Polyhedron 143 (2018) 2–10

Contents lists available at ScienceDirect

Polyhedron
journal homepage: www.elsevier.com/locate/poly

Review

Unusual and rare pincer ligands: Synthesis, metallation, reactivity and

catalytic studies
M.S. Balakrishna
Phosphorus Laboratory, Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400 076, India

a r t i c l e i n f o a b s t r a c t

Article history: The growing interest in pincer ligand synthesis and their transition metal chemistry is due to their
Received 16 June 2017 remarkable thermal stability to tolerate harsh reaction conditions during catalysis. In last one decade sev-
Accepted 26 July 2017 eral pincer ligands have been synthesized and their metal chemistry and catalytic applications have been
Available online 29 July 2017
explored. This article summarizes briefly the synthesis and metal complexes of a few rare and unusual
pincer ligands, viz, cyclodiphosphazane appended PCP, tri- and tetrametaphosphacyclophanes, triazole
Keywords: based PCP, PCS and PCN systems, SiPSi and PCyP pincer ligands.
Pincer
Ó 2017 Elsevier Ltd. All rights reserved.
Phosphametacyclophane
Cyclodiphosphazane
Hydrogenation
Dehydrogenation

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Cyclodiphosphazane based pincer derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1. Catalytic P-arylation reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3. Tri- and tetrametaphosphacyclophanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
4. SiPSi type pincer ligands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
5. Triazole based pincer ligands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
6. Cyclohexane based PCP pincer ligands . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
6.1. Dehydrogenation reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
6.2. Deuterium exchange reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
7. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

1. Introduction
The enormous success of pincer ligands and their metal
complexes in metal mediated organic transformations [1–3] is
essentially due to: i) the robust tridentate coordination, ii) the
metal–ligand cooperation and, iii) the high thermal and the kinetic
stability. Isolation of ortho-metallated complexes and subsequent
reports on tridenate ligands by Shaw [4,5] motivated and diverted
several groups into the fold of pincer chemistry resulting in the
establishment of a variety of pincer ligand systems [6–9]. The enor-
E-mail address: krishna@chem.iitb.ac.in
mous growth of pincer chemistry in the last decade is mainly due
to their application in homogeneous catalysis [10], in particular
activation of Csp3–Csp3 and Csp3–H bonds [11–14]. Significant contri-
butions from the laboratories of van Koten [15], Milstein [8], Gold-
man [16], Ozerov, Yamashita [17], Wendt and several others
[16,18] expanded the scope of pincer complexes to many facets
of transition metal chemistry and catalytic applications. Several
reviews [16,19,20], accounts [10,14,21] and books [15,22,23] pub-
lished in the last 10 years indicate the popularity of pincer
chemistry.
The main objective of this review is to focus on unusual, rare
and miscellaneous pincer ligand systems (Chart 1) containing

http://dx.doi.org/10.1016/j.poly.2017.07.026
0277-5387/Ó 2017 Elsevier Ltd. All rights reserved.
 M.S. Balakrishna / Polyhedron 143 (2018) 2–10 3

Cyclophosphazane based pincer ligand 2,6-{(m-NtBu)P(tBuHN)

O O PO}2C6H3I (1) was synthesized by reacting chlorophosphazane
N
cis-{ClP(m-NtBu)2PN(H)tBu} with 2-iodoresorcinol [24].
O
O O P Ph P O The reactions of 2,6-{(m-NtBu)P(tBuHN)PO}2C6H3I (1) with Ni
t Bu
N I t Bu Ph (COD)2, Pd2(dba)3
CHCl3 and Pt(PPh3)4 afforded the corresponding
tBu P P N Ph
t Bu
N N pincer complexes, [2,6-{(m-NtBu)P(tBuHN)PO}2C6H3MI] (M = Ni (2),
HN t Bu N P
P N P NH Pd (3) and Pt(4)) (Scheme 1). Complexes 2–4 with uncoordinated
t Bu
O O phosphorus centers as well as amine functionalities can be used
for constructing homo- or heteronuclear complexes and high
Balakrishna [24, 25] nuclearity clusters with appropriate metal reagents.
The palladium complex 3 on treatment with two equivalents
of CuI or CuBr produced rhombic [Cu2X2] bridged macrocycles
N N N N N N
[{2,6-{(m-NtBu)P(tBuHN)PO}2C6H3PdI}{Cu2X2}]2 (X = Br(5), I(6)).
N N N Molecular structures of 2, 3, 5 and 6 have been confirmed by
X-ray analysis. The crystal structure of iodo derivative 6 depicted
N
R 2P PR 2 SPh PR2 PPh 2 Pd–I


Cu interactions with one of the copper atoms with Cu–IPd
distance of 2.930(1) Å, whereas the average Cu–I bond distance is
Gandelman [26] 2.557 Å (Chart 2). In the case of bromo derivative 5 alternate cop-
per atoms are coordinated with water molecules which showed
weak interactions with the palladium bound iodine atom with a
Ph H


I distance of 2.239 Å and O–H


I bond angle of 171.8°.

