The 2-(4-Phenyl-1H-1,2,3-triazol-1-yl)ethanol-Based Phosphinite Ligand Ph2POCH2CH2[1,2,3-N3C(Ph)C(H)] – Synthesis, Transition-Metal Complexes, and Structural Studies

Article abstract of DOI:10.1002/ejic.201701058

The synthesis and coordination complexes of the new 1,2,3-triazole phosphinite Ph₂POCH₂CH₂[1,2,3-N₃C(Ph)C(H)] (2) are described. Compound 2 reacts with H₂O₂, S₈, and Se₈ to afford the chalcogenides Ph₂P(=E)OCH₂CH₂[1,2,3-N₃C(Ph)C(H)] [E = O (3), S (4), and Se (5)]. The reaction of 2 with [Ru(η⁶-cymene)Cl₂] yielded [Ru(η⁶-cymene)Cl₂(Ph₂POCH₂CH₂{1,2,3-N₃C(Ph)C(H)})] (6), which produced [Ru(η⁶-cymene)(Ph₂POCH₂CH₂{1,2,3-N₃C(Ph)C(H)})]₂[OTf]₂ (7) on further treatment with silver triflate (AgOTf); in 7, 2 acts as a bidentate (P,N) ligand. The reaction of 2 with [CpRuCl(PPh₃)₂] (Cp = cyclopentadienyl) in 1:1 and 1:2 molar ratios afforded the mono- and disubstituted complexes [CpRuCl(PPh₃)(Ph₂POCH₂CH₂{1,2,3-N₃C(Ph)C(H)})] (8) and [CpRuCl(Ph₂P-OCH₂CH₂{1,2,3-N₃C(Ph)C(H)})₂] (9), respectively. Complex 9 reacted with silver triflate to yield the cationic complex [CpRu(Ph₂POCH₂CH₂{1,2,3-N₃C(Ph)C(H)})(Ph₂POCH₂CH₂{1,2,3-N₃C(Ph)C(H)})][OTf] (10), in which one of the phosphinite ligands shows P,N-chelation. The reactions of 2 with [M(COD)Cl₂] (M = Pd, Pt; COD = 1,5-cyclooctadiene) in 2:1 ratios yielded cis-[MCl₂(Ph₂POCH₂CH₂{1,2,3-N₃C(Ph)C(H)})₂] [M = Pd (11) and Pt (12)]. The similar reaction of 2 with [PdCl(η³-C₃H₅)]₂ in a 2:1 ratio afforded [PdCl(η³-C₃H₅)(Ph₂POCH₂CH₂{1,2,3-N₃C(Ph)C(H)})] (13). The reaction of 2 with [AuCl(SMe₂)] in a 1:1 ratio yielded [Au(Cl)(Ph₂POCH₂CH₂{1,2,3-N₃C(Ph)C(H)})₂] (14). The molecular structures of 6, 7, 9, 11, and 12 were determined by single-crystal X-ray studies.

Full text of DOI:10.1002/ejic.201701058

A Journal of
Accepted Article
Title: 2-(4-Phenyl-1H-1,2,3-triazol-1-yl)ethanol based phosphinite
ligand, Ph2POCH2CH2(1,2,3-N3C(Ph)C(H)): Synthesis,
transition metal complexes and structural studies
Authors: Bimba Choubey, Pandey Sameer Prasad, Joel T Mague, and
Maravanji Shivaramaiah Balakrishna
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To be cited as: Eur. J. Inorg. Chem. 10.1002/ejic.201701058
Link to VoR: http://dx.doi.org/10.1002/ejic.201701058

10.1002/ejic.201701058
European Journal of Inorganic Chemistry
2-(4-Phenyl-1H-1,2,3-triazol-1-yl)ethanol based
phosphinite ligand, Ph2POCH2CH2(1,2,3-N3C(Ph)C(H)):
Synthesis, transition metal complexes and structural
studies
Bimba Choubey, Pandey Sameer Prasad, Joel T. Mague, Maravanji S.
Balakrishna
This paper describes the synthesis and transition metal complexes of a triazolylphosphinite
ligand, Ph2POCH2CH2(1,2,3-N3C(Ph)C(H)).
1
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10.1002/ejic.201701058
European Journal of Inorganic Chemistry
2-(4-Phenyl-1H-1,2,3-triazol-1-yl)ethanol based
phosphinite ligand, Ph2POCH2CH2(1,2,3-N3C(Ph)C(H)):
Synthesis, transition metal complexes and structural
studies
Bimba Choubey,[a] Pandey Sameer Prasad,[a] Joel T. Mague[b], Maravanji S.
Balakrishna*[a]
[a]Phosphorus Laboratory, Department of Chemistry, Indian Institute of Technology Bombay,
Powai, Mumbai 400 076, India.
[b]Department of Chemistry, Tulane University, New Orleans, Louisiana 70118, USA.
Keywords: triazolyl phosphinite; metal complexes, X-ray structure; P,N-
coordination.
The synthesis and coordination complexes of new 1,2,3 triazole-phosphinite
Ph2POCH2CH2(1,2,3-N3C(Ph)C(H)) (2) are described. The ligand 2 reacts with H2O2, S8 or Se8
to give chalcogenides: Ph2P(=E)OCH2CH2(1,2,3-N3C(Ph)C(H)) (E = O (3), S (4) and Se (5)).
The reaction of 2 with [Ru(η6-cymene)Cl2] yielded [Ru(η6-cymene)Cl2{Ph2POCH2CH2(1,2,3-
N3C(Ph)C(H))}] (6) which on further treatment with silver triflate produced [{Ru(η6-
cymene){Ph2POCH2CH2(1,2,3-N3C(Ph)C(H))}]2(OTf)2 (7), in which 2 acts as a bidentate
(P,N) ligand. The reaction of 2 with [CpRuCl(PPh3)2] in 1:1 and 1:2 molar ratios afforded both
mono- and disubstituted complexes, [CpRuCl(PPh3){Ph2POCH2CH2(1,2,3-N3C(Ph)C(H))}]
(8) and [CpRuCl{Ph2P-OCH2CH2(1,2,3-N3C(Ph)C(H))}2] (9), respectively. Complex 9 on
treatment with silver triflate yielded a cationic complex [CpRu{Ph2POCH2CH2(1,2,3-
N3C(Ph)C(H))} {Ph2POCH2CH2(1,2,3-N3C(Ph)C(H))}](OTf) (10) with one of the phosphinite
ligands showing P,N-chelation. The reactions of 2 with [M(COD)Cl2] (M = Pd, Pt) in 2:1 ratio
yielded cis-[MCl2{Ph2POCH2CH2(1,2,3-N3C(Ph)C(H))}2] [M = Pd (11) and Pt (12)]. Similar
reaction of
2
with [PdCl(η3-C3H5)]2 in 2:1 ratio afforded [(PdCl(η3-
2
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10.1002/ejic.201701058
European Journal of Inorganic Chemistry
C3H5){Ph2POCH2CH2(1,2,3-N3C(Ph)C(H))}] (13). The reaction of 2 with [AuCl(SMe2)] in 1:1
ratio yielded [Au(Cl){Ph2POCH2CH2(1,2,3-N3C(Ph)C(H))}2] (14). Molecular structures of 6,
7, 9, 11 and 12 have been determined by single crystal X-ray studies.
