Accepted Manuscript

7-6-7 Ring-Based Transition-Metal Catalysts for the Transfer Dehydrogenation of

Isopropanol

Yuan Shi, Takuya Suguri, Satoshi Kojima, Yohsuke Yamamoto

PII: S0022-328X(15)30111-X
DOI: 10.1016/j.jorganchem.2015.08.008
Reference: JOM 19196

To appear in: Journal of Organometallic Chemistry

Received Date: 10 March 2015

Revised Date: 13 August 2015
Accepted Date: 16 August 2015

Please cite this article as: Y. Shi, T. Suguri, S. Kojima, Y. Yamamoto, 7-6-7 Ring-Based Transition-Metal
Catalysts for the Transfer Dehydrogenation of Isopropanol, Journal of Organometallic Chemistry (2015),
doi: 10.1016/j.jorganchem.2015.08.008.

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 ACCEPTED MANUSCRIPT

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 ACCEPTED
7-6-7 Ring-Based MANUSCRIPT
Transition-Metal Catalysts for the
Transfer Dehydrogenation of Isopropanol

Yuan Shi, Takuya Suguri, Satoshi Kojima, Yohsuke Yamamoto*

Department of Chemistry, Graduate School of Science, Hiroshima University, 1-3-1 Kagamiyama,

Higashi-Hiroshima, 739-8526 Japan
* Corresponding author. Tel.: +81 82 424 7430; fax: +81 82 424 0723.
E-mail address: yyama@sci.hiroshima-u.ac.jp (Y. Yamamoto)

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Keywords:

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dehydrogenation, homogeneous catalysis, NBO analysis, iridium complex, rhodium complex

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ABSTRACT

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A family of 7-6-7 ring-based PCP pincer iridium/rhodium complexes has been applied to the
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transfer dehydrogenation of isopropanol to give acetone using tert-butylethylene (TBE) as the
hydrogen acceptor. For the iridium complexes, high initial activity was achieved with the turnover
number (TON) being as high as 6000 after 2 h at 200°C, even when TBE was present in high
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concentration (6000 equivalents). The inhibition effect of TBE was found to be somewhat weaker
than in the case of alkane dehydrogenation using the same catalysts. Whereas the corresponding
rhodium complex was inactive in alkane dehydrogenation, it was unexpectedly found to have a
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catalytic activity of 2000 TONs (3000/1 TBE/catalyst ratio) after 2 h at 200°C in the same transfer
dehydrogenation. The bonding properties of the reactive complexes were investigated through
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natural bond orbital (NBO) analysis and compared.

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Introduction

Ketones and aldehydes are common functionalized compounds that have a wide range of uses in
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both industry and laboratory research. They possess high reactivity towards not only nucleophiles,
but also electrophiles when enolizable [1]. Thus, the development of efficient methods for the
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production of ketones and their analogs is worthwhile. Among the many processes for the formation
of the C=O function, the oxidation of alcohols by dehydrogenation can be considered to be a good
option because of the accessibility of alcohols in general and the atom-economy of the process
(only the loss of H2) [2]. Although not as common as alkane dehydrogenation, transition
metal-catalyzed dehydrogenative oxidation of alcohols has received much attention over the last
few decades [3]. Since the same catalysts can in principle catalyze the reverse reaction
(hydrogenation), applications to reactions that make use of both dehydrogenation and
hydrogenation reactions in combination have emerged [4]. Examples of such reactions based upon
the “borrowing hydrogen” strategy include redox-neutral alcohol transformations, amine alkylation,
ketone alkylation, etc.

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 ACCEPTED MANUSCRIPT

Figure 1. General backbone of the phenyl-type, the anthracene-type and our 7-6-7-type of pincer
metal complexes.

