Perfluoroalkylation of coordinated ethene in Rh(I) and Ir(I) complexes. Catalytic addition of iodoperfluoroalkanes to ethene

DOI: 10.1021/acs.organomet.6b00929

Source and publish data:

Organometallics p. 1245 - 1258 (2017)

Update date:2022-08-05

Topics:

Authors:

Blaya, María

Bautista, Delia

Gil-Rubio, Juan

Vicente, Joseì

Read Full Text PDF DownLoad Join now for total 90,000,000 free articles

Article abstract of DOI:10.1021/acs.organomet.6b00929

The complexes [M(^η5-Cp^?)(^η2-C₂H₄)₂] (M = Rh, Ir) react with iodoperfluoroalkanes to give [M(^η5-Cp^?)-(CH₂CH₂R_F)(μ-I)]₂ (main

Full text of DOI:10.1021/acs.organomet.6b00929

Article

pubs.acs.org/Organometallics

Perﬂuoroalkylation of Coordinated Ethene in Rh(I) and Ir(I)

Complexes. Catalytic Addition of Iodoperﬂuoroalkanes to Ethene

María Blaya,^†Delia Bautista,^‡Juan Gil-Rubio,*^,†and Jose Vicente*^,†

^†Grupo de Química Organometal

E−30100 Murcia, Spain

ica, Departamento de Química Inorgan

ica, Facultad de Química, and ^‡SAI, Universidad de Murcia,

* Supporting Information

ABSTRACT: The complexes [M(η⁵-Cp*)(η²-C₂H₄)₂] (M = Rh,

Ir) react with iodoperﬂuoroalkanes to give [M(η⁵-Cp*)-

(CH₂CH₂R_F)(μ-I)]₂(main product) and [M(η⁵-Cp*)-

(CH₂CH₂R_F)(μ-I)₂M(η⁵-Cp*)I] (R_F= t-C₄F₉, M = Ir; R_F= c-

C₆F₁₁, M = Ir, Rh). Similarly, the complexes [M(η⁵-Cp*)(η²-

C₂H₄)(PPh₃)] react with iodoperﬂuoroalkanes to give [M(η⁵-

Cp*)(CH₂CH₂R_F)I(PPh₃)] (M = Ir, R_F= t-C₄F₉, i-C₃F₇; M = Rh,

R_F= t-C₄F₉). Evidence for the generation of the heptaﬂuor-

oisopropyl carbanion in the reaction of [Ir(η⁵-Cp*)(η²-C₂H₄)-

(PPh₃)] with I-i-C₃F₇was obtained, which suggests that the

reaction is initiated by the transfer of two electrons from the Ir(I) complex to the iodoperﬂuoroalkane. The iodo-bridged

complexes react with PPh₃to give [M(η⁵-Cp*)(CH₂CH₂R_F)I(PPh₃)] (M = Ir, R_F= t-C₄F₉, c-C₆F₁₁; M = Rh, R_F= c-C₆F₁₁). The

complexes [Ir(η⁵-Cp*)(CH₂CH₂R_F)I(PPh₃)] (R_F= c-C₆F₁₁, i-C₃F₇) react with AgOTf to give [Ir(η⁵-Cp*)H(η²-CH₂

CHR_F)(PPh₃)]OTf. The analogous reaction of [Ir(η⁵-Cp*)(CH₂CH₂-t-C₄F₉)I(PPh₃)] gives CH₃CH₂-t-C₄F₉and [Ir(η⁵-

Cp*)(η²-o-C₆H₄PPh₂)]OTf, which reacts with PPh₃to give [Ir(η⁵-Cp*)(η²-o-C₆H₄PPh₂)(PPh₃)]OTf. This cyclometalated

complex and its analogue [Ir(η⁵-Cp*)(η²-o-C₆H₄PPh₂)(P(p-Tol)₃)]OTf are also prepared by the reaction of [Ir(η⁵-

Cp*)(Me)Cl(PPh₃)] with AgOTf and PPh₃or P(p-Tol)₃. The derivatives [Ir(η⁵-Cp*)(CH₂CH₂R_F)(PPh₃)L]OTf (L = CO, R_F

= c-C₆F₁₁, i-C₃F₇; L = PPh₃, R_F= i-C₃F₇) are isolated in the reactions of the Ir hydrido alkene complexes with CO or PPh₃. The

reactions of [Rh(η⁵-Cp*)(CH₂CH₂R_F)I(PR₃)] (R = Me, R_F= i-C₃F₇, n-C₄F₉, t-C₄F₉; R = Ph, R_F= i-C₃F₇, t-C₄F₉, c-C₆F₁₁) with

AgOTf aﬀord unstable triﬂato complexes that decompose to give CH₂CHR_F, but in the presence of PR₃the complexes

[Rh(η⁵-Cp*)(CH₂CH₂R_F)(PR₃)₂]OTf (R = Ph, R_F= i-C₃F₇, t-C₄F₉, c-C₆F₁₁; R = Me, R_F= i-C₃F₇, t-C₄F₉) were formed. When R

= Ph, these complexes are unstable and decompose quantitatively to give [Rh(η⁵-Cp*)H(PPh₃)₂]OTf and CH₂CHR_F.