∗Author to whom correspondence should be addressed. E-mail: krishna@chem.iitb.ac.in,
msb_krishna@iitb.ac.in (M. S. Balakrishna).
Introduction
The development of well-designed ligand systems with which the catalytic and reactivity
patterns of the metal complexes can be varied in a controlled manner is one of the most
important goals in modern inorganic chemistry.[1] Triazole appended phosphine derivatives are
appropriate for stabilizing the transition metals with low coordination number and/or unusual
oxidation states due to the presence of dangling N-donor arm(s).[2] Over the years, several
triazole based phosphines, also known as Clickphos, have been synthesized and their
coordination chemistry[3] and their catalytic applications[1b, 4] have been explored. Although
1,2,3-triazole based phosphines are known, the chemistry of analogous Click(phosphite)s,
Click(phosphinite)s[3h] or Click(phosphonite)s is scant or unknown.[5] We recently reported a
very simple and efficient synthetic route to prepare two triazole based structural isomers
differing in the positions of phosphorus moieties, 1-(2-(diphenylphosphino)phenyl)-4-phenyl-
1H-1,2,3-triazole and 5-(diphenylphosphino)-1,4-diphenyl-1H-1,2,3-triazole, by temperature-
mediated Li/H exchange reaction of 2-bromo-phenyl triazole and explored their coordination
chemistry.[6] This paper describes the synthesis of a new 1,2,3-triazole based phosphinite,
Ph2POCH2CH2(1,2,3-N3C(Ph)C(H)) and its RuII, PdII, PtII and AuI complexes.
Results and Discussion
Synthesis of Ph2POCH2CH2(1,2,3-N3C(Ph)C(H)) (2)
3
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10.1002/ejic.201701058
European Journal of Inorganic Chemistry
2-(4-Phenyl-1H-1,2,3-triazol-1-yl)ethanol, HOCH2CH2(1,2,3-N3C(Ph)C(H)) (1) prepared by
reacting phenyl acetylene and 2-azido-ethanol in equimolar ratio in the presence of sodium
ascorbate and copper sulphate, was treated with Ph2PCl/Et3N to produce Ph2POCH2CH2(1,2,3-
N3C(Ph)C(H)) (2) in 76% yield.
Scheme 1 Synthesis of phosphinite and its chalcogenides
1
The 31P NMR spectrum of 2 showed a resonance at 117.6 ppm. The H NMR spectrum of 2
consist of a singlet at 7.66 ppm for triazolyl proton and a multiplet in the range of 4.27-4.64
ppm for aliphatic protons. The mass spectrum of 2 displayed molecular ion peak at m/z 374.14
with appropriate isotopic patterns. The structure and molecular composition of 2 were further
confirmed by 13C NMR and elemental analysis.[7]
Treatment of 2 with aqueous H2O2 (30 %) at 0 °C or S8 and Se8 in toluene under refluxing
conditions furnished the corresponding chalcogenides Ph2P(O)OCH2CH2(1,2,3-N3C(Ph)C(H))
(3), Ph2P(S)OCH2CH2(1,2,3-N3C(Ph)C(H)) (4) and Ph2P(Se)OCH2CH2(1,2,3-N3C(Ph)C(H))
(5), respectively. The 31P NMR spectra of 3-5 showed singlets at 35.9, 84 and 88.1 ppm,
1
respectively. The selenide 5 showed characteristic selenium satellites with a JPSe coupling of
808.2 Hz. The large coupling constant indicates the larger s-character of the phosphorus lone
pairs.[8] Usually the magnitude of 1JPSe increases with increase in electron withdrawing ability
of the phosphorus substituents and vice versa.[8a] The electron withdrawing groups leave
4
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10.1002/ejic.201701058
European Journal of Inorganic Chemistry
slightly less ‘p’ and more ‘s’ character in the lone pair which is eventually utilized in making
P=Se bond..
Transition Metal Complexes of 2
Ruthenium(II) Complexes
Treatment of 2 with [Ru(η6-cymene)Cl2]2 in CH2Cl2 at room temperature yielded [Ru(η6-
cymene)Cl2{Ph2POCH2CH2(1,2,3-N3C(Ph)C(H))}] (6) which on further treatment with
AgOTf
afforded
cationic
complex
[Ru(η6-cymene)(Cl){Ph2POCH2CH2(1,2,3-
N3C(Ph)C(H))}]2 (OTf)2 (7) with ligand exhibiting bidentate bridging mode of coordination
(Scheme 2). The 31P NMR spectra of 6 and 7 showed singlets at 118.8 and 120.9 ppm,
1
respectively. The H NMR spectrum of 6 confirmed the presence of cymene group. The
complex 6 showed two doublets centered at 5.15 and 5.18 ppm with a 3JHH coupling of 6.3 Hz.
The isopropyl methyl protons appeared as a doublet centered at 1.03 ppm with a 3JHH coupling
of 6.9 Hz, whereas the (CH(Me)2) protons showed a septet centered at 2.61 ppm. A sharp
singlet was observed at 7.95 ppm for triazolic proton. The 31P NMR spectrum of complex 7
showed a single resonance at 120.9 ppm. The 1H NMR spectrum of 7 consists of two doublets
for cymene ring protons centered at 5.70 and 5.83 ppm with a 3JHH coupling of 6.0 Hz, a doublet
at 0.96 ppm for methyl protons of isopropyl group with a 3JHH coupling of 6.6 Hz and a septet
at 2.97 ppm (3JHH = 6.6 Hz) for methine proton. The molecular structures of 6 and 7 were
confirmed by single crystal X-ray analysis.