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Recently, a high catalytic activity of 4820 turnover numbers (TONs; refers to the moles of
product per mole of catalyst used) after 24 h at 230°C, was achieved by our 7-6-7 ring-based pincer

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iridium catalyst in the dehydrogenation of cyclooctane [5] (Figure 1). The reasoning for our
molecular design of a scaffold consisting of benzene bearing two fused seven-membered rings
(7-6-7-type) was to find a balance between the highly active but somewhat thermally unstable

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phenyl-type catalysts and thermally stable but lowly reactive anthracene-type catalysts. That is, we
envisioned that the 7-6-7-type skeleton based transition-metal catalyst would somewhat resemble
the anthracene system in robustness while retaining a certain degree of flexibility for facilitating the

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conformational changes required for optimal reactivity. Our success encouraged us to apply our
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catalysts to other catalytic reactions that may produce value-added products. Thus, we have
examined the dehydrogenation of alcohols with isopropanol as a representative alcohol.
Additionally, density functional theory (DFT) computations have been carried out in order to
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compare both electronic and steric effects between the phosphorus coordinating groups possessing
different substituents, and to correlate the differences in the properties of the transition metal
complexes with reactivity. Herein, we present our results.
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Results and discussion

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Experimental studies of isopropanol dehydrogenation

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The transfer dehydrogenation of isopropanol was performed using three different transition-metal
catalysts based on the 7-6-7-type backbone, (7-6-7-iPrPCP)Ir (1, iPr = isopropyl) and
(7-6-7-CyPCP)Ir (2, Cy = cyclohexyl) which are iridium complexes possessing (iPr)2P or (Cy)2P
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coordinating groups, respectively, and (7-6-7-iPrPCP)Rh (3) which is a corresponding rhodium

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complex consisting of two (iPr)2P groups. The synthetic details of these complexes have previously
been reported [5,6]. Many transition-metal complexes have been reported to be capable of
catalyzing the transfer dehydrogenation of alcohols using either oxygen, hydrogen peroxide,
carbonyl compounds or alkenes as the hydrogen acceptor [7]. tert-Butylethylene (TBE) was chosen
as the hydrogen acceptor for initial investigations of the reactivity of our catalysts towards alcohols,
as it was found to be efficient in the transfer dehydrogenation of alkanes [5,8]. The secondary
alcohol isopropanol was chosen as the model alcohol, based on the research performed by Koridze
and co-workers [9] in which secondary alcohols were found to be much less prone to
decarbonylation compared with primary alcohols. (7-6-7-RPCP)M(H)(Cl) (M = Ir, Rh) which are
stable pre-catalysts and base (sodium tert-butoxide, (NaOtBu)) were used for the in situ generation
of the catalytically active species in stock solutions containing isopropanol and TBE. The catalytic

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 ACCEPTED
activity is presented as TON, which MANUSCRIPT
was calculated from the ratio of the remaining unreacted
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isopropanol and the resultant acetone through H NMR spectroscopic analysis.
The catalytic reaction and structures of the transition metal pre-catalysts are shown in Scheme 1
and Figure 2, respectively.

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Scheme 1. Catalytic transfer dehydrogenation of isopropanol.

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Figure 2. Structures of the pre-catalysts tested in the catalytic reactions.
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As shown in Table 1, when the catalytic activity was examined using 3000 equivalents of both
isopropanol and TBE (entries 1, 7, 10) to the catalyst, the iridium complexes possessing either
isopropyl or cyclohexyl groups exhibited excellent activity with a 100% conversion of isopropanol
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to acetone after 2 h at 200°C. This is in deep contrast to our previous work on the dehydrogenation
of cyclooctane to give an internal alkene [5], where no product could be detected when the Cy-Ir
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species was employed, a result we attributed to steric hindrance. The rhodium complex that was
completely unreactive in all the reactions examined for alkane dehydrogenation (unreported
findings) was also found to be catalytically active, although the TON was somewhat lower than that
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of the iridium catalysts. Nonetheless, this is the first observation of catalytic activity using the
rhodium analog of 7-6-7-type catalysts. A difference in reactivity between the iPr–Ir and Cy–Ir
species could be observed by increasing the substrates to 6000 equivalents, with TONs being 6000
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and 4500, respectively, after 2 h at 200°C (entries 2 and 8). When 9000 equivalents of the substrates
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were added (entry 3), the activity of the iPr–Ir species went down sharply and resulted in less than
40% conversion under otherwise the same conditions. Accordingly, in the case of 12000 equivalents,
the activity was very poor.
To determine the reason for the decrease in activity when more than 6000 equivalents of the
substrates were used, a supplemental experiment was carried out with 6000 equivalents of TBE and
12000 equivalents of isopropanol (entry 6) at 200°C for 2 h. In this case, 100% conversion was
achieved. This suggested that the main cause of inhibition of the catalytically active species was the
hydrogen acceptor TBE rather than the reactant alcohol or the product acetone. The degree of
inhibition is however not as bad as with the dehydrogenation of cyclooctane with the iPr-Ir species,
in which the TON sharply decreased when 6750 equivalents of TBE was added, giving a TON of
only 2942 after 6 h at 200°C [5].