Complexes of the type [M(η⁵-Cp*)(η²-C₂H₄)₂] (M = Rh, Ir) and [Rh(η⁵-Cp*)(CH₂CH₂R_F)I(L)] are initiators for the radical

addition of IR_Fto ethene.

or carbocationic intermediates.^7,9,12,13Remarkably, organo-

INTRODUCTION

■

metallic intermediates have been proposed in only a few of

these reactions. In some copper-catalyzed reactions, Cu(III)

intermediates containing metal-bound vinyl and perﬂuoroalkyl

groups have been suggested. These intermediates are supposed

to aﬀord the ﬁnal perﬂuoroalkylated alkenes by a reductive

elimination.^14,15In addition, intermediates of the type [M]-

CHR-CH₂R_F(R_F= C_nF_2n+1) have been proposed in some

Pd-¹⁵⁻¹⁷or Cu-catalyzed¹⁸reactions. These Heck-like inter-

mediates would aﬀord the perﬂuoroalkylated alkenes RHC

CHR_Fby β-hydride elimination.

Knowledge of the reactivity of alkene metal complexes and

perﬂuoroalkylating agents, such as iodoperﬂuoroalkanes (IR_F),

is expected to shed some light on the role of the metal catalysts

in these reactions and therefore to be helpful in the design of

more eﬃcient catalytic processes. However, very few studies of

this reactivity have been reported. In this respect, Hughes and

The important applications of organoﬂuorine compounds in

medicinal¹and agricultural chemistry²have strongly stimulated

the search for eﬃcient synthetic methods leading to ﬂuorinated

ﬁne chemicals.^3,4As a consequence of this impulse, many

metal-mediated or -catalyzed perﬂuoroalkylation reactions have

been developed during the past decade.^3,5Among these

reactions, the perﬂuoroalkylation of alkenes has received special

attention, because the presence of a CC bond in the

substrate oﬀers the opportunity to introduce further function-

alization in combination with the perﬂuoroalkylation proc-

ess.⁶⁻⁸Most metal-mediated or -catalyzed alkene perﬂuor-

oalkylation reactions are based on the generation of

perﬂuoroalkyl radicals that add to the alkene CC bond to

give carbon-based radicals, which can evolve in diﬀerent ways to

originate diﬀerent types of reaction products.^6,9−11In general,

the speciﬁc role of the metal species in these reactions is not

clear. In most cases, it is assumed that the metal participates in

the electron-transfer steps, facilitating the formation of the

perﬂuoroalkyl radicals and the oxidation or reduction of radical

Received: December 13, 2016

DOI: 10.1021/acs.organomet.6b00929

Organometallics XXXX, XXX, XXX−XXX

Organometallics

Article

co-workers reported that the complexes [M(η⁵-Cp)₂(η²-C₂H₄)]

(M = Mo, W) react with IR_F(R_F= i-C₃F₇, n-C₄F₉, CF₂C₆F₅,

C₆F₅) to aﬀord diﬀerent types of complexes resulting from the

oxidative addition to the metal, from perﬂuoroalkylation or

-arylation of a Cp ring, or from the perﬂuoroalkylation of the

coordinated ethene.¹⁹We have reported the perﬂuoroalkylation

of coordinated ethene in the reactions of [Rh(η⁵-Cp*)(η²-

C₂H₄)₂] with IR_F(R_F= i-C₃F₇, s-C₄F₉, t-C₄F₉) to give the

complexes [Rh(η⁵-Cp*)(CH₂CH₂R_F)(μ-I)]₂or in the reactions

of [Rh(η⁵-Cp*)(η²-C₂H₄)(PR₃)] with IR_Fto give the

complexes [Rh(η⁵-Cp*)(CH₂CH₂R_F)I(PR₃)] (R = Me, R_F=

i-C₃F₇, t-C₄F₉, C₆F₅; R = Ph, R_F= i-C₃F₇, CF₂C₆F₅).²⁰These

reactions seem to proceed by an unusual ionic mechanism in

which a perﬂuoroalkyl carbanionwhich is generated by

reaction of the iodoperﬂuoroalkane with the electron-rich

metal centersattacks the coordinated alkene.^19,20With these

precedents, we became interested in investigating if Ir(I) ethene

complexes would show a reactivity similar to that of their Rh(I)

analogues and if perﬂuoroalkylated alkenes can be formed in a

stoichiometric or catalytic way from the resulting [M]-

CH₂CH₂R_Fcomplexes through β-hydride elimination reac-

tions.^21,22Thus, in this paper we report the results of the study

of the reactivity of [Ir(η⁵-Cp*)(η²-C₂H₄)₂] and [Ir(η⁵-Cp*)(η²-

C₂H₄)(PPh₃)] with primary, secondary, or tertiary iodoper-

ﬂuoroalkanes and new reactions of their Rh(I) analogues with

I-c-C₆F₁₁and I-t-C₄F₉. We have also studied β-hydride

elimination reactions of the resulting [M]CH₂CH₂R_Fcom-

plexes that lead to alkenes of the type CH₂CHR_Fand C−H

activation reactions giving polyﬂuoroalkanes of the type

CH₃CH₂R_F. Finally, we have studied the Rh- and Ir-catalyzed

reactions of ethene with iodoperﬂuoroalkanes which lead to

products of the type ICH₂CH₂R_F. Evidence for a metal-initiated

radical addition has been obtained.