5
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10.1002/ejic.201701058
European Journal of Inorganic Chemistry
Ph
Ru
N
O
Ru
N
P
Cl
O
PPh2
Ph2
P
CF3SO3
N
Ph2
N
N
N
N
O
PPh3
N
N
8
10
Ph
Ph
0.5[CpRu(PPh3)2Cl]
AgOTf
[CpRu(PPh3)2Cl]
CH2Cl2
CH2Cl2
OPPh2
Ru
[Ru( 6-cymene)Cl2]2
Cl
N
0.5[CpRu(PPh3)2Cl]
Toluene
Cl
Ru
N
OPPh2
Cl
CH2Cl2
Ph
P
O
Ph2P
N
Ph2
O
N
N
N
2
N
N
[Ru( 6-Cymene)Cl2]2
N
N
AgOTf
N
Ph
CH2Cl2
9
6
N
Ph
Ph
Ph
Ph2
N
N
O
Cl
P
N
O
N
Ru
(OTf)2
Ru
N
P
Cl
N
Ph2
7
Ph
Scheme 2 Ruthenium (II) complexes of ligand 2
The 1:1 reaction of 2 with [CpRuCl(PPh3)2] at room temperature yielded monosubstituted
complex [CpRuCl(PPh3){Ph2POCH2CH2(1,2,3-N3C(Ph)C(H))}] (8),[9] whereas the same
reaction in 2:1 ratio in toluene at 80 °C afforded disubstituted [CpRuCl{(Ph2POCH2CH2(1,2,3-
N3C(Ph)C(H))}2] (9) as dark yellow solid. Treatment of 9 with silver triflate resulted in cationic
complex [CpRu{Ph2POCH2CH2(1,2,3-N3C(Ph)C(H))}2](OTf) (10), wherein one of the ligands
acts as a chelating ligand via P and one of the triazolyl-N (Scheme 2). The 31P NMR spectrum
2
of complex 8 displayed two doublets centered at 43.9 and 144.9 ppm with a JPP coupling of
58 Hz. The high field chemical shift was assigned to PPh3, whereas the low field shift was due
to the phosphinite centre. The 31P NMR spectrum of 9 showed a single resonance at 146.6 ppm.
The 31P NMR spectrum of compound 10 displayed two doublets centered at 145 and 148.5
ppm (2JPP = 59 Hz), indicating the presence of two phosphinite centres with chelating κ2- and
6
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10.1002/ejic.201701058
European Journal of Inorganic Chemistry
monodentate κ1-modes of coordination. The EI-mass spectrum of 8 showed peak at 802.16 as
1
[M-Cl]+, whereas 10 displayed base peak at 913.23 [M+H-OTf]+. The H NMR spectra of
complexes 8-10 consist of singlets in the range of 4.22-4.42 ppm for Cp protons and 7.88-8.00
ppm for triazolic protons. The structure of 9 was determined by single-crystal X-ray analysis.
In order to examine the reversibility of the hemilabile nature of ligand 2, complex 10 was
31
treated with one equivalent of PPh3 and refluxed in toluene for 24 h. The P NMR spectrum
of the reaction mixture showed signals due to the unreacted 10 (~90%) along with two doublets
for the formation of [CpRuCl(PPh3){2-Ph2POCH2CH2(1,2,3-N3C(Ph)C(H))-κP, κ-N}] as a
minor product. Reaction of 10 with CO under refluxing conditions also did not show Ru—N
bond dissociation and complex 10 remained intact even after 24 h.
Perspective views of the molecular structures of compounds 6, 7 and 9 with atom numbering
schemes are shown in Figures 1- 3. Crystal data and the details of the structure determination
are given in the Experimental section, while the pertinent bond distances and interbond angles
are included in figure captions.
The compound 6 crystallizes in monoclinic crystal system with P21/n space group having
crystallographically imposed centrosymmetry. The geometry around RuII center is distorted
octahedral having phosphorus atom, two chlorine atoms and η6-cymene ring. The Ru-Cl bond
distances and Cl-Ru-Cl bond angles are normal and comparable with those observed in
analogues RuII complexes.[10] The average Ru-P distance is 2.3000(5) Å. The triazole is tilted
with respect to Cl-Ru-Cl plane. The N2-N1-C14-C13, C15-N1-C14-C13, C15-N1-N2-N3
torsion angles are 93.15(19)°, -88.5(2)° and -0.20(18)°, respectively. Molecules of 6 appear to
be associated by intermolecular H-bonding namely C12-H12…Cl2 (2.66 Å), C14-H14B…Cl1
(2.81 Å), C18-H18…Cl2 (2.79 Å), C28-H28…N3 (2.46 Å) and C6-H6…O1 (2.46 Å).[11]
7
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10.1002/ejic.201701058
European Journal of Inorganic Chemistry
Figure 1. Molecular structure of 6. All hydrogen atoms have been omitted for clarity.
Displacement ellipsoids are drawn at the 50% probability level. Selected bond lengths (Å) and
bond angles (˚): N1-N2 1.347(2), N2-N3 1.317(2), P1-O1 1.6154(13), Ru1-Cl1 2.419(4), Ru1-
Cl2 2.4085(4), Ru1-P1 2.3006(5), P1-C1 1.8163(17), P1-C7 1.828(17), C14-N1 1.457(2), Cl2-
Ru1-C11 89.466(16), O1-P1-Ru1 114.24(5), C1-P1-O1 98.13(7), C7-P1-O1 104.69(7), C7-P1-
Ru1 122.04(6), N1-C14-C13 112.05(14), N1-N2-N3 106.86(14), N2-N1-C14 119.87(14), P1-
Ru1-Cl1 91.472(16).
In contrast to complex 6, the cationic complex 7 is dimeric with ruthenium atoms bridged by
triazolyl phosphinite in a head-to-tail fashion. The molecule has crystallographically imposed
centrosymmetry. The Ru-Cl and P-O bond lengths are similar to those observed in 6. Ru1-N1
and Ru1-P1 bond distances are 2.112(3) and 2.3250(11) Å, respectively. The Cl1-Ru1-P1 bond
angle is 84.18(4)° which is smaller than 6. The two triazole and two aliphatic moieties of both
the molecules are oriented in chair conformation connecting the two ruthenium centers. The
8
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European Journal of Inorganic Chemistry
O1-C20-C19-N3, C19-C20-O1-P1 and N2-N3-C19-C20 dihedral angles are 169.7(3)° (anti-
conformation), 168.4(3)° (anti-conformation) and 68.8(5)°, respectively, with each phenyl ring
on phosphorus arranged in an antiparallel manner. The O1-P1-C27, O1-P1-Ru1, O1-C20-C19
and N3-C19-C20 bond angles are 99.91(18)°, 110.82(12)°, 105.7(3)° and 110.6(3)°,
respectively. Interestingly, molecule shows intermolecular hydrogen bonding interactions,
which probably give extra stability to the cationic complex. The C20-H20…O2 (2.452 Å),
C18-H18…O4 (2.341 Å), C22-H22…O3 (2.662 Å) and C31-H31…F2 (2.579 Å) bond
distances and the angles C20-H20…O2 (152.43°), C18-H18…O4 (139.26°), C22-H22…O3
(142.97°) C31-H31…F2(149.67°) indicate the substantial hydrogen bonding existing in the
lattice.
Figure 2. Molecular structure of 7. All hydrogen atoms have been omitted for clarity.