P
H H
Si Si
Me Me
Me Me Pt Bu 2
Sabo-Eenne [27]
Chart 1. Pincer ligands.
mainly phosphorus donor atom(s). The synthetic procedures, the
reactivity and the catalytic applications of these pincer systems
are briefly discussed.
2. Cyclodiphosphazane based pincer derivatives
Cyclodiphosphazanes are four-membered saturated inorganic
rings containing phosphorus and nitrogen atoms arranged alter-
nately with phosphorus in trivalent state [29–31]. Due to the
negative hyper conjugation involving N(2p) ? P(r⁄) interaction,
P–N bonds show double bond character and are relatively shorter
compared to the normal P–N single bond distances. The geometry
around nitrogen atoms is trigonal planar with sum of the bond
angles close to 360°. Cyclodiphosphazanes have been extensively
studied in the last 2 decades because of their remarkable utility
in main group [32–34] and transition metal chemistry [35] as anio-
nic or neutral ligands, macrocyclic chemistry [36] as linkers, birad-
ical chemistry [37,38] and, their catalytic [39–42] and biological
applications [43–45] as potential antitumor reagents. Pincer
ligands appended with cyclodiphosphazane moieties have also
been prepared and their coordination chemistry has been explored.
2.1. Catalytic P-arylation reactions
PtBu 2 Aryl phosphine oxides find applications in polymer chemistry
[46], photoelectric materials [47], and also as ligands in transition
and lanthanoid chemistry and catalysis [48]. Synthesis of arylphos-
Wendt [28]
phine oxides using Li or Mg reagents is not ideally suitable because
they lack functional groups tolerance and hence metal mediated C–
P bond forming reactions are preferred [46,49]. Several palladium
[50], nickel [51] and copper [52] based catalysts have been
employed for the preparation of aryl phosphonates and phosphine
oxides by P-arylation of H-phosphine oxides. Success of palladacy-
cles as catalysts in C–P bond forming reactions [50] prompted to
evaluate the catalytic efficiency of copper-palladium pincer com-
plex 3. The P-arylation reactions were performed under microwave
irradiation conditions.
The coupling of bromobenzene with diphenylphosphine oxide
using 3 mol% of palladium complex 3 and Cs2CO3 as a base at
100 °C under microwave irradiation resulted in the formation of
triphenylphosphine oxide in quantitative yield. Several arylphos-
phine oxides obtained are shown in Scheme 2. The coupling
reaction of 2-bromopyridine and 4-chloroacetophenone with
diphenylphosphine oxide were unsuccessful and yielded negligible
quantity of products.
3. Tri- and tetrametaphosphacyclophanes
Recently our group reported [25] the synthesis of bisphospho-
mides (A) and their pincer complexes and catalytic studies. Bispho-
sphomides were prepared by treating picolinoyldichloride and
isopathaloyl chloride with Ph2PH in the presence of a base in

Ni(COD)Cl2
HO OH
Pd2 (dba) 3.CHCl3 O
I O
O O OR
+ Et 3N, Et 2O t t t
Bu Bu Pt(PPh3 )4 t P M P Bu
N P I N Bu N N
t P
t t 0 oC Bu t t
Bu Bu
HN P t
t
Bu THF, Δ, 6h Bu N tBu I Bu N t
Bu
HN N Cl N BuN P HN P P NH
t NH
P P Bu 1
N 2 M = Ni, 3 M = Pd, 4 M = Pt
t
Bu
[COD = 1,5-Cyclooctadiene; dba = dibenzylideneacetone]

Scheme 1. Synthesis and complexation reactions of ligand 1.

4 M.S. Balakrishna / Polyhedron 143 (2018) 2–10

O O O O
tBu
tBu P Pd P tBu
N t P Pd P
N Bu N
t tBu tBu tBu N
N
Bu
HN I
N
P NH tBu N tBu tBu
N
tBu
P HN I P NH
H P
Cu Cu
H O Cu Cu
Br Br Br Br
O I I I
H I
Cu H Cu
Cu Cu
tBu tBu
P I tBu tBu
HN N But t P NH P I
BuN HN N tBu tBu N P NH
t
Bu N
P Pd P N tBu tBu N t
P Pd P N Bu
O O
O O
5
6

Chart 2. Metallomacrocycles containing two [Cu(l-X)2Cu] and two palladium-pincer units.

moderate yields as shown in Scheme 3. As a continuation, reaction
of picolinoyldichloride with PhPH2 in the presence of Et3N was car-
ried out. The equimolar reaction between PhPH2 and picoli-
noyldichloride led to the formation of both tri- (7) and
tetraphosphametacyclophanes (8) which were separated by frac-
tional crystallization. Both the compounds have been thoroughly
characterized by spectroscopic methods and by single crystal X-
ray analysis [25].
With an anticipation of forming a pincer complex, the reaction
of 7 with 1.5 equiv. of [Pd(g3-C3H5)Cl]2 was carried out, which
resulted in the formation of a hexapalladium(II) complex 9 con-
taining two pincer moieties with Pd–P covalent bonds, involving
the cleavage of two P–C bonds (Scheme 4). The broken acylium
ion (-C(O)+) containing fragment got allylated via nucleophilic
attack by allyl anions coming from [Pd(g3-C3H5)Cl]2 to form
coupling product, PhP{C(O)C5H3NC(O)-CH2CH = CH2}2 (10).

3 (3 mol%), Cs 2 CO3
ArBr Ph2 P(O)H ArP(O)Ph2
CH3 CN, MW,
10 min, 100 o C

O O O O O
PPh2 PPh 2 PPh2 MeO PPh 2 NC PPh2

94% 91% 95% 82% 69%

O
O O O
O PPh 2
P PPh2 PPh2
Ph2
O
79% OH MeO
43% 89% 92%

Scheme 2. Catalytic P-arylation reaction.