Scheme 1

RESULTS AND DISCUSSION

■

Reactions of Rh and Ir Ethylene Complexes with

Perﬂuoroalkyl Iodides. The reaction of the complex [Ir(η⁵-

Cp*)(η²-C₂H₄)₂] with I-t-C₄F₉in n-pentane gave ethene and

[Ir(η⁵-Cp*)(CH₂CH₂-t-C₄F₉)(μ-I)]₂(1) as a red precipitate

(Scheme 1). Analogously, the reactions of [Ir(η⁵-Cp*)(η²-

C₂H₄)₂] or [Rh(η⁵-Cp*)(η²-C₂H₄)₂] with I-c-C₆F₁₁gave the

homologous complexes [M(η⁵-Cp*)(CH₂CH₂-c-C₆F₁₁)(μ-I)]₂

(M = Ir (2), Rh (3)) as the main products, but in these cases

the unsymmetrical iodo-bridged complexes [(η⁵-Cp*)IM(μ-

I)₂M(η⁵-Cp*)(CH₂CH₂-c-C₆F₁₁)] (M = Ir (2_I), Rh (3_I)) and

minor amounts of unidentiﬁed byproducts were also formed.

Compounds 2 and 3 could not be obtained free of 2_Ior 3_Iby

crystallization, but the 2 + 2_Iand 3 + 3_Imixtures were

successfully used in the synthesis of pure derivatives containing

phosphine ligands. Other investigated iodoperﬂuoroalkanes did

not react with [Ir(η⁵-Cp*)(η²-C₂H₄)₂] (ICF₃at 80 °C, I-n-C₃F₇

at room temperature) or gave mixtures containing mainly

[Ir(η⁵-Cp*)I(μ-I)]₂(I-i-C₃F₇or I-s-C₄F₉, both at room

temperature).

(Scheme 2). Thus, the reactions with I-t-C₄F₉or I-i-C₃F₇gave

respectively compound 4, which was identiﬁed by NMR, or

[Ir(η⁵-Cp*)(CH₂CH₂-i-C₃F₇)I(PPh₃)] (7), which was isolated

Scheme 2

The reaction of 1 with PPh₃gave [Ir(η⁵-Cp*)(CH₂CH₂t-

C₄F₉)I(PPh₃)] (4) (Scheme 1). Analogously, the bridge-

splitting reactions of the mixtures 2 + 2_Iand 3 + 3_Igave the

compounds [M(η⁵-Cp*)(CH₂CH₂c-C₆F₁₁)I(PPh₃)] (M = Ir

(5), Rh (6)) together with the byproducts [M(η⁵-Cp*)-

I₂(PPh₃)] (M = Ir, Rh). Compounds 4−6 were isolated in 43−

78% yields by column chromatography.

We have also explored the reactivity of the complex [Ir(η⁵-

Cp*)(η²-C₂H₄)(PPh₃)] toward diﬀerent perﬂuoroalkyl iodides

DOI: 10.1021/acs.organomet.6b00929

Organometallics XXXX, XXX, XXX−XXX

Organometallics

Article

in 23% yield by column chromatography. The analogous

reactions with ICF₃, I-n-C₃F₇, I-s-C₄F₉, and I-c-C₆F₁₁gave

mixtures containing mainly [Ir(η⁵-Cp*)I₂(PPh₃)]. In contrast,

the reaction of the rhodium homologue [Rh(η⁵-Cp*)(η²-

C₂H₄)(PPh₃)] with I-t-C₄F₉gave [Rh(η⁵-Cp*)(CH₂CH₂-t-

C₄F₉)I(PPh₃)] (8), which was isolated in 61% yield. A parallel

behavior has been previously observed in the analogous

reactions between [Rh(η⁵-Cp*)(η²-C₂H₄)(PMe₃)] and IR_F

(R_F= i-C₃F₇, t-C₄F₉, C₆F₅).²⁰

= Ir, Rh, respectively). As expected, an increase in the NMR

signals assigned to the mixed complexes 2_Iand 3_Iwas observed,

which was produced by the cleavage of the iodo bridges of 2 or

3 and [M(η⁵-Cp*)I(μ-I)]₂and recombination of the resulting

fragments.

Compounds 4−9 gave the expected signals in their H or

³¹P{¹H} NMR spectra, and their chemical shifts and coupling

constants were similar to the corresponding values reported for

complexes [Rh(η⁵-Cp*)(CH₂CH₂-i-C₃F₇)I(PR₃)] (R = Me,

Ph).²⁰In accord with to the lack of symmetry of these

compounds, their ¹H spectra showed four second-order

multiplets in the range from 1.56 to 3.74 ppm for the CH₂−

CH₂unit. For the same reason, all of the ﬂuorine nuclei of 5

and 6 (see the Supporting Information), the CF₃groups of 7,

and the CH₂CF₂group of 9 appeared inequivalent in their ¹⁹F

NMR spectra.

As the previously reported reaction of I-n-C₄F₉with [Rh(η⁵-

Cp*)(η²-C₂H₄)(PMe₃)] gives mainly the oxidative addition

product [Rh(η⁵-Cp*)(n-C₄F₉)I(PMe₃)],²⁰we prepared the

complex [Rh(η⁵-Cp*)(CH₂CH₂-n-C₄F₉)(PMe₃)] (9) by re-

action of [Rh(η⁵-Cp*)(η²-C₂H₄)(PMe₃)] with ICH₂CH₂-n-

C₄F₉(Scheme 2).