Displacement ellipsoids are drawn at the 50% probability level. Selected bond lengths (Å) and
bond angles (˚): N1-N2 1.324(4), N2-N3 1.336(5), N3-C19 1.458(5), C19-C20 1.505(6), C20-
9
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10.1002/ejic.201701058
European Journal of Inorganic Chemistry
O1 1.430(5), P1-O1 1.624(3), Ru1-Cl1 2.4029(11), Ru1-P1 2.3250(11), Ru1-N1, 2.112(3) Cl1-
Ru1-P1 84.18(4), P1-Ru1-N1 93.54(9), N1-N2-N3 106.2(3), N2-N1-Ru1 118.4(3) O1-P1-Ru1
110.82(12), O1-C20-C19 105.7(3), N2-N3-C19 119.7(3), O1-P1-C27 99.91(18).
Figure 3. Molecular structure of 9. All hydrogen atoms have been omitted for clarity.
Displacement ellipsoids are drawn at the 50% probability level. Selected bond lengths (Å) and
bond angles (˚): N1-N2 1.349(3), N2-N3 1.319(3), N4-N5 1.343(3), N5-N6 1.313(3), Ru1-Cl1
2.4249(7), Ru1-P1 2.2668(6), P2-O2 1.6375(18), Ru1-P2 2.2436(7), Ru1-C45 2.256(2), P2-
C29 1.837(2), P2-Ru1-P1 93.10(2), P2-Ru1-Cl1 93.47(2), N1-N2-N3 106.89(19), P1-Ru1-Cl1
89.60(2), C45-Ru1-P1 121.19(8), Ru1-P1-O1 121.74(6), P1-O1-C13 122.31(14), C45-Ru1-
Cl1 89.81(8), Ru1-P1-C7 116.58(7), O2-C35-C36 107.35(18).
The coordination geometry around ruthenium centre in complex 9 described as pseudo
octahedral three-legged piano stool flanked by a chloride ion, two triazole-phosphinites and
η5–C5H5 moiety. The Ru1-P1 (2.2668(6) Å) and Ru1-P2 (2.2436(7) Å) bond lengths are
slightly longer when compared to the same in [CpRu{P(OMe)3}2Cl] (2.234(2) and 2.199(3) Å)
but are shorter than those observed in analogous complexes containing tertiaryphosphines.[12]
This may be attributed to the better π-acceptor nature of the phosphinite ligands compared to
tertiaryphosphines and their steric attributes as the M-P distances are sensitive to the bulkiness
10
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10.1002/ejic.201701058
European Journal of Inorganic Chemistry
of the phosphine ligands. The P1-Ru1-Cl1 and P2-Ru1-Cl1 bond angles are 89.60(2)°,
(93.47(2)°, respectively. The triazole ring with P1 is oriented above the Cl(1)-P2-P1 plane
whereas other triazole ring is in the plane of Cl(1)-P2-P1, but is slightly tilted.
Group 10 and 11 Metal Complexes of 2
Treatment of 2 with [M(COD)Cl2] (M = Pd or Pt) in 2:1 ratio afforded exclusively cis-
complexes, cis-[MCl2{Ph2POCH2CH2(1,2,3-N3C(Ph)C(H))}2] (Pd (11), Pt (12)) with the
31
ligand showing only P-coordination (Scheme 3). The P NMR spectra of complexes 11 and
12 showed singlets at 110.7 and 84.2 ppm, respectively. The large 1JPtP coupling of 4116 Hz is
consistent with the proposed cis-geometry[13] for 12. The 2:1 reaction between 2 and [PdCl(η3-
C3H5)]2 in dichloromethane gave [(PdCl(η3-C3H5){Ph2POCH2CH2(1,2,3-N3C(Ph)C(H))}]
1
(13). The 31P NMR spectrum of 13 showed a single resonance at 125.5 ppm. The H NMR
spectrum displayed two doublets at 3.72 and 4.72 ppm and a multiplet at 5.49 ppm for allylic
protons. The 1:1 reaction of 2 with [AuCl(SMe2)] in dichloromethane at room temperature
yielded [Au(Cl){Ph2POCH2CH2(1,2,3-N3C(Ph)C(H))}] (14). The 31P NMR spectrum presents
a single resonance at 117.3 ppm. The 1H NMR confirms the presence of triazolic proton which
appears at 7.72 ppm.
Scheme 3 Palladium(II), Platinum(II) and Gold(I) complexes of 2
11
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10.1002/ejic.201701058
European Journal of Inorganic Chemistry
The molecular structures of 11 and 12 are depicted in Figures 4 and 5. Crystal data and the
details of the structure determination are given in the Experimental section, while pertinent
bond distances and bond angles appear in respective figure captions.
The asymmetric unit of 11 contains one molecule of metal complex and one molecule of
dichloromethane as solvent of crystallization. The palladium adopts square-planar geometry,
coordinated by two chlorine and two phosphorus atoms. The bond distances: Pd1-P2
(2.2471(5) Å), Pd1-P1 (2.2480(5) Å), Pd1-Cl2 (2.3392(5) Å) and Pd1-Cl1 (2.3567(5) Å) are
normal and comparable with those observed in other PdII complexes.[14] The bond angles P2-
Pd1-P1 (96.77(14)°), Cl2-Pd1-Cl1 (90.89(17)°), Cl1-Pd1-P1 (85.42(17)°) and Cl2-Pd1-P2
(87.15(18)°) clearly indicate the distortion in the square-planar geometry. Both the triazole
rings are displaced from Pd—P square-plane with P1-O1-C13-C14, P2-O2-C35-C36, O2-C35-
C36-N4 and O1-C13-C14-N1 torsion angles being -151.64(13)°), 178.37(12)°, 67.38(19)°) and
64.1(2)°, respectively. Molecules of 11 appear to be associated via intermolecular hydrogen
bonding, some important one are as follows; C22-H22…N3 (2.58 Å), C10-H10…Cl1 (2.80
Å), C2-H2…O1 (2.37 Å) and C24-H24…O2 (2.46 Å).
12
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10.1002/ejic.201701058
European Journal of Inorganic Chemistry
Figure 4. Molecular structure of 11. All hydrogen atoms have been omitted for clarity.
Displacement ellipsoids are drawn at the 50% probability level. Selected bond lengths (Å) and
bond angles (˚): Pd1-Cl1 2.3567(5), Pd1-Cl2 2.3392(5), Pd1-P2 2.2471(5), Pd1-P1 2.248(5),
P2-O2 1.6062(13), O2-C35 1.452(2), P2-C29 1.8159(19), P2-C23 1.809(2), N4-N5 1.346(2),
Cl2-Pd1-Cl1 90.893(17), Cl2-Pd1-P2 87.154(18), P2-Pd1-P1 96.774(18), Cl1-Pd1-P1
85.425(17), C29-P2-Pd1 118.14(6), O2-P2-C23 100.44(8), Pd1-P2-O2 112.10(5), C29-P2-C23
99.50(9), N1-N2-N3 107.22(16).
The molecular structure of 12 is isostructural with 11. The average Pt—P distance is 2.2300(6)
Å. The Cl(2)-Pt(1)-P(1) angle is 173.153(17)°, whereas the Cl(1)-Pt(1)-P(1) angle is
86.473(19)°. As in 11, weak hydrogen bonding exists in the crystal lattice, viz, C12-H12…O1
(2.38 Å, 108°), C22-H22…N3 (2.58 Å, 100°) and C37-H37...Cl2 (2.76 Å, 148°).
