a yellow
powder (yield 533 mg, 81%). Anal. calcd. for C37H34N2P2PtSe2: C, 48.22; H, 3.72, N; 3.04%.
1
Found: C, 48.25; H, 3.76; N; 3.04%. H NMR (CDCl3) δ: 2.83 (br); 3.14–3.23 (m, CH2); 6.61–
7.83 (m, Ph + C5H4N) 8.13 (d, 4.8 Hz, 2-H, C5H4N).31P{1H} NMR (CDCl3) δ: –10.1 [(1J(Pt–P) =
2760 Hz)].
2.2.4. [{Pt(C5H4N)(SeC5H4N)(dppp)}ZnCl2] (2a)
To a benzene solution (12 cm3) of [Pt(SeC5H4N)2(dppp)] (90 mg, 0.10 mmol) was added
a methanol- solution (10 cm3) of Zn(OAc)2.2H2O (22 mg, 0.10 mmol). The reactants were stirred
for 5 h at room temperature to give a yellow solution. The solvents were removed under vacuum
and the residue was washed with diethyl ether and dried under reduced pressure. The product
was extracted with dichloromethane, filtered and passed through a Florisil column. The resulting
solution was concentrated (5 cm3) under vacuum which on refrigeration at –4°C gave pale
yellow crystals (yield 49 mg, 52%). Anal. calcd. for C37H34Cl2N2P2PtSe2Zn: C, 45.39; H, 3.50,
1
N; 2.86%. Found: C, 45.85; H, 3.46; N; 2.69%. H NMR (CDCl3) δ: 2.84 (br, -PCH2), 3.1 (br,
PCH2-CH2-), 6.80 (br, C5H4N) 7.32 (br, Ph), 7.61 (br, Ph), 7.78-7.80 (m, Ph + C5H4N), 8.26 (6.2
Hz, 2-H, C5H4N); 31P{1H} NMR (CDCl3) δ: –8.06 [(1J Pt–P) = 2846 Hz)], –10.34 (satellites
were merged with the former one so it is diffucult to resolve.) 77Se{1H} NMR (CDCl3) δ: 156.1
[1J(Pt–Se) = 614 Hz].
2.2.5. [{Pt(SeC5H4N)2(dppp)}CdCl(OAc)] (2b)
To a benzene solution (15 cm3) of [Pt(SeC5H4N)2(dppp)] (150 mg, 0.16 mmol) was
added a methanol- solution (15 cm3) of Cd(OAc)2.2H2O (44 mg, 0.16 mmol). The reactants were
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stirred for 5 h at room temperature to give a turbid yellow solution. The resulting solution is
passed through G-3 assembly, clear yellow solution was collected. The solvents were removed
under vacuum and the residue was washed with diethyl ether and dried under reduced pressure.
The product was extracted with dichloromethane, filtered and passed through a Florisil column.
The resulting solution was concentrated (3 cm3) under vacuum which on slow evaporation at
room temperature gave yellow crystals (yield 101 mg, 55%). Anal. calcd. for
1
C39H37ClN2O2P2CdPtSe2: C, 41.51; H, 3.30, N; 2.48%. Found: C, 42.01; H, 3.32; N; 2.49%. H
NMR (CDCl3) δ: 2.11(s, -PCH2), 2.94 (br, -PCH2CH2), 3.73(s, CH3), 6.92 (d, 6.3 Hz, C5H4N)
7.44 (br, Ph), 7.62 (br, Ph), 7.75-7.81 (m, Ph + C5H4N), 8.48 (d, 4.5 Hz, 2-H, C5H4N); 31P{1H}
NMR (CDCl3) δ: –7.53 [(1J(Pt–P) = 2880 Hz)], –11.29 [(1J(Pt–P) = 3139 Hz)]; 77Se{1H} NMR
(CDCl3) δ: 83.0 [1J(Pt–Se) = 832 Hz], 196.7 [1J(Pt–Se) = 660 Hz].