The identity of complexes 1−3 was established on the basis

of their H, ¹³C{¹H}, and ¹⁹F NMR data. Their signals appear

Our previous mechanistic studies of the reactions of [Rh(η⁵-

Cp*)(η²-C₂H₄)(PMe₃)] with various secondary or tertiary

iodoperﬂuoroalkanes showed that CH₃OD eﬃciently inhibits

the perﬂuoroalkylation of coordinated ethene, giving DR_Fas

the main reaction product. This suggests an ionic mechanism

(Scheme 3, pathway a), where the generated perﬂuoroalkyl

in the same ranges as those previously reported for the

complexes [Rh(η⁵-Cp*)(CH₂CH₂R_F)(μ-I)]₂(R_F= i-C₃F₇, s-

C₄F₉).²⁰In particular, the ¹H NMR spectra show characteristic

signals for the methylenic protons, which appear as second-

order multiplets in the range between 2.9 and 3.8 ppm. The

presence of the perﬂuorocyclohexyl group in complexes 2 and 3

was conﬁrmed by their ¹⁹F NMR spectra, which showed seven

signals in both cases, in agreement with the C_2hsymmetry of

the complexes (see the Supporting Information). In addition,

the crystal structure of 1 was determined by single-crystal X-ray

diﬀraction and shows a centrosymmetric iodo-bridged dimer

with the pairs of η⁵-Cp* and CH₂CH₂-t-C₄F₉ligands placed in

mutually trans positions (Figure 1). This disposition was also

observed for the complexes [Rh(η⁵-Cp*)(CH₂CH₂R_F)(μ-I)]₂

(R_F= i-C₃F₇, s-C₄F₉)²⁰and is likely adopted to reduce the steric

hindrance.

Scheme 3

anions can be trapped by a D⁺source. In contrast, the

analogous reactions of [Rh(η⁵-Cp*)(η²-C₂H₄)₂] were not

aﬀected by methanol but were inhibited by the radical

scavenger 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO), sug-

gesting that in this case a radical mechanism could be the

dominant one (Scheme 3, pathway b).²⁰

To get insight into the mechanism of the perﬂuoroalkylation

reactions of [Ir(η⁵-Cp*)(η²-C₂H₄)(L)] by IR_F, we carried out

representative reactions in the presence of CH₃OH or CH₃OD

(2 equiv) using D₈-toluene as solvent. Thus, in analogy with the

previous studies on Rh(I) complexes,²⁰the reactions of [Ir(η⁵-

Cp*)(η²-C₂H₄)(PPh₃)] with I-i-C₃F₇and CH₃OX gave X-i-

C₃F₇(X = H, D) almost quantitatively.²³These results provide

support to an ionic mechanism as the main reaction pathway

(Scheme 3, pathway a). Moreover, the absence of DR_Famong

the products of the reactions performed in D₈-toluene with

added CH₃OH suggests that free perﬂuoroalkyl radicals are not

signiﬁcantly involved in these reactions, because perﬂuoroalkyl

Figure 1. Crystal structure of 1 (50% thermal ellipsoids). Selected

bond lengths (Å) and angles (deg): Ir(1)−CNT1 (CNT1 = centroid

of C1−5) 1.824(4), Ir(1)−C(11) 2.176(9), Ir(1)−I(1) 2.7171(6),

Ir(1)−I(1A) 2.7107(6), I(1)−Ir(1)−I(1A) 83.624(18), C(11)−

Ir(1)−I(1) 88.8(2), C(11)−Ir(1)−I(1A) 86.6(2), Ir(1A)−I(1)−

Ir(1) 96.378(17).

In the H NMR spectra, complexes 2_Iand 3_Igave two

singlets corresponding to their inequivalent η⁵-Cp* groups and

a multiplet for the methylenic hydrogens. In the ¹⁹F NMR

spectra, the signals of 2_Ior 3_Icoincide with those of 2 or 3. To

conﬁrm these assignments, NMR samples containing 2 and 2_I

or 3 and 3_Iin C₆D₆were treated with [M(η⁵-Cp*)I(μ-I)]₂(M

DOI: 10.1021/acs.organomet.6b00929

Organometallics XXXX, XXX, XXX−XXX

Organometallics

Article

radicals are good hydrogen scavengers¹⁰and thus are expected

to abstract a deuterium atom from D₈-toluene to give DR_F.

These observations point to an ionic mechanism (Scheme 3,

pathway a) in which a cationic Ir(III) ethene complex and a

perﬂuoroalkyl anion are initially generated by reaction of the

Ir(I) complexes with the IR_F. Addition of the perﬂuoroalkyl

anion to the coordinated ethene molecule would aﬀord the

perﬂuoroalkylated complex. However, similar experiments

carried out with other combinations of the complexes [Ir(η⁵-

Cp*)(η²-C₂H₄)(L)] and IR_F(L = PPh₃, C₂H₄and R_F= t-C₄F₉;

L = C₂H₄and R_F= c-C₆F₁₁) did not provide conclusive

evidence for the anionic or radical nature of the mechanisms of

these reactions.

Among the decomposition products, the complex 12 and

organic products CH₃CH₂R_Fand CH₂CHR_F(R_F= c-C₆F₁₁,

i-C₃F₇) were detected. No hydride signals were observed in the

¹H NMR spectra of the reaction mixtures other than those of

10 or 11, which suggests that the unstable hydrido complex

formed after decoordination of the alkene evolves to give other

products which could not be identiﬁed. In contrast, addition of

PPh₃to 10 and heating at 50 °C for 15 h gave mainly the

complex 13 and CH₃CH₂-c-C₆F₁₁, along with minor amounts

of [Ir(η⁵-Cp*)H(PPh₃)₂]OTf (14) and CH₂CH₂-c-C₆F₁₁

(Scheme 4). The hydride 14 was identiﬁed by comparison of

its NMR data with those reported for [Ir(η⁵-Cp*)H(PPh₃)₂]-

BF₄.²⁵

Elimination of Perﬂuoroalkylated Organic Com-

pounds in the Ir Complexes. The reaction of the complexes

5 and 7 with AgOTf in CH₂Cl₂gave AgI and the complexes

[Ir(η⁵-Cp*)H(η²-CH₂CHR_F)(PPh₃)]OTf (R_F= c-C₆F₁₁

(10), i-C₃F₇(11)) (Scheme 4). These complexes were isolated

The reactions of the diastereomeric pairs of 10 or 11 with

CO quantitatively aﬀorded the complexes [Ir(η⁵-Cp*)-

(CH₂CH₂R_F)(CO)(PPh₃)]OTf (R_F= c-C₆F₁₁(15), i-C₃F₇

(16)) (Scheme 5). The crystal structure of 16 supports the

proposed structure (Figure 2).