Figure 5. Molecular structure of 12. All hydrogen atoms have been omitted for clarity.
Displacement ellipsoids are drawn at the 50% probability level. Selected bond lengths (Å) and
bond angles (˚): Pt1-Cl1 2.3631(6), Pt1-Cl2 2.3489(6), Pt1-P2 2.2262(6), Pt1-P1 2.2305(6),
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P1-O1 1.6125(14), P1-C7 1.805(2), N1-N2 1.347(2), N2-N3 1.312(3), Cl2-Pt1-Cl1
88.260(19), Cl1-Pt1-P1 86.473(19), P2-Pt1-P1 97.049(19), Cl2-Pt1-P1 173.153(17), C7-P1-
Pt1 113.59(6), O1-P1-C7 99.17(8), C1-P1-C7 107.01(9), O1-P1-C1 102.60(8), Cl1-Pt1-P2
176.156(16).
Conclusions
In summary, this paper describes a hemilabile phosphinite ligand [Ph2POCH2CH2(1,2,3-
N3C(Ph)C(H))], its chalcogenides and some transition metal complexes. The ligand displays
both mono- and bidentate [(-P,N) and (-P,N)] modes of coordination. The reaction of
phosphinite with [Ru(η6-cymene)Cl2] led to the isolation of a mononuclear complex which on
further treatment with silver triflate yielded a dimeric cationic complex, with ligand showing
bridging (-P,N) coordination mode. The reactions of [CpRuCl(PPh3)2] with phosphinite
afforded both mono- and disubstituted ruthenium(II) complexes. Hemilabile functionalities are
very useful in homogeneous catalysis to stabilize electronically unsaturated species in-between
oxidative addition and reductive elimination reactions and also after the organic
transformation. At present we are exploring the catalytic reactions of palladium(II) and
ruthenium(II) complexes in cross-coupling, cyclization and transfer-hydrogenation reactions.
Experimental Section
General Procedures. All manipulations were performed using standard vacuum-line, in oven
dried glassware under nitrogen atmosphere. All the solvents were purified by conventional
procedures and distilled prior to use. The compounds 2-azido-ethanol[15] and metal reagents
[Ru(η6-p-cymene)Cl2]2,[16] [CpRu(PPh3)2Cl],[17] [M(COD)Cl2] (M = Pd, Pt),[18] [PdCl(η3-
C3H5)]2,[19] and [AuCl(SMe2)][20] were prepared according to the published procedures. Other
chemicals were obtained from commercial sources and purified prior to use.
Instrumental Methods. The NMR spectra were recorded at the following frequencies: 400
MHz (1H), 100 MHz (13C), 162 MHz (31P) ( in ppm) using either Varian VXR 400 or Bruker
14
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AV 400 or Bruker AV 500 spectrometers. The spectra were recorded in CDCl3 (or DMSO-d6)
solutions with CDCl3 (or DMSO-d6) as an internal lock; TMS and 85% H3PO4 were used as
external standards for 1H and 31P{1H} NMR, respectively. Positive shifts lie downfield to the
standard in all of the cases. Infrared spectra were recorded on a Nicolet Impact 400 FTIR
instrument in KBr disk or nujol mull. The microanalyses were performed using a Carlo Erba
Model 1112 and flash EA 1112 series elemental analyzer. Mass spectra were recorded using
Waters Q-Tof micro (YA-105), maXis impact and 410 Prostar Binary LC. The melting points
of all compounds were determined on a Veego melting point apparatus and are uncorrected.
Synthesis of [HOCH2CH2(1,2,3-N3C(Ph)C(H))] (1): 2-Azidoethanol (0.81 g, 9.3 mmol) and
phenylacetylene (0.950 g, 9.3 mmol) were suspended in a 1:1 mixture of water and
dichloromethane. Sodium ascorbate (1.1 mmol, freshly prepared solution in water) was added
followed by CuSO4.5H2O (3.7 mmol, freshly prepared solution in water). The mixture was
stirred for 24 h at room temperature and the product was extracted with dichloromethane. The
combine dichloromethane extracts were kept over Na2SO4 and concentrated under reduced
pressure to give white solid. Yield: 75% (1.32 g). Mp: 86-88 °C. Anal. Calcd. for C10H11N3O:
C, 63.12; H, 5.55; N, 21.13. Found: C, 63.48; H, 5.86; N, 21.45.1H NMR (CDCl3): δ 3.16 (s,
br, OH, 1H), 4.14 (t, 3JHH = 5 Hz, CH2, 2H), 4.51 (t, 3JHH = 5 Hz, CH2, 2H), 7.26-7.74 (m, Ph,
5H), 7.82 (s, CH, 1H). ESI-MS(+) (m/z): 188.1 [M-H]+.
Synthesis of [Ph2POCH2CH2(1,2,3-N3C(Ph)C(H))] (2): Chlorodiphenylphosphine (1.47
mL, 8.02 mmol) was added dropwise to a mixture 1 (1.5 g, 8.02 mmol) and triethylamine (1.11
mL, 8.02 mmol) in THF (70 mL) at room temperature. After the completion of addition, the
reaction mixture was stirred for 18 h and then filtered through celite to remove amine
hydrochloride salt. Solvent was removed under reduced pressure to obtain 2 as a white solid.
Yield: 76% (2.27 g). Mp: 92-94 °C. Anal. Calcd for C22H20N3OP: C, 71.1; H, 5.97; N, 10.84.
Found: C, 71.0; H, 5.85; N, 10.81. 1H NMR (400 MHz, CDCl3): δ 4.27 (m, CH2, 2H), 4.64 (t,
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13
3JHH = 5 Hz, CH2, 2H), 7.26-7.73 (m, Ph, 15H), 7.66 (s, CH, 1H). C{1H} NMR (100 MHz,
CDCl3): δ 147.7, 130.8, 130.6, 129.9, 128.89, 128.7, 128.6, 128.2, 125.8, 120.9, 68.3, 51.6.
31P{1H} NMR (162 MHz, CDCl3): δ 117.6 (s). MS(EI,m/z): 374.14 [M+H]+.
Synthesis of [Ph2P(O){OCH2CH2(1,2,3-N3C(Ph)C(H))] (3): A 30% aqueous solution of
H2O2 (0.007 g, 0.025 mL, 0.249 mmol) in THF (5 mL) was added dropwise to a well-stirred
THF solution (10 mL) of 2 (0.0846 g, 0.227 mmol) and stirring was continued for 5 h at room
temperature. The solvent was removed under reduced pressure to give 3 as off white liquid.