O O
O O
N
O O P
PhPH 2 , Et3 N N N
Cl Cl N
Et2 O Ph
Ph 2PH O O
P Ph Ph P O O
Et3N +
o
-78 C to RT P Ph Ph P
Ph Ph
16 h N N O
O
O O P N P N
N
PPh2 PPh 2 O O O O
A 8
7

Scheme 3. Synthesis of tri- and tetraphosphametacyclophanes.

 M.S. Balakrishna / Polyhedron 143 (2018) 2–10 5

O O O
O N
N Ph P N
Pd P Ph
O Ph Cl Cl
P P O 1.5 [Pd(allyl)Cl] 2 Cl O
Ph Pd Pd Pd Pd Ph P
Ph Cl Cl
N N Cl
O
P Ph P Pd P Ph
N N
O O
O O
7
9 10 O

Scheme 4. Reaction of 7 with [Pd(allyl)Cl]2.

Hexanuclear palladium(II) complex 9 is a rare example of dipincer 5. Triazole based pincer ligands
complex having both Pd–P covalent and coordinate bonds. The
molecular structure and composition was confirmed by extensive Pincer ligands appended to cyclic systems other than benzene
NMR studies, IR and mass spectral data, and also by single crystal (ECE) or pyridine (ENE) are less extensive. Only a few such pincer
X-ray analysis [25]. capable ligand systems have been studied (Chart 3). Herein, the
The molecule adopts an armchair conformation with bisphos- discussion is limited to the synthesis, metal chemistry and cat-
phomide units binding to palladium atoms in a pincer fashion via alytic applications of only triazole based pincer systems developed
both Pd–P covalent and coordination bonds. The lone pairs on by Gandelman’s group.
covalently bonded phosphorus and the phosphide end from two Pincer ligands 14–21 were prepared using typical copper(I)–
pincer units bridge the two [(g3-C3H5)Pd(l-Cl)2Pd] units to com- catalyzed [2+3] cycloaddition strategy popularly known as ‘‘click”
plete the hexanuclear core (Fig. 1). This is the first example of a reaction as depicted in Scheme 6 [26]. Reactions of ligands 14–21
pincer complex containing Pd–P covalent bonds. with [PdCl2(TMEDA)] (TMEDA = tetramethylethylenediamine), K2-
PdCl4 or PtCl2(COD) in DMF at 70 °C in the presence of Et3N pro-
4. SiPSi type pincer ligands duced the corresponding air-stable pincer complexes 22–29
(Scheme 7) [26]. Mixed donor ligands 16–19 on treatment with K2-
Another interesting and rare pincer ligand PhP{(o-C6H4CH2) PdCl4, [PdCl2(TMEDA)] or PtCl2(COD) at room temperature, even in
SiMe2H}2 (11) was reported [27] by Sabo-Etienne and co-workers, the absence of a base, afforded P,N-coordinated complexes 30–35,
in a one-pot reaction, by dilithiating PhP(o-tolyl)2 with nBuLi/ however, which on heating transformed to the corresponding pin-
TMEDA followed by the addition of Me2Si(H)Cl as shown in cer complexes [63]. Due to the presence of internal base (pyridine
Scheme 5. The reaction of 11 with [RuH2(H2)2(PCy3)2] in C6D6 at group), ligand 21, on treatment with Na2PdCl4 at room tempera-
20 °C inside the drybox resulted in 12. The compound was found ture give a mixture of both P,N-coordinated and PCN pincer com-
to be thermally stable up to 15 °C, however, on applying vacuum, pounds, which on heating in the presence of Et3N converted to
transformed to complex 13. Both the complexes 11 and 12 have pincer complex 29.
been structurally characterized. The structure of complex 12 is Addition of MeI to the pincer complex 23 resulted in triazolyli-
quite interesting if the two Si–H bonds considered to be coordi- dene complex 36 [64]. Similar reaction of platinum complex 24
nated to the ruthenium atom via egostic interactions and involved with 4-(trifluoromethyl)benzyl bromide afforded complex 36a
in Ru–H/Si–H exchange process (complex 12). The Ru–Si bond dis- (Scheme 8) which showed better solubility in organic solvents.
tances of 2.420(1) and 2.542(2) Å support the Si–H bond activation Reaction of 36 with silver triflate in 1:1 M ratio produced complex
leading to the formation of a nonclassical g2-Si–H bonds resulting 37 which on addition of another mole of AgOTf in acetonitrile
in a rare pincer complex. Due to the presence of Si–H bond in close yielded 38. Same reaction when carried out in THF under CO
proximity to the metal center in pincer complexes, interesting
coordination chemistry is anticipated from this ligand system
[27]. Also, pincer metal complexes of 12 and 13 may find utility
in hydrogenation and transfer hydrogenation reactions. Me Me
N N Me Me
Si Si
Li Li 2 ClSiMe2 H H H
N N
P
P 195 K Ph
Ph
11
2 nBuLi
hexane 2 TMEDA
RuH2 (H 2) 2(PCy 3) 2 20 o C
PhP(o-tolyl) 2
Me 2Si
Me2 Si
Cy 3P H
H
35 o C, -H2 H Ru P
Cy 3P Ru P Ph Ph
H H
o H
Me 2Si 20 C, +H 2
Si
Me 2
13 12