2.2.6. [{Pt(SeC5H4N)2(dppp)}HgCl(OAc)] (2c)
Prepared in a similar fashion to 2b by using [Pt(SeC5H4N)2(dppp)] (140 mg, 0.15 mmol)
and Hg(OAc)2.2H2O (48 mg, 0.15 mmol) and recrystallized from dichloromethane as yellow
powder in yield 49% (91 mg). Anal. calcd. for C39H37ClN2O2P2HgPtSe2: C, 38.49; H, 3.06, N;
2.30%. Found: C, 38.91; H, 3.08; N; 2.62%.1H NMR (CDCl3) δ: 2.83(s, -PCH2), 2.99 (br, -
PCH2CH2), 3.72 (s, CH3), 6.92 (br, C5H4N), 7.35-7.45 (m, Ph + C5H4N), 7.66-7.72 (m, Ph +
C5H4N), 8.12 (d, 5.4 Hz, 2-H, C5H4N); 31P{1H} NMR (CDCl3) δ: –7.43 [(1J(Pt–P) = 2876 Hz)], –
11.58 [(1J(Pt–P) = 3195 Hz)]. On keeping the compound for crystallization in CH2Cl2 results
decomposition of product with settlement of balck pasty mass.
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2.2.7. [{Pt(SeC5H4N)2(dppp)}Cu(OAc)2] (2d)
Prepared similar way to 2b by using [Pt(SeC5H4N)2(dppp)] (125 mg, 0.14 mmol) and
Cu(OAc)2.2H2O (27 mg, 0.14 mmol) in yield 61% (91 mg). Anal. calcd. for
C41H40N2O4P2CuPtSe2: C, 44.63; H, 3.65, N; 2.54%. Found: C, 44.69; H, 3.68; N; 2.56%.1H
NMR (CDCl3) δ: phosphine protons could not be resolved, 3.56(s, CH3), 6.95-7.03 (m, Ph +
C5H4N), 7.45 (br, Ph), 7.59 (br, Ph), 7.62-7.94 (m, Ph + C5H4N), 8.19 (d, 6.4 Hz, 2-H, C5H4N);
31P{1H} NMR (CDCl3) δ: – 7.53 [(1J(Pt–P) = 2848 Hz)], –11.41 [(1J(Pt–P) = 3158 Hz)], 32.65
(phosphine oxide); 77Se{1H} NMR (CDCl3) δ: 102.3 [1J(Pt–Se) = 850 Hz], 140.5 [1J(Pt–Se) =
620 Hz]; 195Pt{1H} NMR (CDCl3) δ: – 4411, – 4455 (dd, [1J(Pt–P) = 2869 Hz], [(1J(Pt–P) =
3158 Hz)]). One more resoance appears on longer acquisition. 195Pt{1H} NMR: – 4700 (t, [1J(Pt–
P) = 2718Hz]) (presumbaly belongs to [{Pt(SeC5H4N)2(dppp)}Cu(OAc)2]).
3.
Results and Discussion
When one mole of [PtCl2(P∩P)] (P∩P = dppm, dppp) was treated with two equivalents of
NaSeC5H4N, (prepared by reductive cleavage of the Se-Se bond in di-2-pyridyl diselenide with
NaBH4), afforded mononuclear pyridylselenolate complexes of type [Pt(SeC5H4N)2(P∩P)] (P∩P
= dppm, dppp). The 31P{1H} NMR spectrum exhibited single resonance at ~ –50.4 and –10.1
ppm with 195Pt–31P coupling of 2704 and 2755 Hz for dppm, dppp analogue respectively. The
negative value of chemical shift considered as chelating behaviour of phosphine. The magnitude
1
of J(Pt–P) for compound 1 and 2 showed presence of selenolate group trans to the phosphine
ligand [24].
The reaction of [Pt(SeC5H4N)2(dppm)] with one equivalent of ZnX2 (X = OAc, Cl) gave
an off white powder which on extraction with dichloromethane resulted a product of
compoistion [PtCl2(dppm)]. Alternatively, compound 1a was formed when a in dichloromethane
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solution of platinum precursor, [Pt(SeC5H4N)2(dppm)], was treated with MX2 (M = Cd, Hg; X =
31
OAc, Cl) in same solvent. The P NMR spectra of 1a displayed a single resonance at δ ~ –64
ppm with 195Pt–31P coupling of ~ 2600 Hz indicative a strong trans influence of chloro group
[23]. The complexes 1a appear to be formed due to nucleophilic attack at coordinated selenolate
ligand by chlorinated solvent like CDCl3 or CH2Cl2. Nucleophilic attack of chlorinated solvent at
coordinated selenolate ligand is well known [29].