Scheme 4

Scheme 5

as mixtures of two diastereomers, which arise from the

coordination of the diastereotopic faces of the alkenes to the

chiral metal fragment (see below). In contrast, the analogous

reaction of the complex 4 with AgOTf in CD₂Cl₂gave

CH₃CH₂-t-C₄F₉and the previously reported cyclometalated

complex [Ir(η⁵-Cp*)(η²-o-C₆H₄PPh₂)(OTf)] (12).²⁴Addition

of PPh₃to this mixture gave the complex [Ir(η⁵-Cp*)(η²-o-

C₆H₄PPh₂)(PPh₃)]OTf (13), which was isolated and crystallo-

graphically characterized (see below).

Figure 2. ORTEP representation (50% thermal ellipsoids) of the

cation in the crystal structure of 16. Selected bond lengths (Å) and

angles (deg): Ir−CNT1 (CNT1 = centroid of C1−5) 1.9120(15),

Ir(1)−C(16) 1.872(3), Ir(1)−C(11) 2.152(3), Ir(1)−P(1) 2.3240(8),

C(16)−Ir(1)−C(11) 93.23(12), C(16)−Ir(1)−P(1) 94.54(10),

C(11)−Ir(1)−P(1) 87.62(8).

After 10 h in solution at room temperature, both 10 and 11

partially decomposed to give a mixture of products.

Decomposition was complete on heating for 2 h at 45 °C.

DOI: 10.1021/acs.organomet.6b00929

Organometallics XXXX, XXX, XXX−XXX

Organometallics

Article

Interestingly, when the reaction of both diastereomers of 11

with PPh₃was carried out at room temperature for a shorter

time (2 h), the complex [Ir(η⁵-Cp*)(CH₂CH₂-i-C₃F₇)-

(PPh₃)₂]OTf (17) was isolated in 48% yield. The result of

the thermal decomposition of 17 (CD₂Cl₂, 50 °C) was

analogous to that of the reaction of 11 with PPh₃, aﬀording

compounds 13 and CH₃CH₂-i-C₃F₇(main products), 14, and

CH₂CH-i-C₃F₇.

which can eﬀectively hinder the approach of the β-hydrogen

atom to the metal center in the β-agostic complex. Never-

theless, compound 12 was also observed as one of the products

resulting from the decomposition of 10 and 11, and

cyclometalation is the main decomposition pathway of these

compounds in the presence of an extra equiv of PPh₃.

Formation of compounds 15−17 in the reactions of 10 and

11 with CO or PPh₃can also be explained by considering that

the formation of the hydrido oleﬁn complexes is reversible.

Thus, migratory insertion of the oleﬁn into the Ir−H bond

followed by coordination of the added ligand would give the

observed products (Scheme 6).

The reactivity shown in Schemes 4 and 5 can be rationalized

by considering that the reactions of 4, 5, or 7 with AgOTf ﬁrst

aﬀord the triﬂato complexes [Ir(η⁵-Cp*)(CH₂CH₂R_F)(OTf)-

(PPh₃)] (R_F= c-C₆F₁₁, i-C₃F₇, t-C₄F₉) (Scheme 6). Owing to

The diastereomeric ratios of 10 and 11 were 78:22 and

Scheme 6

62:38, respectively, as determined by integration of their NMR

spectra. The H NMR spectra of 10 or 11 showed two signals

in the hydride region, a broad singlet at −14.6 ppm and a

doublet at −15.8 ppm, corresponding to the major and minor

diastereomers, respectively. The broad singlet transformed into

a doublet on cooling to 0 °C. The J_PHvalues of the major

diastereomers (26.5 and 25.6 Hz) were sligthly lower than

those of the minor diastereomers (29.1 and 30.4 Hz), and both

the δ and J_PHvalues are similar to those reported for the related

Ir complexes containing terminal hydrido ligands [Ir(η⁵-

Cp)H(PPh₃)(C₂H₄)]⁺(−15.60 ppm, 27 Hz),²⁷[Ir(η⁵-Cp*)-

H(PPh₃)₂]⁺(−15.47 ppm, 27.8 Hz),²⁵and [Ir(η⁵-Cp*)H-

(PPh₃)(CO)]⁺(−14.28 ppm, 26.1 Hz).²⁸The instability of

these hydrido oleﬁn complexes in solution hampered their

study by high-temperature NMR spectroscopy, but mutual

interconversion of the diastereomers at room temperature was

observed in the NOESY spectra of both 10 and 11, which

showed EXSY peaks that correlate the major and minor

diastereomers (see Supporting Information). This interconver-

sion could take place through β-agostic complexes (Scheme 6)

where the interaction of each of the two diastereotopic β-

hydrogen atoms (H_Aor H_B) with the metal would give a

diﬀerent diastereomer of the hydrido oleﬁn complex. We could

not obtain single crystals of these compounds for an X-ray

crystal structure determination despite repeated attempts.