Yield: 89% (0.791 g). Anal. Calcd for C22H20N3O2P: C, 67.84; H, 5.18; N, 10.79. Found: C,
67.58; H, 5.26; N, 10.69. 1H NMR (CDCl3): δ 4.34 (s, br, CH2, 2H), 4.63 (s, br, CH2, 2H), 7.15-
7.66 (m, Ph, 15H), 7.82 (s, CH, 1H). 31P{1H} NMR (CDCl3): δ 35.9 (s). ESI-MS (m/z): 390.13
[M+H]+.
Synthesis of [Ph2P(S)OCH2CH2(1,2,3-N3C(Ph)C(H))] (4): A mixture of 2 (0.136 g, 0.3646
mmol) and sulfur (0.0116 g, 0.3646 mmol) in toluene (20 mL) was refluxed for 18 h. Then the
solution was cooled to room temperature and filtered through celite. The solvent was removed
under reduced pressure to get compound 4 as a white residue. Yield: 87% (0.128 g). Anal.
Calcd for C22H20N3OSP: C, 65.17; H, 4.97; N, 10.36; S, 7.91. Found: C, 65.19; H, 4.75; N,
10.50; S, 7.55. 1H NMR (CDCl3): δ 4.45 (t, 3JHH = 5 Hz, CH2, 2H), 4.73 (t, 3JHH = 5 Hz, CH2,
31
2H), 7.13-7.80 (m, Ph, 15H), 7.89 (s, CH, 1H). P{1H} NMR (CDCl3): δ 84.04 (s). ESI-MS
(m/z): 406 [M+H]+.
Synthesis of [Ph2P(Se)OCH2CH2(1,2,3-N3C(Ph)C(H))] (5): A mixture of 2 (0.068 g, 0.1816
mmol) and selenium (0.0143 g, 0.1816 mmol) in toluene (25 mL) was refluxed for 18 h. Then
the solution was cooled to room temperature and filtered through celite. The solvent was
removed under reduced pressure to give analytically pure product of 5 as a colorless
microcrystalline residue. Yield: 89% (0.073 g). Anal. Calcd for C22H20N3OSeP: C, 58.41; H,
4.46; N, 9.29. Found: C, 58.79; H, 4.56; N, 9.66. 1H NMR (CDCl3): δ 4.47 (m, CH2, 2H), 4.74
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(t, 3JHH = 6 Hz, CH2, 2H), 7.15-7.79 (m, Ph, 15H), 7.80 (s, CH, 1H). 31P{1H} NMR (CDCl3):
δ 88.1 ppm (s, 1JPSe= 808 Hz). ESI-MS (m/z): 453.13 [M+H]+.
Synthesis of [Ru(η6-cymene)Cl2{Ph2POCH2CH2(1,2,3-N3C(Ph)C(H))}] (6):
A
dichloromethane solution (5 mL) of [Ru(η6-cymene)Cl2]2 (0.026 g, 0.0427 mmol) was added
dropwise to a solution of 2 (0.032g, 0.0804 mmol) in the same solvent at room temperature.
The resultant solution was stirred for 4 h at room temperature and the solvent was removed
under reduced pressure to give 6 as a dark red solid. The X-ray quality crystals were obtained
by recrystallizing it in a mixture of CH2Cl2-petroleum ether (2:1) at RT. Yield: 63% (0.036 g).
Mp: 202 °C. Anal. Calcd. for C32H34N3OCl2PRu: C, 56.56; H, 5.04; N, 6.18. Found: C, 56.36;
H, 5.01; N, 6.50. 1H NMR (400 MHz, CDCl3): δ 1.03 (d, 3JHH = 6.9 Hz, ipr-CH3, 6H), 1.83 (s,
p-CH3, 3H), 2.61 (sept, 3JHH = 6.9 Hz, ipr-CH, 1H), 4.2 (q, 3JHH = 5 Hz, CH2, 2H), 4.53 (t, CH2,
3
3
2H), 5.15 (d, JHH = 6.3 Hz, Ph-CH, 2H), 5.18 (d, JHH = 6.3 Hz, Ph-CH, 2H), 7.25-7.85 (m,
Ph, 15H), 7.95 (s, CH, 1H). 31P{1H} NMR (162 MHz, CDCl3): 118.8 (s). MS (m/z): 644.11
[M-Cl]+.
Synthesis of [Ru(η6-cymene)(Cl){Ph2POCH2CH2(1,2,3-N3C(Ph)C(H))}]2(OTf)2 (7):
A
dichloromethane solution (5 mL) of [Ru(η6-cymene)Cl2]2 (0.026 g, 0.0427 mmol) was added
dropwise to a solution of 2 (0.032g, 0.0804 mmol) in the same solvent at room temperature.
The resultant solution was stirred for 4 h at room temperature. Then in the same solution was
added AgOTf (0.0206g, 0.0804 mmol). Then stirred this mixture for 1 h. Filtered it through
celite.The solvent was removed under reduced pressure to afford the product 7 as an orange
solid. The X-ray quality crystals were obtained by recrystallizing it in a mixture of CH2Cl2-
petroleum ether (2:1) at RT. Yield: 77% (0.098 g). Mp: 125-127 °C. Anal. Calcd. for
C66H68N6O8Cl2F6P2Ru2S2: C, 49.96; H, 4.32; N, 5.29; S, 4.04. Found: C, 50.36; H, 4.30; N,
5.41; S, 4.30. 1H NMR (400 MHz, CDCl3): δ 0.96 (d, 3JHH = 6.6 Hz, ipr-CH3, 12H), 2.16 (s, p-
CH3, 6H), 2.97 (sept, 3JHH = 6.6 Hz, ipr-CH, 2H), 4.2 (q, 3JHH = 5 Hz, CH2, 4H), 4.54 (t, 3JHH
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3
3
= 5 Hz, CH2, 4H), 5.7 (d, JHH = 5.9 Hz, Ph-CH, 4H), 5.83 (d, JHH = 6.0 Hz, Ph-CH, 4H),
7.25-7.85 (m, Ph, 30H), 7.95 (s, CH, 2H).31P{1H} NMR (162 MHz, CDCl3): 120.9 (s).
Synthesis of [CpRuCl{Ph2POCH2CH2(1,2,3-N3C(Ph)C(H))}PPh3] (8): A dichloromethane
(4 mL) solution of [CpRu(PPh3)2Cl] (0.029 g, 0.040 mmol) was added to a solution of 2 (0.015
g, 0.040 mmol) also in dichloromethane (6 mL) and the solution was stirred for 2 days at room
temperature. The yellow solution obtained was concentrated under reduced pressure and the
yellow residue obtained was washed 4-5 times with petroleum ether to remove PPh3, dried in
vacuo to give 8 as analytically pure yellow microcrystals. Yield: 86% (0.029 g). Mp: 97-100
°C. Anal. Calcd. for C45H40N3OClP2Ru: C, 64.55; H, 4.81; N, 5.01. Found: C, 64.40; H 4.80;
N, 5.19. 1H NMR (400 MHz, CDCl3): δ 3.61-3.63 (m, CH2, 2H), 4.10 (m, CH2, 2H), 4.22 (s,
Cp, 5H), 6.76-8.01 (m, Ph, 30H), 8.0 (s, CH, 1H). 31P{1H} NMR (162 MHz, CDCl3): 43.9 (d),
144.9(d) (2JPP = 58 Hz). ESI-MS(m/z): 802.16 [M-Cl]+.