However, reactions of [Pt(SeC5H4N)2(dppp)] with Zn(OAc)2.2H2O at room temperature
yielded plae yellow product of [{Pt(C5H4N)(SeC5H4N)(dppp)}ZnCl2] (2a). The 31P{1H} NMR
spectrum of complex 2a displayed two resonances at –8.06 and –10.34 ppm which were flanked
1
by their 195Pt satellites. The magnitude of J(Pt–P) indicates that the phosphine ligand is trans to
selenolate ligand [30]. However coupling trans to carbon centre was not resolvable. The
77Se{1H} NMR spectrum of [{Pt(C5H4N)(SeC5H4N)(dppp)}ZnCl2] (2a) displayed a triplet at 156
ppm with platinum satellites (1J(Pt–Se) = 614 Hz). The observed triplet in fact is due to coupling
with platinum nuclei. In the complex 2a, the unexpected loss of chalcogen atom is well
documented in literature [14, 30-32]. For instance, reaction of Zinc metal precursor with [Pt2(P-
P)2(ꢀ-S)2] (P-P = PPh3, PMe2Ph, dppp, dppy) did not afford the expected product, instead
product [Pt2Cl(P-P)2(ꢀ-S2CH2)]PF6 (P-P = PPh3, PMe2Ph, dppp, dppy) formed by the
decomposition of [(P-P)2Pt2(ꢀ3-S)2Zn][PF6]2 in CH2Cl2 [30, 32]. Similarly, the bridging thio
complex [Pt2(dppf)2(ꢀ-S)2] in dichloromethane solution yields mononuclear compound
[Pt(SCH2Cl)2(dppf)] which indicates the formation of terminal bis thiolato complexes from the
bridging one [31] . In the present study, the removal of selenium atom and acetate group appears
to be brought out by strong nucleophilicity of CH2Cl2.
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Simaliarly, an addition product [{Pt(SeC5H4N)2(dppp)}MX2] (M = Cd, Hg, Cu; X =
OAc, Cl) could also be obtained by the reaction of [Pt(SeC5H4N)2(dppp)] with MOAc2. 2H2O
(M = Cd, Hg, Cu). Unlike the [M{Pt2(P-P)2(ꢀ3-S)2}X2] (M = Zn, Cd and Hg, P-P = PPh3, dppe)
in the reported case the metal center like Zn, Cd, Hg has only attached with one selenium atom
which was corroborated by NMR and crystal structure of complex 2b. The 31P NMR spectrum of
complex 2b, 2c, 2d exhibited two 31P resonance at δ ~ –7 ppm and –11 ppm with different 1J(Pt–
P) coupling constants. The former resonance is deshielded compared to latter one, with 195Pt–31P
coupling of ~ 2850 Hz indicative of selenolate ligand trans to the phosphine ligand [33-35].
While latter resonance ~ –11 ppm with the coupling constant ~3150Hz is phenomenal agreement
with reported heterometallic complexes [M{Pt2(dppe)2(ꢀ3-S)2}X2] (M = Zn, Cd and Hg) [29,
36]. Hence, this resonance belongs to selenolate ligand which is attached to platinum as well as
with Cd, Hg, Cu also. Due to bonding with latter metal centres, electron density around selenium
atom gets reduced. As a result it showed shielded resonance compares to other one [36]. The
77Se{1H} NMR spectrum of complex 2b displayed two different resonance at 83 ppm and 196
ppm with their platinum satellite. Two dissimilar resonances correspond to un-equivalent type of
selenium. It seems that in complex [{Pt(SeC5H4N)2(dppp)}MX2] (M = Cd, Hg, Cu), chlorinated
solvent (CH2Cl2, CDCl3) partially substituted the acetate group from metal acetate due to their
strong nuclophilicity [14, 29].
The presence of two different selenolate ligand in above discussed compound is further
corroborated by 195Pt NMR spectrum of [{Pt(SeC5H4N)2(dppp)}CuCl(OAc)] which showed a
doublet of doublet centerd at – 4411ppm [1J(Pt–P) = 2869 Hz], – 4455 ppm [(1J (Pt–P) = 3158
Hz)] [37-38]. Apparently, during the longer acquisition 195Pt NMR spectrum of 2d also displayed
a triplet at δ = – 4700 ppm [1J(Pt–P) = 2718 Hz] as well, indicating coordination of two
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equivalent phosphorus nuclei [39]. The appearence of new resoance suggests the slowly
disintigration of compound in CDCl3 solution to give an unknown moiety. This decomposition
is probably facilitated by nucleophilic attack of chlorinated solvent [29].