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 When 15000 equivalents of theACCEPTED
substrates wereMANUSCRIPT
used (entries 5, 9, and 11), although the reactivity
was low as a whole, the Cy–Ir catalyst was found to exhibit double the activity of the iPr–Rh
species, but only about half of that of the iPr–Ir species.
A comparison with reported phenyl-type PCP pincer iridium catalysts with phosphine (4 and 6)
or phosphinite (5) substituents [9] used under similar reaction conditions (iPrOH/TBE/catalyst =
6000/6000/1 for 1 and 2, 4000/4000/1 for 5 and 6) shows that our 7-6-7 ring-based catalysts
favorably compare with catalyst 5. Since we have established a TON of 6000 (not fully optimized)
to 4000 for 5 at 100% alcohol conversion, it is likely that our catalyst is much better at least in
terms of TON. Furthermore, our iridium catalysts are significantly more active than 6. To be more

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specific, a 6000 TON was achieved after 2 h at 200°C (0.017% catalyst loading, 100% conversion)
by using the [(7-6-7-iPrPCP)Ir] catalyst, while a 4000 TON was obtained by the phenyl-type
[(tBuPOCOP)Ir] catalyst 5 (0.025% catalyst loading, 1 h, 200°C, 100% conversion). On the other

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hand, the TON was only 1520 for the ruthenocene-based iridium catalyst 6 after 8 h at 150°C,
which was a better temperature for obtaining better results than 200°C. Entries 15 and 16 suggest
that decarbonylation occurs more readily with 6 at higher temperatures, thereby lowering the

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catalytic efficiency. As was seen for alkane dehydrogenation, the activity exhibited by the
phosphine-type catalyst 4 was orders of magnitude lower than those of other catalysts [10]. On the
whole, our 7-6-7-type iridium catalysts, possessing either (iPr)2P or (Cy)2P groups, exhibited

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outstanding activity in the transfer dehydrogenation of isopropanol. Although inhibition of the
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active species caused by the alkene substrate is still an issue, it is of less impact in alcohol
dehydrogenation than in alkane dehydrogenation. Coordination of small substrates to the metal
center is not inhibited by the steric hindrance of the bulky cyclohexyl groups, mainly due probably
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to the flexibility of the seven-membered ring system. Though moderate, the realization of activity
for the corresponding rhodium catalyst indicates the applicability and effectivity of our 7-6-7-type
skeleton again, and further structural optimization should lead to promising results.
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Table 1. Results of the transfer dehydrogenation of isopropanol in the presence of TBE.

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a
Calculated from the equivalents ACCEPTED
of isopropanol MANUSCRIPT
used.
b
Based upon the amount of the catalyst.
c
Calculated from the consumed equivalents of TBE.
d
Data from reference 10; 2-hexanol was used as the substrate and the reaction was performed in
benzene solutions.
e
Data from reference 9.

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Figure 3. 1H NMR spectrum for the product mixture of entry 4 in Table 1. The representative
resonances at 3.90 and 2.07 ppm, which were assigned to unreacted isopropanol (methane proton)
and formed acetone, respectively, were used to estimate the turnover number (TON) for each
independent reaction. In this case, the other large resonances, besides the doublet at 1.05 for the
methyl groups of isopropanol, correspond to those of tert-butylethylene with signals for
2,2-dimethylbutane being small.