Fig. 1. Molecular structure of hexapalladium complex 9. Scheme 5. Synthesis and ruthenium complexes of 11.
6 M.S. Balakrishna / Polyhedron 143 (2018) 2–10

N N
N
N N
D1 D2
N N
D1=D2=PPh 2
D1=PPh2 ,D2=Py Pi Pr2 Pi Pr 2 PCy2 PCy 2 tBu
2P
D1=SPh, D2=PPh2

Gandelman [26] Fryzuk [53] Frech [54] Millstein [55]

N N
N N
N N N N N
t Bu
Ph2 P Ph2 P 2P M PtBu2
PPh2 Ph2 P Ph 2P
PPh 2 PPh2 Ph 2P

Rieger [56] Hahn [57] Lee [58] Wendt [28] Gandelman [59]

R 2P PR 2
N N
M M
N N N N N N
R 2P PR 2 B Ge
t t Bu P tBu P Pt Bu 2 Pi Pr 2
R = Ph, Cy, i Pr Bu 2P 2 2 Pi Pr2

Gade [60] Yamashita [17] Cabeza [61] Gelman [62]

Chart 3. Selected PCP pincer ligands with cyclic pivotal moieties. (See above-mentioned references for further information.)

O N N N N
i. CuSO4 /Na ascorbate, N N
Ph2 P N3 THF/H 2 O, 23 °C, 24 h
N ii.DABCO, 70 °C, 5 h, PR2 PhS PR2
R 2P
for 14 - 16 16 R = Ph
or or HSiCl3/NEt3 , 120 °C, 14 R = i Pr
17 R = o-MeOC6 H 4
BH3 12 h for 14 and 17 15 R = Ph
18 R = i Pr
PhS N3 R2 P 19 R = Cy
N N
R = Cy, C 6 H5 , i Pr, o-MeOC 6H 4 N N N
PhS N
PR2
R = P(o-MeOC 6 H4 )2 PPh 2 N
20 21

Scheme 6. Synthesis of triazole based pincer ligands.

atmosphere resulted in Pt–CO complex 39 with mCO at 2124 cm 1. N N

Me
I
This is a rare pincer complex containing 1,2,3-triazolylidene car- N
N N
bene moiety. N N MeI
N
i
Pr 2P Pd PiPr 2 N
Palladium complexes 22, 26, 28 and 29 were employed in Heck
reaction for probing their catalytic ability [26]. In a typical catalytic N 36 I R 2P M PR 2
Pd PPh2
reaction, methyl acrylate was reacted with bromobenzene in the Cl
29 Cl Na2 PdCl4 K2PdCl4 or
presence of above complexes (7  10 4 mol%) in dimethylfor- PdCl2(TMEDA) or M = Pd
Δ 22 R = Ph
mamide (solvent) using sodium carbonate at 140 °C for 48 h N N
PtCl2 (COD)
N N 23 R = i Pr
(Scheme 9). Complexes 22 and 29 showed good conversions (94% N n
BuLi
Et3N, DMF,
70 oC,12 h M =Pt
and 88%, respectively), whereas 26 and 28 showed very poor con- -78 Co
N
24 R = Ph
versions (29% and 5%). PhS Li PR2
E1 E2 25 R = i Pr
14-21
-LiCl [PdCl2 (TMEDA)] K2PdCl4 or
6. Cyclohexane based PCP pincer ligands PdCl2(TMEDA) M = Pd
or
PtCl2 (COD) 30 R = Ph
N N
Majority of PCP type pincer ligands reported to-date are aro- 31 R = o-MeOC6 H4
N Et3 N, Δ Cl
matic based or having 7-6-7 fused-ring systems, whereas PCP pin- Cl 32 R = i Pr
M
cers containing aliphatic backbone are less extensive. In this N N 33 R = Cy
PhS Pd PR2 PhS PR 2
N M = Pt
context, Wendt and co-workers have reported the improved syn- Cl 34 R = Ph
thesis [65] of cyclohexane-based pincer ligand 40 as shown in 26 R = Ph, 27 R = i Pr, 28 R = o-MeC6 H4 35 R = Cy
Scheme 10. Reaction of 40 with [Ir(COD)Cl2] in toluene at 170 °C
afforded 41 in 62% yield [28]. Scheme 7. Synthesis of palladium and platinum complexes of 22–35.
 M.S. Balakrishna / Polyhedron 143 (2018) 2–10 7

F3 C OTf
F3 C N N
Br
N N
N N N
p-CF3 C6 H4 CH 2 Br N AgOTf
N
Ph2 P Pt PPh2
Ph2 P Pt PPh2 CH 3CN
Ph2 P Pt PPh2
37 Cl
Cl
Cl 36a
24 2AgOTf CO AgOTf CH 3CN
THF

F3 C F3 C [OTf ]2
[OTf ]2 N N
N N
N N

Ph2 P Pt PPh2 Ph2 P Pt PPh2

CO 38 NCCH3
39

Scheme 8. Reactions of platinum complex 24.