Crystal structures
Molecular structures of [{Pt(C5H4N)(SeC5H4N)(dppp)}ZnCl2] was established by single
crystal X-ray diffraction analyses. ORTEP drawings with atomic numbering scheme are depicted
in Figures 1 while selected inter-atomic parameters are given in Tables 2.
The platinum atom in the complex [{Pt(C5H4N)(SeC5H4N)(dppp)}ZnCl2] (2a) adopts a
distorted square planar geometry defined by trans “P2SeC” coordination environment while the
zinc atom acquires distorted tetrahedral shape. The Pt….Zn (3.1526(13) Å) bond is in close
proximity but not lie in metal - metal bonding range [36]. The Pt−Se (2.4821(11) Å), distance is
slightly longer than the normal metal chalcogen reported for the known heterometallic complex,
[Zn{Pt2(ꢀ-S)2(PPh3)4]Cl2 (2.352(2) /2.378(2) Å) [29], [Zn{Pt2(ꢀ-S)2(dppe)4]Cl2 (2.374(7) –
2.379(7) Å) [36] however in good conformity with those reported for [{Pt2(dppy)4(ꢀ3-
Se)2}2Ag3](PF6)3 (2.459(1) – 2.477(1) Å) [15]; {Pt2(µ3-Se)2(PPh3)4[Pt(cod)]}{PF6}2 (2.4392(6)
– 2.4919(6) Å) [40].The Pt–C (2.015(10) Å) distance is in agreement with the one reported for
[PtX(Ph)(PPh3)2] (X = Cl, I) (Pt–C = 2.01(1), 2.015(9) Å) [35, 36]. The Zn–N and Zn–Cl
distances are as expected [29, 36, 43-46].
The molecular structure of complex [{Pt(SeC5H4N)2(dppp)}CdCl(OAc)] (2b) is solvated
in nature. The complex shows eight member puckered ring restrained between platinum and
cadmium metal center. The geometry around the Pt metal center is confined with ‘P2Se2’
fragments with distorted square planner geometry however Cd atom opts distorted octahedral
shape which is defined with ‘N2O2Cl’ frame with Cl and Se atom at axial position. The Pt–P and
11

ACCEPTED MANUSCRIPT
Pt–Se distances are as expected [29, 36]. Due to a poor refinement of the complex, structural
data is not reported here. The Cd–N distances (2.36
Å) are well in agreement with the
avg
reported values [47-49]. The Cd….Se (2.969(4) Å) are slightly longer than the reported value
for [Cd{Pt2(ꢀ-Se)2(PPh3)4]Cl2 (Cd….Se = [2.6852(10) Å]) [19], [Cd{Pt2(ꢀ-S)2(dppe)4]Cl2
(Cd….S = 2.561(2) - 2.553(2) Å) [36]. Because of these interactions Cd….Se pyridyl selenolate
group move out from metal plane.
4.
Conclusion
The reactions of d10 metal precursors with platinum selenolato compounds
[Pt(SeC5H4N)2(P∩P)] (P∩P = dppm, dppp) yield a different type of complexes depending on the
nature of the phosphine ligand and d10 metal centre. In comparison to dppm analogue, the
complex [Pt(SeC5H4N)2(dppp)] is nucleophilic enough to trap the metal precursor of d10 system
results an addition product.
Acknowledgements
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 Dr. V. K. Jain and A. Wadawale
(BARC) for encouragement of this work and assistance for crystal solving.
Supporting Information
CCDC-Nos. 1497006 for Pt(C5H4N)(SeC5H4N)(dppp)].ZnCl2, and contain the
supplementary 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,
12 Union Road, Cambridge CB2 1EZ, UK [Fax:
deposit@ccdc.cam.ac.uk].
+
44-1223/336-033; E-mail:
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1
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Table
1.
Crystallographic
and
structural
determination
data
for
[Pt(C5H4N)(SeC5H4N)(dppp)].ZnCl2 (2a)
Complex
[Pt(SeC5H4N)(C5H4N) (dppp)].ZnCl2
Chemical formula
C37H34N2Cl2P2PtSeZn
978.92
0.30 x 0.30 x 0.20
Mo-Kα
Formula wt.