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Figure 4. Structures of the three reference catalysts used for comparison with 7-6-7-type catalysts.

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Inhibition effect of TBE

The decrease in activity seen with increasing equivalents of the hydrogen acceptor was similar to

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that observed in alkane dehydrogenation, but on a lesser scale. As mentioned in our previous report
[5], because there is an abundance of olefin (TBE) in the initial stage, coordination to the electron
deficient metal of the 14e active species (from 1-3) cannot be avoided, thereby leading to a resting

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state. Therefore, the inhibition effect needs to be considered. Although the TBE-adduct of the active
species appears to be stable in the condensed phase, a delicate equilibrium seems to exist between
these resting states and the 14e active species which helps to drive the catalytic cycle (Scheme 2)

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[11]. Thus, the reason for the decrease in activity under high TBE concentrations could be explained
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as the equilibrium shifting largely to the side of the TBE-adduct, the resting state. Entropy factors at
high temperatures most likely shift the equilibrium to the side of the free 14e species, thereby
leading to a significantly larger acceleration in reaction rates than would be expected for strictly
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temperature dependent reaction rates. These inferences are in good agreement with experimental
results. It is possible that such deactivation by high concentration of the resting state may be
suppressed by the continuous addition of TBE rather than providing all of the TBE at the beginning
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of the reaction [12].

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Scheme 2. Reaction equilibrium of the active species and TBE-adduct independent of the catalytic
cycle (M = Ir, Rh; R = iPr, Cy).

Computational studies

The stability of the olefin adduct resting states ((7-6-7-RPCP)Ir(olefin)) relative to the reactive
14e species for catalytic systems possessing different R2P groups or central metal atoms was
estimated from the calculated stabilization energies. The sum of the energies of the 14e species,
butane and butene was set at zero, and the data for the rhodium complex was calculated separately

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[13]. This gave an order of iPr–Ir ACCEPTED MANUSCRIPT
> Cy–Ir > iPr–Rh with ∆G of −8.1, −7.2, and 0.1 kcal mol−1,
respectively. These results indicate that the catalyst most inhibited by olefins is the iPr–Ir species,
not the least active rhodium one. It is suggested that the weaker interactions are due to the smaller
4d orbitals of the rhodium atom compared with the 5d orbitals of the iridium atom, making it
relatively difficult for the substrates (including alcohols, alkanes, and alkenes) to coordinate with
the metal. To confirm this point and to gain a deeper understanding of the bonding state of the
intermediates involved in the catalytic cycle, NBO calculations were performed on the olefin
adducts. The NBO method [14] is generally used to describe Lewis-like bonding patterns of
electron pairs from the viewpoint of electron density distribution in atoms and in bonds between the

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atoms. Thus, this method should be suitable for explaining the differences in strength, interactions,
and so forth in bonding sets of orbitals, especially for the M–H, M–C, and M–O bonds of the
adducts, which are key to the catalytic reactions. In order to investigate more comprehensively the

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electronic effects which should strongly influence interaction with olefins, the corresponding
(7-6-7-PhPCP)Ir olefin adduct, possessing electron withdrawing Ph2P groups, was also examined.
Quantitative analysis of the donor–acceptor strength of the metal-olefin interactions was performed

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using the second order perturbation theory analysis of the Fock Matrix in the NBO basis [15], with
n-butene being used in the place of bulky TBE for improvement of computational accuracy. The
obtained results are summarized in Table 2.

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Table 2. Donor–acceptor stabilization energies of the metal–olefin interactions.
(σ-Type Donation) (π-Type Back Donation)
iPr–Ir 42.1 kcal mol−1 iPr–Ir 62.7 kcal mol−1
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Ph–Ir 50.4 kcal mol−1 Ph–Ir 59.1 kcal mol−1