carried out in the presence of 1 mM quantity of complex 41

Br COOMe
Cat. (Scheme 11A) [28]. The iridium complex 41 showed a turnover
COOMe
Na2 CO 3, DMF number (TON) of 50 after 24 h at 200 °C, with more than 30
140 o C, 48 h observed within the first ten min of the reaction. However, the cat-
5 mmol 6 mmol
alytic efficiency was found to be relatively low compared to the
Cat. loading: 7 x 10 -4 mol%
aromatic analogues. Aromatic PCP system [{2,6-(tBu2PO)2C6H3}Ir
Scheme 9. Heck reaction using complexes 22, 26, 28 and 29. (H)Cl] has demonstrated a TON of 1583 under identical reaction
conditions in 40 h [66]. Authors of this work correlated the low
activity to the low thermal stability of the catalytically active
6.1. Dehydrogenation reactions species. A very low TON of 5 was observed in the acceptorless
dehydrogenation of COA by 41 (Scheme 11 B). In view of the low
In a typical test reaction, transfer hydrogenation of cyclooctane thermal stability of 41, the dehydrogenation of tertiary amines
(COA) using tert-butylethylene (TBE) as a hydrogen acceptor was was considered as they do not require high temperature. At

i. [Ir(cod)Cl]2
I2, PPh 3
tBuLi, toluene, 170 oC
imidazole Et2O
ii. H2 , 160 o C
CH2 Cl2 ClPtBu2

Pt Bu 2 PtBu2
tBu P
2 Ir PtBu2
OH OH I I
H
40 41 Cl

Scheme 10. Synthesis of PCyP ligand 40 and its iridium complex 41.

cat, 1 mM
(A)
200 o C, 24 h

Cat. tBu 2P Ir PtBu 2

H
41 Cl
(B) cat, 1 mM

Δ, 18 h

(C) N N
cat, 1 mM

120 o C, 18 h N
toluene

Scheme 11. (A) Transfer hydrogenation of COA, (B) Acceptorless hydrogenation of COA and (C) Transfer hydrogenation of triethylamine by iridium complex 41.
8 M.S. Balakrishna / Polyhedron 143 (2018) 2–10

120 °C, a mixture of Et3N/TBE/Complex 41 taken in 100/200/1 ratio
in toluene showed a TON of 18.9 with relative yields of N,N-
diethylvinaylamine and N,N-divenylethylamine being, 15.7% and
1.6%, respectively (see Scheme 11C).
Aromatic-PCP-iridium pincer complexes have demonstrated
their efficiency in various dehydrogenation reactions, whereas
the aliphatic-PCP analogues due to the relatively low thermal sta-
bility, not so effective in dehydrogenation reactions. Wendt and co-
workers correlated the low thermal stability of PCyP-iridium com-
plexes to the behavior of the ligands due to the presence of all Csp3-
H bonds and are of the opinion that such system would show inter-
esting reactivity with coordinatively-unsaturated metal centers. In
this context, complex 41 was treated with tBuONa and PhH to form
a hydrido-phenyl complex (42) to make it appear like hydrido-
alkyl intermediate involved in dehydrogenation reactions. Com-
plex 42 is found to be extremely labile and also exhibit dynamic
behavior evinced by NMR studies. Addition of CO to 42 resulted
in 18 e species 43 (Scheme 12). IR spectrum of syn isomer (43-
syn) showed mCO at 1951 cm 1, whereas the same for anti-isomer
(43-anti) appeared at 1966 cm 1.
On heating the complex 42 at 120 °C in the presence of TBE,
complex 44 was formed in almost quantitative yield, which has
been structurally characterized. Complex 44 on exposure to
1 atm H2 at room temperature readily transformed into a mixture
of complexes 45 and 46 in 93:7 ratio. This ratio was found to be
temperature and pressure dependent; thus the ratio of 45:46 chan-
ged to 74:26, 86:14 and 98:2, respectively, at 4 °C, 8 °C and 25 °C,
under 1.5 atm of H2. On heating the mixture of 45 and 46 to 140 °C
for 24 h under H2 atmosphere, led to the formation of tetrahydride
complex 47 in which the Ccy–Ir bond is re-established [67]. This

H H H
H
t
Bu2 P Ir PtBu2 t
Bu2 P Ir PtBu2 + tBu2P Ir PtBu2
OC OC
H
41 Cl
t
BuONa, PhH
CO 43-syn 43-anti
65 oC

H H
t
Bu2 P Ir PtBu2 + t
Bu2 P Ir PtBu2
H H
H Δ H H
t
Bu2 P Ir PtBu2
t
Bu2 P Ir PtBu2

H H H H
42-syn 42-anti
48 47
-2 H 2 140 o C
120 o C

t
Bu2 P Ir PtBu t
Bu2 P Ir Pt Bu
H2 t
Bu2 P Ir PtBu H H
H H
RT, -PhH H H H
45 46
44

Scheme 12. Reaction of 41 with benzene and subsequent reactions.

CF3 COO
H
OC CF3 COOH
tBu
2P Ir Pt Bu tBu P Pt Bu
2 Ir
H C6 D6 or CD2 Cl2 OC
RT O
51
tBu
2P Ir Pt Bu
52 O
CO RT O2 50
No reaction
N2 or
CO2
H O
CHCl3
tBu Pt Bu tBu
2P Ir Pt Bu
tBu
2P Ir Pt Bu 2P Ir
Cl
OCOCF3 49
53 44

Scheme 13. Reactions of iridium complex 44.