However, (¹⁹F,¹H)-HOESY experiments revealed that, as

expected on steric grounds, in both diastereomers of 10 and

11 the R_Fgroup is oriented away from the PPh₃ligand

(Scheme 6) and that in the major diastereomers the R_Fgroup is

placed close to the methylic hydrogens of the Cp* ligand (see

the Supporting Information).

Compound 13 and its congener [Ir(η⁵-Cp*)(η²-o-

C₆H₄PPh₂){P(p-Tol)₃}]OTf (18) were synthesized more

directly by the sequential reaction of [Ir(η⁵-Cp*)(Me)Cl-

(PPh₃)] with AgOTf and PPh₃or P(p-Tol)₃, respectively

(Scheme 7). It is noteworthy that in 18 the P(p-Tol)₃ligand is

not cyclometalated. This suggests that the C−H activation step

is previous to the coordination of the second phosphine and

the poor donor ability of the triﬂate anion, these complexes are

unstable and evolve in diﬀerent ways depending on R_F. Thus,

when R_Fis t-C₄F₉, the triﬂato complex would undergo an

intramolecular cyclometalation to give mainly CH₃CH₂-t-C₄F₉

and 12, a reaction analogous to that observed for [Ir(η⁵-

Cp*)Me(OTf)(PPh₃)].²⁴In contrast, when R_Fis c-C₆F₁₁or i-

C₃F₇, the intermediate triﬂato complex would evolve to the

hydrido oleﬁn complex 10 or 11 through a β-agostic

intermediate^22,26(Scheme 6). This diﬀerent behavior is

attributable to the greater bulk of the t-C₄F₉substituent,

Scheme 7

DOI: 10.1021/acs.organomet.6b00929

Organometallics XXXX, XXX, XXX−XXX

Organometallics

Article

that the cyclometalated and the noncyclometalated phosphine

ligands do not undergo exchange.

Scheme 8

In the crystal structure of 13 (Figure 3) the coordination

environment of the Ir center is highly distorted with respect to

Figure 3. ORTEP representation of the cation in the crystal structure

of 13. Selected bond lengths (Å) and angles (deg): Ir−CNT1 (CNT1

= centroid of C1−5) 1.9133(15), Ir(1)−C(11) 2.103(4), Ir(1)−P(2)

2.3099(11), Ir(1)−P(1) 2.3209(9), C(11)−Ir(1)−P(2) 87.65(10),

C(11)−Ir(1)−P(1) 66.79(11), P(2)−Ir(1)−P(1) 94.79(4). The pair

of ortho hydrogens of one of the Ph groups of the PPh₃ligand

showing shortest distances to the phenylic rings of the Ph₂PC₆H₄

ligand is represented. H−[ring centroid] distances (Å): H(66)−

cent[C(31)−C(36)] 3.468; H(62)−cent[C(11)−C(16)] 2.628.

a symmetrical piano-stool complex because of the formation of

a four-membered metallacycle. The rigid disposition of the

cyclometalated P(C₆H₄)Ph₂ligand and the steric crowding can

explain the slow rotation around the Ir−PPh₃observed for both

13 and 18 by variable-temperature H and ³¹P{¹H} NMR

spectroscopy (see the Supporting Information). In addition,

one of the phenyl rings of the PPh₃ligand (labeled as C61−

C66) is very close to the metalated ring and to one of the

phenyl rings of the Ph₂PC₆H₄ligand. In such a disposition, the

ortho hydrogens of this ring are placed very close to the nearby

aromatic rings, as reﬂected by the short distances between these

hydrogen atoms and the centroids of the phenyl rings. This

would explain the slow rotation around one of the P−Ar bonds

observed in the low-temperature ¹H NMR spectra of 13 and 18

and the unusually low chemical shift values of the ortho protons

of this Ph ring, which appear in the range from 4.9 to 6.1 ppm

(see the Supporting Information).

β-Elimination of Perﬂuoroalkylated Alkenes in the Rh

Complexes. To promote β-hydride elimination in the

complexes [Rh(η⁵-Cp*)(CH₂CH₂R_F)I(PR₃)], we reacted

complexes 6, 8, and 9 and their previously reported congeners

[Rh(η⁵-Cp*)(CH₂CH₂R_F)I(PR₃)] (R = Me, R_F= i-C₃F₇, t-

C₄F₉; R = Ph, R_F= i-C₃F₇)²⁰with AgOTf (OTf = OSO₂CF₃)

in CH₂Cl₂(Scheme 8). These reactions gave rise to

precipitation of AgI and formation of the triﬂato complexes

[Rh(η⁵-Cp*)(CH₂CH₂R_F)(OTf)(PR₃)] (19−24). These un-

stable complexes were not isolated, and their structures were

tentatively proposed on the basis of their NMR spectra (see

below). Thus, in situ generated samples in CD₂Cl₂showed

signals corresponding to the alkenes H₂CCHR_F(R_F= i-

C₃F₇, n-C₄F₉, t-C₄F₉, c-C₆F₁₁) and several unidentiﬁed Rh

complexes after 2−3 h at room temperature. Since these

alkenes are likely produced by a β-hydride elimination reaction,

we examined the high-ﬁeld region of the H NMR spectra of

the mixtures to detect [Rh]−H species. However, no hydrido

complexes were detected, except in the decomposition of 21,

which gave [Rh(η⁵-Cp*)(H)(PPh₃)₂]OTf (25) as the main

metal-containing product. These observations suggest that

hydrido alkene complexes of the type [Rh(η⁵-Cp*)(H)(H₂C

CHR_F)(PR₃)]OTf, which should be formed from 19−24 by a

β-hydride elimination, are unstable and decompose to aﬀord

the free alkenes and a mixture of unidentiﬁed Rh complexes.