iPr–Rh 33.2 kcal mol−1 iPr–Rh 41.5 kcal mol−1
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The calculated results are in good agreement with expected electronic properties of the respective
species and reasonably explain the relative magnitude of the interactions. The phenyl groups bound
to phosphorus in the Ph–Ir species decrease electron density on the iridium atom compared to the
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iPr–Ir species. Therefore, σ–type donation from the coordinated olefin is stronger (50.4 versus 42.1
kcal mol−1), the back donation from the metal is weaker (59.1 versus 62.7 kcal mol−1) and the
overall interaction is stronger (109.5 versus 104.8 kcal mol−1) for the former. These interactions in
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the rhodium species are largely weakened, and this presumably is because of the small size of the
4d orbitals and weak donating ability of the electrons therein, as partially mentioned above. This
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explains the relative high energy level of the resting state (0.1 kcal mol−1), which would be
beneficial for shifting the chemical equilibrium to the right (Scheme 2), thus favoring the formation
of the active species.
Since the low activity of the rhodium catalyst seems not to be due to TBE-inhibition according to
the above analysis, we decided to investigate the stability of other intermediates. Wiberg bond
index analysis [16], which can be used as another criterion for interaction (bond strength), was
performed for the M(H)(OR) species, a key oxidative adduct in the catalytic cycle of alcohol
dehydrogenation. As shown in the upper half of Table 3, the relative Wiberg bond index data
demonstrates that the bond strength of the rhodium species is weaker than that of the corresponding
iridium species (0.6310 bond order for Rh–O bonds and 0.6953 for Ir–O bonds). The weaker
interactions suggest less overlap of bonding orbitals and the likeliness of higher activation energy

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levels. This could be the reason whyACCEPTED
the rhodiumMANUSCRIPT
species is less reactive in the dehydrogenation of
alcohols. Similar tendencies can also be found in the metal-alkane oxidative adducts (lower half of
Table 3), where the weakest bond is calculated to be only 0.5756 bond order for the Rh–C bond of
the Rh–cyclooctane adduct.
The reason for the experimentally observed lower energy barrier for alcohol dehydrogenation
than alkane dehydrogenation could be due to stronger interaction between the metal atom and the
substrate. Thus, the sum of the bond orders of the Ir–H and the Ir–O bonds of the iPrOH adduct is
larger than that of the Ir–H and the Ir–C bonds of either alkane adduct (1.4276 versus 1.3873 or
1.3411). A similar tendency is found for the rhodium species, where the value of 1.3196 for the

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iPrOH adduct is larger than 1.2449 or 1.2408 for the n-butane or the cyclooctane adduct,
respectively.
Calculations indicated a larger difference for the Rh-H bond orders (0.0708) between the alcohol

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adduct and the alkane adduct compared with that for Ir-H bonds (0.0430) between corresponding
adducts, and a reversal in bond order with Rh–O (0.6310) being stronger than Rh–C (0.6271) as
opposed to the corresponding iridium pair. These aspects imply that the reactivity of rhodium

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catalysts is more sensitive to the identity of the reaction than that of iridium counterparts.

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Table 3. Wiberg bond index data for substrate adducts
(upper: Metal-alcohol adducts; lower: Metal-alkane adducts).
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Bond R = iPr

Iridium Ir–H 0.7323

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species Ir–O 0.6953

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Rhodium Rh–H 0.6886

species Rh–O 0.6310
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Bond R’ = nBu R’ = cycloocta

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Iridium Ir–H 0.6893 0.7345

species Ir–C 0.6980 0.6066
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Rhodium Rh–H 0.6178 0.6652

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species Rh–C 0.6271 0.5756

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Conclusion ACCEPTED MANUSCRIPT

In conclusion, three 7-6-7-type catalysts, (7-6-7-iPrPCP)Ir, (7-6-7-CyPCP)Ir or (7-6-7-iPrPCP)Rh,

have been investigated in the transfer dehydrogenation of isopropanol with the use of TBE as the
hydrogen acceptor. The iridium catalysts exhibited very high activities, even in the presence of
more than 6000 equivalents of TBE, a potential inhibitor. These catalytic reactions have proven to
be more efficient than those of alkanes, as expected. Noteworthy is that the 7-6-7 ring-based
rhodium catalyst, completely inert in the transfer dehydrogenation of alkanes, also activated the
reaction with isopropanol, allowing for comparisons with the iridium analogs. Compared with

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reported data on phenyl-type catalysts, our 7-6-7-type transition-metal catalysts fare favorably or
are likely to be much better in terms of TON, owing to the high degree of flexibility retained for
facilitating conformational changes required for optimal reactivity even in the case of small

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molecule reactions. However, our catalysts are expected to show their worth in long and high
temperature reactions due to their durability somewhat resembling that of highly robust but lowly
active anthracene based catalysts.