 M.S. Balakrishna / Polyhedron 143 (2018) 2–10 9

H D
D D Cat. 1 mol% (48)
H N2 H RH
H
RD t
Bu2 P Ir PtBu2
tBu P
2 Ir PtBu2 t
Bu2 P Ir PtBu2 D D
150 o C, 24 h
H H
H H N H D
48
48 54 N
15%
50%
Scheme 14. Formation of dinitrogen complex 54. 25% N 9%

reaction sequence clearly demonstrates: i) the initial formation of a
C–C double bond, via a reversible Csp3–H activation, ii) and pro-
ceeding forward with the addition of TBE as hydrogen acceptor
but, iii) reversing on applying H2 pressure and iv) eventually
resulting in the cleavage of unactivated Csp3–Csp3 bond. DFT calcu-
lations have been carried out to give more insight into these trans-
formations. The complex 47 on heating yields dihydride complex
48 [68].
The complex 44 due to its reactivity, readily activates small
molecules as depicted in Scheme 13 [69]. Reaction of 44 with chlo-
roform yields chloro complex 49, whereas on exposure to O2 and
CO, respective 18 e complexes, 50 and 51, are formed. However,
there was no reaction between 44 and CO2 or N2.
Addition of trifluoroacetic acid to a solution of 51 in C6D6
resulted in the formation of an unstable complex 52 which gradu-
ally transformed to 53. Formation of 52 was presumably due to the
outer-sphere protonation of the double bond or involving b-inser-
tion of the double into the Ir–H bond (evinced by deuterium
exchange and NMR studies). Due to this the electron density on
iridium in 52 reduces and this in turn weakens the Ir–CO back
bonding, thus facilitating the insertion of CO into the Ir–Ph bond
to form 53 and benzaldehyde. This is a rare and opposite to the
more common reaction of deinsertion of CO, among iridium pincer
complexes, as seen in decarbonylative dehydrogenation or cat-
alytic decarbonylation reactions observed with rhodium and irid-
ium complexes. Variable temperature NMR studies have revealed
[70] the formation of dinitrogen complex 54 from 48 at low tem-
peratures (Scheme 14).
6.2. Deuterium exchange reactions
Hydride complexes 47 and 48 have been investigated for their
fluxionality and deuterium exchange reactions [68]. Slow bubbling
of D2 gas through a C6D6 solution of 47 resulted in complete
deuteration, whereas in the case of 48, due to the deuterium
scrambling, instead of D2, C6D6 was used. On heating 48 with
C6D6 around 100 °C resulted in deuteration of hydride and a-C–H
positions and above 100 °C, tert-butyl groups get deuterated. After
keeping at 120 °C for several hours, complete deuteration of 48
>95% 9%
O
>95% >95% >95% >95%
20% 15%
60% 19% 57% 60%
23% 60%
>95% 17% 31%
<2% 10% cat
Scheme 16. Promotion of deuterium exchange by complex 48.
was achieved (Scheme 15). These results prompted to look into
the catalytic ability of 48 for deuteration of various organic mole-
cules. Organic molecules such as benzene, toluene, naphthalene,
TBE, pyridine, Et3N, THF etc., taken in C6D6 with 1 mol% of complex
48, on heating to 150 °C for 24 h resulted in moderate to quantita-
tive deuteration (Scheme 16) [70].
7. Summary
Chemistry of pincer ligands has grown rapidly in recent years.
Tridentate mode of coordination with a covalent pivot bond results
in two metalacycles which is robust and tolerate harsh conditions.
This exceptional property makes pincer complexes special in
homogeneous catalysis, especially in challenging reactions involv-
ing Csp3–Csp3 and Csp3–H bond activations.
In catalytic dehydrogenation, the activity of PCyP ligand was
found to be low compared to the corresponding PArP systems pri-
marily due to the low thermal stability of the catalytically active
species. However, iridium complexes with electron rich P-sub-
stituents showed Csp3–H activation as well as intramolecular
coupling reactions which can be made reversible by altering the
reaction conditions. Further, in these complexes, reversible a-
and b-hydrogen elimination was observed showing the non-inno-
cent nature of the PCyP ligand system. Although, non-innocent nat-
ure has been displayed by arene system in some dearomatization
reactions, the observation made in the case of PCyP system appears
unique, where non-activated Csp3–H bonds expel two molecules of
H2 resulting in a C@C bond which under H2 pressure reverts back
to C–C bond to regenerate the original ligand structure, essentially
resulting in a net Csp3–Csp3 bond cleavage, thus making it an inter-
esting system.

H D

H H D2 D D
t
Bu2 P Ir PtBu2 tBu P Ir PtBu2
2
C 6D 6
H H D D
47

70 o C >100 oC
H H D C 6D 6
H C 6D 6
tBu P PtBu2
t
Bu2 P Ir PtBu2 t
Bu2 P Ir PtBu2 D
2 Ir t
Bu2 P Ir PtBu2
C 6D 5 D D D
H D
48 H H
other isotopomers