Crystal size (mm3)
Radiation used for data collection
Crystal system
Space group
Unit cell dimensions
a (Å)
Monoclinic
P121/c
20.307(7)
8.971(3)
21.000(4)
90
103.02(4)
90
b(Å)
c(Å)
α(0)
β(0)
γ(0)
Volume (Å3)
Z
3727(2)
4
ρcalcd, g cm−3
θ for data collection (ο)
µ (mm−1)/F(000)
Index range
1.744
7.8-10.9
5.627 / 1904
–25≤ h≤26
–11≤ k≤0
–27≤ l≤15
10213
No of reflections collected
No of independent reflection / No. of observed 9922 / 4457
reflections with I>2σI
Data/restraints/parameters
9922 / 0 / 484
0.0474 / 0.0905
0.1702 / 0.1211
0.932
Final R1, ωR2 indices
R1, ωR2 (all data)
Goodness of fit on F2
21

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Table 2. Selected bond lengths (Å) and angles (ο) of [Pt(SeC5H4N)(C5H4N) (dppp)].ZnCl2 (2a)
Pt1–P1
2.279(3)
Pt1–P2
Pt1–C1
2.335(3)
Pt1–Se1
2.4821(11)
2.015(10)
Zn1–N1
Zn1–Cl1
Pt1–Zn1
2.013(8)
2.255(3)
3.1526(13)
Zn–N2
2.084(9)
2.282(3)
1.903(11)
Zn1–Cl2
Se1–C6
P1–Pt1–P2
94.24(9)
88.0(3)
C1–Pt1–Se1
P2–Pt1–Se1
P2–Pt1–C1
N1–C1–Pt1
C1–Pt1–Zn1
P2–Pt1–Zn1
N2–Zn1–Cl2
N2–Zn1–Cl1
N1–Zn1–N2
N2–Zn1–Pt1
Cl2–Zn–Pt2
85.4(3)
P1–Pt1–C1
92.37(8)
177.8(3)
116.5(7))
63.3(3)
P1–Pt1–Se1
C6–Se1–Pt1
Se1–Pt1–Zn1
P1–Pt1–Zn1
N1–Zn1–Cl1
N1–Zn1–Cl2
Cl1–Zn1–Cl2
N1–Zn1–Pt1
Cl1–Zn1–Pt1
172.09(7)
108.1(4)
82.55(4)
98.34(7)
125.4(2)
102.1(2)
107.72(11)
63.5(2)
116.42(8)
103.1(3)
105.6(3)
110.8(4)
86.6(3)
79.91(8)
165.07(9)
22

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Figure Captions
Figure 1. ORTEP drawing of [Pt(C5H4N)(SeC5H4N)(dppp)].ZnCl2with atomic number scheme.
Hydrogen atoms are omitted for clarity. The ellipsoids were drawn at the 50%
probability.
23

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Figure 1. ORTEP drawing of [Pt(C5H4N)(SeC5H4N)(dppp)].ZnCl2 (1) with atomic number
scheme. The ellipsoids were drawn at the 50% probability.
24

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Ph Ph
N
Se
Cl
Cl
P
Zn(OAc)2.2H2O
CH2Cl2
Zn
Pt
[PtCl2(dppp)]
N
P
Ph Ph
2
(3)
2a
N
SeNa
Cl
Ph Ph
N
Ph Ph
P
Se
Se
O
O
P
N
N
Se
Se
M(OAc)2.2H2O
CH2Cl2
M
CH3
Pt
Pt
N
P
P
Ph Ph
Ph Ph
(2)
(4) [M = Cd], (5) [M = Hg]
2c
2b
Ph Ph
P
N
N
Se
Se
OAc
Cu(OAc)2.2H2O
C6H6
Cu
Pt
OAc
P
Ph Ph
(6)
2d
Scheme 1
25

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Highlights
•
•
•
Reactions of [Pt(SeC5H4N)2(dppm)] with d10 metal system resulted [PtX2(dppm)].
Reactions of [Pt(SeC5H4N)2(dppp)] with d10 metal system yielded an additive product.
Interaction between Pt-d10depends on the size of metal.