Compound 25 was unambiguously identiﬁed by comparison of

its NMR signals with those reported for [Rh(η⁵-Cp*)(H)-

(PPh₃)₂]PF₆.²⁹

Formation of 25 suggests that the decomposition of the

triﬂato complexes could proceed in a more clean way in the

presence of 1 equiv of phosphine ligand. Thus, addition of PPh₃

to a solution of 19, 20, or 21 in CD₂Cl₂led to a mixture

containing the initial triﬂato complex, the respective H₂C

CHR_F, the hydrido complex 25, and another complex which

was tentatively assigned as [Rh(η⁵-Cp*)(CH₂CH₂R_F)(PPh₃)₂]-

OTf (R_F= t-C₄F₉(26), c-C₆F₁₁(27), i-C₃F₇(28)) (Scheme 8).

Complexes 26−28 could not be isolated, and their structure

was proposed on the basis of their characteristic NMR signals

(see below). On standing for 1−3 days at 30−40 °C, the

mixture evolved to give H₂CCHR_Fand 25 almost

DOI: 10.1021/acs.organomet.6b00929

Organometallics XXXX, XXX, XXX−XXX

Organometallics

Article

quantitatively (see the Supporting Information). In contrast,

addition of PMe₃to solutions of in situ generated 23 or 24

(Scheme 4) gave the stable complexes [Rh(η⁵-Cp*)-

(CH₂CH₂R_F)(PMe₃)₂]OTf (R_F= t-C₄F₉(29), i-C₃F₇(30)),

which were isolated. When these complexes were heated in

CD₂Cl₂solution, they decomposed to give a mixture of

products where no hydrido complexes were observed and only

traces of the alkenes H₂CCHR_F(R_F= i-C₃F₇, t-C₄F₉) were

detected by NMR spectroscopy. [Rh(η⁵-Cp*)Cl(PMe₃)₂]OTf

was the main component of these mixtures. It was identiﬁed in

the ¹⁹F NMR spectra the CF₃SO₃signal appeared as a broad

singlet around −79 ppm. Similar δ(¹⁹F) values have been found

in ionic triﬂates, such as complexes 29 and 30, and in Rh(III)

or Ir(III) triﬂato complexes.³⁰It is noteworthy that in

complexes 21 and 24 the diastereotopic CF₃groups of the

perﬂuoroisopropyl moiety gave only one ¹⁹F NMR signal

instead of the expected two signals, which were observed for

the analogous iodo complexes.²⁰The broadening of the triﬂato

signals and the equivalence of the CF₃goups of complexes 21

and 24 could be produced by fast triﬂate dissociation followed

by inversion of the conﬁguration at the metal and triﬂate

recoordination.³¹

solution by comparing its H and ³¹P{¹H} NMR signals with

those of an independently prepared sample (see the Supporting

Information). In addition, its X-ray structure (Figure 4) was

determined.

Diagnostic features of the H NMR spectra of complexes

26−30 were the triplet signal observed for the Cp* methyl

protons, which is originated by the coupling with two

equivalent ³¹P nuclei, and the homotopic character of the

CH₂protons. The ¹⁹F NMR spectra showed a sharp singlet for

−

the CF₃SO₃and, in 28 and 30, a sharp doublet for the two

equivalent CF₃groups. The ¹J_RhPvalues of 26−28 were similar

to those of 29 and 30. These ¹J_RhPvalues are about 19 Hz lower

than those of their parent triﬂato complexes, in agreement with

the substitution of the triﬂate by a phosphine ligand.

Catalytic Addition of Iodoperﬂuoroalkanes to Ethene.

After observing the formation of alkenes H₂CCHR_Ffrom

[M]−CH₂CH₂R_Fcomplexes (M = Rh or Ir), we investigated if

these alkenes could be obtained from ethene and I-i-C₃F₇by

using [M(η⁵-Cp*)(η²-C₂H₄)₂] and [M(η⁵-Cp*)(CH₂CH₂-i-

C₃F₇)I(PPh₃)] (M = Rh, Ir) as catalysts. The hypothetical

catalytic cycle is outlined in Scheme 9A. The perﬂuoroalkyla-

tion and β-elimination steps have been observed in the present

and previous works.²⁰Stoichiometric generation of a Rh(I)

oleﬁn complex by the deprotonation of a Rh(III) hydrido

complex has been previously reported.³²

The results of the performed catalytic tests are presented in

Table 1. Only traces of the expected alkenes were detected in

some cases. Instead, the compound ICH₂CH₂-i-C₃F₇, resulting

from the addition of the iodoperﬂuoroalkane to the alkene

double bond, was formed. The complexes [M(η⁵-Cp*)(η²-

C₂H₄)₂] (M = Rh, Ir) are able to initiate the addition of I-i-

C₃F₇to ethene (entries 1−4) in the absence of any additive,

although addition of a base (NaOAc) modestly increases the

Figure 4. ORTEP representation (50% thermal ellipsoids) of the

cation in the crystal structure of [Rh(η⁵-Cp*)Cl(PMe₃)₂]OTf.