Scheme 15. Deuterium exchange with D2 and C6D6 for complexes 47 and 48.
10 M.S. Balakrishna / Polyhedron 143 (2018) 2–10
Cyclodiphosphazane based dipincer molecular balloons are
equally interesting owing to their multimetallic nature and large
void available in the molecule to capture and activate smaller
molecules via both non-covalent- and with some modifications
covalent-interactions as well.
Another promising ligand is SiPSi pincer and especially its
ruthenium complex with two egostic g2-Si–H bonds and their
involvement in Ru–H/g2-Si–H exchange process. The potential of
this complex in various hydrogenation process is yet to be
explored.
The air and thermally stable triazole based pincer ligands and
their complexes are equally interesting in terms of their high cat-
alytic activity in Heck reaction. The presence of additional donor
sites makes it more interesting owing to their possible secondary
interactions which can influence the kinetics of the catalytic
reactions.
Acknowledgements
This work was supported by a grant SR/S1/IC-08/2014 from the
Science & Engineering Research Board, New Delhi, India.
References
[1] H.P. Dijkstra, M.D. Meijer, J. Patel, R. Kreiter, G.P.M. van Klink, M. Lutz, A.L.
Spek, A.J. Canty, G. van Koten, Organometallics 20 (2001) 3159.
[2] G. van Koten, R.J.M.K. Gebbink, Dalton Trans. 40 (2011) 8731.
[3] R. Ahuja, B. Punji, M. Findlater, C. Supplee, W. Schinski, M. Brookhart, A.S.
Goldman, Nat. Chem. 3 (2011) 167.
[4] C.J. Moulton, B.L. Shaw, J. Chem. Soc., Dalton Trans. (1976) 1020.
[5] S.D. Perera, B.L. Shaw, M. Thornton-Pett, J. Chem. Soc., Dalton Trans. (1995)
1689.
[6] W. Leis, H.A. Mayer, W.C. Kaska, Coord. Chem. Rev. 252 (2008) 1787.
[7] N. Selander, J. Szabó Kálmán, Chem. Rev. 111 (2011) 2048.
[8] M.E. van der Boom, D. Milstein, Chem. Rev. 103 (2003) 1759.
[9] M.C. Haibach, D.Y. Wang, T.J. Emge, K. Krogh-Jespersen, A.S. Goldman, Chem.
Sci. 4 (2013) 3683.
[10] S. Chakraborty, P. Bhattacharya, H. Dai, H. Guan, Acc. Chem. Res. 48 (2015)
1995.
[11] J. Choi, D.Y. Wang, S. Kundu, Y. Choliy, T.J. Emge, D. Krogh-Jespersen, A.S.
Goldman, Science 332 (2011) 1545.
[12] A.S. Goldman, A.H. Roy, Z. Huang, R. Ahuja, M. Brookhart, Science 312 (2006)
257.
[13] M.C. Haibach, S. Kundu, M. Brookhart, A.S. Goldman, Acc. Chem. Res. 45 (2012)
947.
[14] T. Zell, D. Milstein, Acc. Chem. Res. 48 (2015) 1979.
[15] G. van Koten, R.A. Gossage, The privileged pincer-Metal platform: coordination
chemistry & applications, Heidelberg: Springer, Top. Organometal. Chem. 54
(2016).
[16] J. Choi, A.H.R. MacArthur, M. Brookhart, A.S. Goldman, Chem. Rev. 111 (2011)
1761.
[17] Y. Segawa, M. Yamashita, K. Nozaki, J. Am. Chem. Soc. 131 (2009) 9201.
[18] C. Gunanathan, D. Milstein, Chem. Rev. 114 (2014) 12024.
[19] M.Q. Slagt, D.A.P. van Zwieten, A.J.C.M. Moerkerk, R.J.M. Klein Gebbink, G. van
Koten, Coord. Chem. Rev. 248 (2004) 2275.
[20] H.A. Younus, N. Ahmad, W. Su, F. Verpoort, Coord. Chem. Rev. 276 (2014) 112.
[21] Q.-H. Deng, R.L. Melen, L.H. Gade, Acc. Chem. Res. 47 (2014) 3162.
[22] D. Morales-Morales, C.M. Jensen, The Chemistry of Pincer Compounds, Elsevier
Science B.V, Amsterdam, 2007.
[23] K.J. Szabo, O.F. Wemdt, Pincer and Pincer-Type Complexes, Applications in
Organic Synthesis and Catalysis, Wiley-VCH, Singapore, 2014.
[24] G.S. Ananthnag, J.T. Mague, M.S. Balakrishna, Dalton Trans. 44 (2015) 3785.
[25] V.S. Kashid, L. Radhakrishna, M.S. Balakrishna, Dalton Trans. 46 (2017) 6510.
[26] E.M. Schuster, M. Botoshansky, M. Gandelman, Angew. Chem. Int. Ed. 47
(2008) 4555.
[27] V. Montiel-Palma, M.A. Muñoz-Hernández, C.A. Cuevas-Chávez, L. Vendier, M.
Grellier, S. Sabo-Etienne, Inorg. Chem. 52 (2013) 9798.
[28] A.V. Polukeev, R. Gritcenko, K.J. Jonasson, O.F. Wendt, Polyhedron 84 (2014)