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NBO calculations allowed the quantitative analysis of donor–acceptor interactions of olefin
adducts of iridium and rhodium catalysts. According to second order perturbation theory analysis,
the stabilization energies of both donation and back donation in the olefin-adducts are weaker in the

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rhodium species compared with those of corresponding iridium complexes, thereby providing
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support for the rhodium catalyst adduct being least stable. This weak coordination between the
metal atom and inhibitor olefin implied high potential for catalytic activity contrary to experimental
results. However, the Wiberg bond index analysis suggested weaker bonding and thus lower
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stability for catalytic intermediates of the rhodium system compared with iridium analogs, which is
in line with the decreased activity in both the dehydrogenation of alcohols and alkanes for the
rhodium system. Further applications of our unique catalysts are currently under consideration.
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Experimental

General procedure for the transfer dehydrogenation of isopropanol

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To a reaction vessel placed in a thick-walled TAIATSU reactor, isopropanol (15.0 mmol, 3000
equiv., distilled from CaH2 and degassed), tert-butylethylene (15.0 mmol, 3000 equiv., distilled
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from Na and degassed), the iridium or rhodium pre-catalyst (5.00 µmol, 1.0 equiv.), and NaOtBu
(10.0 µmol, 2.0 equiv.) were added in a argon-filled glovebox. The reactor was then sealed, taken
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out, and placed in an oil bath that had been preheated to the desired temperature. After the time
specified in Table 1, the reactor was cooled with ice water. A portion of the ice-cold solution was
transferred into an NMR tube containing CDCl3 immediately after opening the reactor. This was
then analyzed by 1H NMR spectroscopy. TONs were calculated from the quantities of the reactants
remaining unreacted and products determined from the integrals of their corresponding resonances.

Theoretical calculations

All geometry optimizations, harmonic vibrational frequencies calculations and NBO analyses
were performed with the Gaussian 09W software package [17] at the PBEPBE level using the

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LanL2DZ basis set for iridium, ACCEPTED
rhodium, and MANUSCRIPT
phosphorus atoms, the 6-31G(d, p) basis set for
carbon, hydrogen, and oxygen atoms directly connected to the transition-metal atom and 6-31G for
all other carbon and hydrogen atoms. Vibrational frequency calculations were performed on all
structures to determine whether the optimized structures were true minima (no imaginary
frequencies).

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840.
13. Only the data of iridium species were reported in our previous work, and the additional
stabilization energy of the corresponding rhodium species was calculated using the same

RI
method.
14. E. D. Glendening, C. R. Landis, F. Weinhold, WIREs Comput. Mol. Sci. 2 (2012) 1.
15. F. Weinhold, C. R. Landis, Valency and Bonding: A Natural Bond Orbital Donor-Acceptor

SC
Perspective, Cambridge Univ. Press, 2005.
16. K. B. Wiberg, Tetrahedron 24 (1968) 1083.
17. Gaussian 09, Revision D.01, M. J. Frisch, et al., Gaussian, Inc., Wallingford CT, 2009.

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 ACCEPTED MANUSCRIPT

Three kinds of 7-6-7-ring based iridium or rhodium catalysts catalyze

the transfer dehydrogenation of isopropanol efficiently.

The rhodium complex of 7-6-7 type was found to be active in the

catalytic dehydrogenation for the first time.

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The rhodium species may not be inhibited by the hydrogen acceptor in
the view of donor-acceptor interactions.

RI

The bonding strength in catalytic intermediates might result in a

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difference of reactivity between the iridium and rhodium species based
on the Wiberg bond index analysis.

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