Synthesis of [CpRuCl{(Ph2POCH2CH2(1,2,3-N3C(Ph)C(H))}2] (9): A toluene (4 mL)
solution of [CpRu(PPh3)2Cl] (0.029 g, 0.040 mmol) was added to a solution of 2 (0.030 g,
0.080 mmol) also in toluene (6 mL). The reaction mixture was then refluxed for 24 h and the
orange solution formed was dried under reduced pressure and the orange residue obtained was
washed 4-5 times with petroleum ether to remove PPh3. The X-ray quality crystals were
obtained by recrystallizing the residue in a mixture of CH2Cl2-petroleum ether (2:1) at 25 oC.
Yield: 78% (0.030 g). Mp: 185-190 °C. Anal. Calcd. for C49H45N6O2ClP2Ru: C, 62.05; H, 4.78;
1
N, 8.86. Found: C, 61.9; H, 4.69; N, 8.64. H NMR (400 MHz, CDCl3): δ 3.7-3.8 (m, CH2,
4H), 4.09-4.11 (m, CH2, 4H), 4.42 (s, Cp, 5H), 7.0-7.86 (m, Ph, 30H), 8.0 (s, CH, 2H). 31P{1H}
NMR (162 MHz, CDCl3): 146.6 (s).
Synthesis of [CpRu{Ph2POCH2CH2(1,2,3-N3C(Ph)C(H))}2](OTf) (10): AgOTf (0.0032 g,
0.0126 mmol) was added to a solution of 9 (0.012 g, 0.0126 mmol) also in dichloromethane (6
mL). The reaction mixture was then stirred for 3 h at room temperature. Filtered it through
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celite to remove silver chloride salt. The yellow solution was then concentrated to 1 mL,
saturated with 3 mL petroleum ether, filtered and dried under vacuo to give 10 as analytically
pure yellow color product. Yield: 81% (0.011 g). Mp: 87 °C. Anal. Calcd. for
C50H45N6O5P2RuF3S: C, 56.55; H, 4.27; N, 7.91; S, 3.01. Found: C, 56.43; H, 4.04; N, 8.12; S,
1
3.18. H NMR (400 MHz, CDCl3): δ 3.7-3.8 (m, CH2, 4H), 4.09-4.11 (m, CH2, 4H), 4.42 (s,
Cp, 5H), 7.0-7.86 (m, Ph, 30H), 7.88 (s, CH, 2H). 31P{1H} NMR (162 MHz, CDCl3): 145.0
(d), 148.5 (d) (2JPP = 59 Hz). ESI-MS (m/z) 913.23 [M+H-OTf]+.
Synthesis of cis-[PdCl2{Ph2POCH2CH2(1,2,3-N3C(Ph)C(H))}2] (11): A solution of 2 (0.061
g, 0.163 mmol) in dichloromethane (5 mL) was added to [Pd(COD)Cl2] (0.023 g, 0.081 mmol)
dissolved in dichloromethane (4 mL). The reaction mixture was allowed to stir at room
temperaturefor 4 h.The solution was concentrated to 2 mL and stored at room temperature to
give analytically pure yellow crystals. X-ray quality crystals were obtained by recrystallizing
it in mixture of CH2Cl2/petroleum ether.Yield: 81% (0.040 g). Mp: 199-200 ºC (dec.). Anal.
Calcd for C45H42N6O2P2Cl4Pd: C, 53.56; H, 4.19; N, 8.33. Found: C, 53.21; H, 4.39; N, 8.48.
1H NMR (400 MHz, CDCl3): δ 4.05 (s, br, CH2, 4H), 4.33 (s, br, CH2, 4H), 5.12 (s, CH2Cl2,
2H), 7.26-7.70 (m, Ph, 30H), 7.72 (s, CH, 2H). 31P{1H} NMR (162 MHz,CDCl3): 110.7 ppm
(s). MS (m/z): 887.14 [M-Cl]+.
Synthesis of cis-[PtCl2{Ph2POCH2CH2(1,2,3-N3C(Ph)C(H))}2] (12): A solution of 2 (0.030
g, 0.080 mmol) in dichloromethane (5 mL) was added [Pt(COD)Cl2] (0.015 g, 0.040 mmol)
dissolved in dichloromethane (2 mL). The reaction mixture was allowed to stir at room
temperaturefor 4 h.The solution was concentrated to 2 mL and stored at room temperature to
give analytically pure white crystal. X-ray quality crystals were obtained by recrystallizing it
in mixture of CH2Cl2/petroleum ether.Yield: 76% (0.044 g). Mp: 197 ºC. Anal. Calcd for
C45H42N6O2P2Cl4Pt: C, 49.23; H, 3.85; N, 7.65. Found: C, 49.56; H, 3.64; N, 8.12. 1H NMR
(400 MHz, CDCl3): δ 4.07 (q, 1JHH = 4.9 Hz, CH2, 4H), 4.32 (t, 1JHH = 4.9 Hz, CH2, 4H), 5.22
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(s, CH2Cl2, 2H), 7.25-7.73 (m, Ph, 30H), 7.74 (s, CH, 2H). 31P{1H} NMR (162 MHz,CDCl3):
84.2 ppm (s, 1JPtP = 4116 Hz). MS (m/z): 976.20 [M-Cl]+.
Synthesis of [Pd(η3-C3H5)Cl{Ph2POCH2CH2(1,2,3-N3C(Ph)C(H))}] (13): A solution of
[PdCl(η3-C3H5)]2 (0.0264 g, 0.0723 mmol) in dichloromethane (5 mL) was added dropwise to
a solution of 2 (0.054 g, 0.1443 mmol) also in dichloromethane (5 mL) at room temperature
and stirred for 4 h. The solvent was removed under vacuum, washed with 4×3 mL of petroleum
ether, filtered and dried under vacuo to give analytically pure product of 13 as a yellow solid.
Yield: 59% (0.048 g). Mp: 79-82 °C (dec.). Anal Calcd for C25H25N3OClPPd: C, 53.98; H,
4.53; N, 7.55. Found: C, 54.01; H, 4.50; N, 7.87. 1H NMR (CDCl3): δ 3.72 (d, anti, 2JHH = 13
3
Hz , CH2, 2H), 4.43 (t, 3JHH = 5 Hz, CH2, 2H), 4.46 (q, JHH = 5 Hz, CH2, 2H), 4.72 (d, syn,
2JHH = 7.6 Hz, CH2, 2H), 5.49 (sept, 3JHH = 9.3 Hz, CH, 1H), 7.26-7.86 (m, Ph, 15H), 8.06 (s,
CH, 1H). 31P{1H} NMR (CDCl3): 125.5 (s). MS (m/z): 520.07 [M-Cl]+.