63.
[29] M.S. Balakrishna, V.S. Reddy, S.S. Krishnamurthy, J.F. Nixon, J.C.T.R.B.S. Laurent,
Coord. Chem. Rev. 129 (1994) 1.
[30] M.S. Balakrishna, P. Chandrasekaran, R. Venkateswaran, J. Organomet. Chem.
692 (2007) 2642.
[31] M.S. Balakrishna, Dalton Trans. 45 (2016) 12252.
[32] L. Stahl, Coord. Chem. Rev. 210 (2000) 203.
[33] Y.X. Shi, R.Z. Liang, K.A. Martin, D.G. Star, J. Diaz, X.Y. Li, R. Ganguly, F. Garcia,
Chem. Commun. 51 (2015) 16468.
[34] Y.X. Shi, R.Z. Liang, K.A. Martin, N. Weston, R. Ganguly, Y. Li, Y. Lu, S. Gonzalez-
Calera, A.J.M. Ribeiro, M.J. Ramos, P.A. Fernandes, F. Garcia, Inorg. Chem. 54
(2015) 6423.
[35] G.G. Briand, T. Chivers, M. Krahn, Coord. Chem. Rev. 233–234 (2002) 237.
[36] S.G. Calera, D.S. Wright, Dalton Trans. 39 (2010) 5055.
[37] T. Beweries, R. Kuzora, U. Rosenthal, A. Schulz, A. Villinger, Angew. Chem., Int.
Ed. 50 (2011) 8974.
[38] A. Hinz, R. Kuzora, U. Rosenthal, A. Schulz, Chem. - Eur. J. 20 (2014) 14659.
[39] M.M. Siddiqui, S.M. Mobin, I. Senkovska, S. Kaskel, M.S. Balakrishna, Chem.
Commun. (Cambridge, U. K.) 50 (2014) 12273.
[40] T. Roth, H. Wadepohl, D.S. Wright, L.H. Gade, Chem. - Eur. J. 19 (2013) 13823.
[41] K.V. Axenov, I. Kilpeläinen, M. Klinga, M. Leskelä, T. Repo, Organometallics 25
(2006) 463.
[42] S. Mohanty, M.S. Balakrishna, J. Chem. Sci. 122 (2010) 137.
[43] A. Rashid, G.S. Ananthnag, S. Naik, J.T. Mague, D. Panda, M.S. Balakrishna,
Dalton Trans. 43 (2014) 11339.
[44] M.S. Balakrishna, D. Suresh, A. Rai, J.T. Mague, D. Panda, Inorg. Chem. 49 (2010)
8790.
[45] D. Suresh, M.S. Balakrishna, K. Rathinasamy, D. Panda, J.T. Mague, Dalton
Trans. (2008) 2285.
[46] K.A. Watson, F.L. Palmieri, J.W. Connell, Macromolecules 35 (2002) 4968.
[47] C.-H. Chien, C.-K. Chen, F.-M. Hsu, C.-F. Shu, P.-T. Chou, C.-H. Lai, Adv. Funct.
Mater. 19 (2009) 560.
[48] H. Morimoto, T. Yoshino, T. Yukawa, G. Lu, S. Matsunaga, M. Shibasaki, Angew.
Chem. Int. Ed. 47 (2008) 9125.
[49] A.L. Schwan, Chem. Soc. Rev. 33 (2004) 218.
[50] K. Xu, F. Yang, G. Zhang, Y. Wu, Green Chem. 15 (2013) 1055.
[51] Y.-L. Zhao, G.-J. Wu, Y. Li, L.-X. Gao, F.-S. Han, Chem. Eur. J. 18 (2012) 9622.
[52] M. Stankevic, A. Wlodarczyk, Tetrahedron 69 (2013) 73.
[53] T. Steinke, B.K. Shaw, H. Jong, B.O. Patrick, M.D. Fryzuk, Organometallics 28
(2009) 2830–2836.
[54] R. Gerber, O. Blacque, C.M. Frech, ChemCatChem 1 (2009) 393–400.
[55] E. Balaraman, B. Gnanaprakasam, L.J.W. Shimon, D. Milstein, J. Am. Chem. Soc.
132 (2010) 16756–16758.
[56] A. Plikhta, A. Pöthig, E. Herdtweck, B. Rieger, Inorg. Chem. 54 (2015) 9517–
9528.
[57] F.E. Hahn, M.C. Jahnke, T. Pape, Organometallics 25 (2006) 5927–5936.
[58] H.M. Lee, J.Y. Zeng, C.-H. Hu, M.-T. Lee, Inorg. Chem. 43 (2004) 6822–6829.
[59] Y. Tulchinsky, M.A. Iron, M. Botoshansky, M. Gandelman, Nat. Chem. 3 (2011)
525–531.
[60] S. Langbein, H. Wadepohl, L.H. Gade, Organometallics 35 (2016) 809–815.
[61] L. Alvarez-Rodriguez, J. Brugos, J.A. Cabeza, P. Garcia-Alvarez, E. Perez-Carreno,
D. Polo, Chem. Commun. 53 (2017) 893–896.
[62] C. Azerraf, D. Gelman, Chem. - Eur. J 14 (2008) 10364–10368.
[63] E.M. Schuster, M. Botoshansky, M. Gandelman, Organometallics 28 (2009)
7001.
[64] E.M. Schuster, M. Botoshansky, M. Gandelman, Dalton Trans. 40 (2011) 8764.
[65] S. Sjovall, O.F. Wendt, C. Andersson, J. Chem. Soc., Dalton Trans. (2002) 1396.
[66] I. Göttker-Schnetmann, P. White, M. Brookhart, J. Am. Chem. Soc. 126 (2004)
1804.
[67] A.V. Polukeev, R. Marcos, M.S.G. Ahlquist, O.F. Wendt, Chem. Sci. 6 (2015)
2060.
[68] A.V. Polukeev, R. Marcos, M.S.G. Ahlquist, O.F. Wendt, Chem. - Eur. J 22 (2016)
4078.
[69] A.V. Polukeev, O.F. Wendt, Organometallics 34 (2015) 4262.
[70] A.V. Polukeev, R. Marcos, M.S.G. Ahlquist, O.F. Wendt, Organometallics 35
(2016) 2600.