Synthesis of [AuCl{Ph2POCH2CH2(1,2,3-N3C(Ph)C(H))}] (14): To a solution of 2 (0.041
g, 0.1093 mmol) in 5 mL of CH2Cl2, was added AuClSMe2 (0.032 g, 0.1093 mmol) dissolved
in 3 mL CH2Cl2 and the mixture was stirred for 4 h at room temperature. The solvent was
removed under vacuum, washed with 4×3 mL of pet ether, filtered and dried under vacuo to
give analytically pure product 14 as a colorless solid. Yield: 71% (0.047 g). Mp: 141 ºC (dec.).
Anal. Calcd. for C22H20N3OClPAu: C, 43.62; H, 3.33; N, 6.94. Found:. C, 43.21; H, 3.23; N,
7.07. 1H NMR (CDCl3): 4.52 (q, 3JHH = 5 Hz, CH2, 2H, 4.76 (t, 3JHH = 5 Hz, CH2, 2H,), 7.37 -
7.80 (m, Ph, 15H), 7.72( s, CH, 1H). 31P{1H} NMR (CDCl3): 117.25 ppm.
Single-Crystal X-ray Crystallography: A crystal of each of the compounds in the present
work suitable for X-ray crystal analysis were mounted on a Cryoloop with a drop of Paratone
oil and placed in the cold nitrogen stream of the Kryoflex attachment of the Bruker APEX CCD
diffractometer. Full spheres of data were collected using a combination of three sets of 606
scans in ω (0.3º per scan) at φ = 0, 120 and 240º or 3 sets of 400 frames, each of width 0.5º in
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ω, collected at φ = 0.00, 90.00 and 180.00º and 2 sets of 800 frames, each of width 0.45º in φ,
collected at ω = -30.00 and 210.00 under the control of the APEX2 program suite.[21] The few
of the crystals used for the structure determinations proved to be twinned by a 180° rotation
about the a axis or by a 180° rotation about the c axis (CELL_NOW).[22] The raw data were
reduced to F2 values using the SAINT+ software[23] and a global refinement of unit cell
parameters using ca. 7662-112534 reflections chosen from the full data sets were performed.
Multiple measurements of equivalent reflections provided the basis for an empirical absorption
correction as well as a correction for any crystal deterioration during the data collection
(SADABS or TWINABS)[24]. The structure 6 was solved by Patterson method while the
structures of 11 and 12 were solved by heavy atom method. All the other crystal structures
were solved by direct method and refined by full-matrix least-squares procedures using the
SHELXTL program package.[25] Hydrogen atoms attached to carbon were placed in calculated
positions and included as riding contributions with isotropic displacement parameters tied to
those of the attached non-hydrogen atoms. The details of X-ray structure determination are
given in Table 1.
Crystallographic data for the structures reported in this paper have been deposited with the
Cambridge Crystallographic Data Centre as supplementary publication no. CCDC 1572097
(compound 6), 1572100 (compound 7), 1572098 (compound 9), 1572099 (compound 11),
1572096 (compound 12).
Associated content
Supporting Information
NMR and mass spectra of compounds 1-14, X-ray crystallographic files in CIF format for the
structure determinations of compounds 6, 7, 9, 11 and 12.
AUTHOR INFORMATION
[a] Phosphorus Laboratory, Department of Chemistry
21
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10.1002/ejic.201701058
European Journal of Inorganic Chemistry
Indian Institute of Technology Bombay, Powai,
Mumbai 40076, India
*E-mail: krishna@chem.iitb.ac.in or msb_krishna@iitb.ac.in (M. S. Balakrishna),
http://www.chem.iitb.ac.in/people/Facutly/prof/msb.html
[b] Department of Chemistry, Tulane University,
New Orleans, Louisiana 70118, USA
Acknowledgements
We are grateful to the Science & Engineering Research Board, New Delhi, for financial support
of this work through grant No.SB/S1/IC-08/2014. We also thank the Department of Chemistry
Instrumentation Facilities, IIT Bombay, for spectral and analytical data and J.T.M. thanks the
Louisiana Board of Regents for the purchase of the APEX CCD diffractometer, an NSF-MRI
grant No. 1228232 for the purchase of the D8 VENTURE diffractometer and the Chemistry
Department of Tulane University for support of the X-ray laboratory. BC thanks UGC, New
Delhi for Research Fellowship (JRF & SRF).
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European Journal of Inorganic Chemistry
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European Journal of Inorganic Chemistry
Table S1. Crystallographic data for 6, 7, 9, 11 and 12.
6
7
9
11
12
Formula
FW
C32H34Cl2N3OPRu C66H68Cl2F6N6O8P2Ru2S2 C49H45ClN6O2P2Ru C45H42Cl4PdP2N6O2
C45H42Cl4N6P2PtO2
679.56
1586.36
948.37
1008.99
Triclinic
1097.68
Triclinic
Crystal system Monoclinic
Monoclinic
Monoclinic
Space group
a Å
P21/n
10.0211(9)
P21/n
9.2530(6)
P21/n
16.114(3)
Pī
Pī
12.3375(8)
12.348(2)
b Å
20.0738(18)
24.8662(15)
15.286(3)
12.3447(8)
12.383(2)
c Å
14.9671(13)
90.00
98.564(1)
90.00
2977.2(5)
4
14.7576(9)
90
100.851(1)
90
3334.8(4)
2
17.576(4)
90.00
99.841(3)
90.00
4265.6(14)
4
15.903(1)
108.800(1)
100.164(1)
98.250(1)
2204.1(2)
2
15.867(3)
100.078(2)
108.830(2)
98.286(2)
2207.9(7)
2
α deg
β deg
γ deg
V Å3
Z
ρcalc gcm-3
µ(Mo Kα),
mm-1
1.516
0.791
1.580
0.720
1.477
0.554
1.520
0.782
1.651
3.538
F(000)
1392
1616
1952
1028
1092
crystal size,
mm
0.09×0.13×0.26
0.10×0.12×0.25
0.08×0.25×0.32
0.09×0.12×0.25
0.12×0.23×0.25
T (K)
100(2)
100(2)
100(2)
100(2)
2.5-29.1
39512
100(2)
2θ range, deg
Total reflns
indep. reflns
2.29-29.20
55162
8022 [Rint=0.037] 116566[Rint=0.066]
2.2-28.3
116566
2.3-29.03
74427
2.5-29.1
39445
11185 [Rint = 0.031]
10962 [Rint = .049] 11181[Rint = 0.036]
R
wR2
S
0.0257
0.0614
1.084
0.0542
0.1218
1.023
0.0414
0.1033
1.02
0.0304
0.0807
1.04
0.0197
0.0497
1.04
26
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