Selected bond lengths (Å) and angles (deg): Rh−CNT1 (CNT1 =

centroid of C1−5) 1.8663(16), Rh−P(2) 2.2876(11), Rh−P(1)

2.3141(12), Rh−Cl 2.4064(10), P(2)−Rh−P(1) 97.11(3), P(2)−

Rh−Cl 86.11(4), P(1)−Rh−Cl 87.03(4).

The ¹H NMR spectra of the triﬂato complexes 19−24

displayed the expected signals for the η⁵-Cp* and phosphine

ligands, as well as for the methylenic protons. Their ³¹P{¹H}

NMR spectra showed a doublet with a J_RhPvalue higher by

3.9−7.5 Hz than those of their iodo analogues, which is in

agreement with the poor donor ability of the TfO⁻anion. In

Scheme 9

DOI: 10.1021/acs.organomet.6b00929

Organometallics XXXX, XXX, XXX−XXX

Organometallics

Article

Table 1. Catalytic Addition of Perﬂuoroalkyl Iodides to Ethene

entry

initiator

additive

time (h)

T (°C)

conversn of ICH₂CH₂R_F(%)

[Rh(η⁵-Cp*)(η²-C₂H₄)₂]

[Ir(η⁵-Cp*)(η²-C₂H₄)₂]

none

[Ir(η⁵-Cp*)(η²-C₂H₄)₂]

none

[Rh(η⁵-Cp*)(η²-C₂H₄)₂]

[Rh(η⁵-Cp*)(CH₂CH₂-i-C₃F₇)(μ-I)]₂

NaOAc

AgOTf

none

[Rh(η⁵-Cp*)(CH₂CH₂-i-C₃F₇)I(PPh₃)]

2.5

PPh₃

[Rh(η⁵-Cp*)I₂(PPh₃)₂]

none

[Rh(η⁵-Cp*)(η²-C₂H₄)₂]

TEMPO

Conditions unless speciﬁed otherwise: C₂H₄(0.12 mmol), I-i-C₃F₇(0.12 mmol), initiator (0.0060 mmol), additive (0.15 mmol of NaOAc, 0.12

mmol of AgOTf, or 0.012 mmol of TEMPO) in C₆D₆, except for entries 13 and 14, where the amount of ethene used was not determined.

Determined by integration of the ¹⁹F NMR spectrum of the reaction mixture using a internal standard. Reference 20. CD₂Cl₂was used as solvent.

conversion (entry 5). The Ir complexes are less active than the

corresponding Rh complexes, and Rh(III) or Ir(III) complexes

are also able to initiate the addition, although with lower

activity than the corresponding Rh(I) or Ir(I) complexes

(entries 6−9). An exception to this trend was the reaction

initiated by a mixture of [Rh(η⁵-Cp*)(CH₂CH₂-i-C₃F₇)I-

(PPh₃)] and AgOTf (entry 10), which gave the fastest reaction

among all tested. Although PPh₃has been reported to initiate

the addition of iodoperﬂuoroalkanes to alkenes,³³initiation by

dissociated PPh₃from the Rh(III) complexes seems unlikely

because no reaction was observed when PPh₃and [Rh(η⁵-

Cp*)I₂(PPh₃)] were used as initiators (entries 11 and 12). I-n-

C₄F₉gave a sluggish reaction at 80 °C using [Rh(η⁵-Cp*)(η²-

C₂H₄)₂] as initiator and, in addition to ICH₂CH₂-n-C₄F₉, other

unidentiﬁed organoﬂuorine products were detected.

norbornane. The selective formation of this product is typical

for a radical-initiated addition.³⁶The byproducts ICH₂CH₂-i-

C₃F₇and C₂H₄were also detected. Since norbornene does not

replace the coordinated ethene in [Rh(η⁵-Cp*)(η²-C₂H₄)₂]

under the experimental conditions (from room temperature to

80 °C), the observed ethene should be liberated after the

radical initiation step. Radical addition of I-i-C₃F₇to the

generated ethene would form ICH₂CH₂-i-C₃F₇.

On the basis of these observations, a radical chain mechanism

is proposed (Scheme 9B). The reaction is initiated by single

electron transfer from the Rh(I) or Ir(I) initiator to a molecule

of IR_F, to give I⁻and a R_Fradical, which would add to the

•

alkene. The resulting radical would react with other molecule of

•

IR_Fto give ICH₂CH₂R_Fand another R_Fradical, which would

continue the reaction. The M(II) species (M = Rh, Ir)

generated in the initiation step could undergo a disproportio-

nation reaction, which would generate a M(I) complex, a

M(III) diiodo complex, and free ethene, or be oxidized by IR_F

to give a M(III) diiodo complex and ethene.

No reaction was observed in the absence of the complexes

(Table 1, entry 13). During the course of the reaction the

initiators were progressively transformed into the correspond-

ing diiodo complexes [M(η⁵-Cp*)I(μ-I)]₂(M = Rh, Ir) and

[Rh(η⁵-Cp*)I₂(PPh₃)].

According to the proposed mechanism, in those experiments

where M(III) complexes are used as initiators (Table 1, entries

6−10) there should be a previous reduction process to generate

the true M(I) initiators. The detection of traces of the alkene

H₂CCH-i-C₃F₇in the reaction mixtures of the experiments

shown in entries 6 and 8 suggests that these M(I) species could

be generated by a β-elimination reaction followed by

deprotonation of the resulting hydrido complex. In entry 10,

where no base was used, the active species could be formed by

decomposition of the hydrido oleﬁn intermediate. The

generated [M(η⁵-Cp*)(η²-C₂H₄)L] complexes would react

with IR_Fto give [M(η⁵-Cp*)(CH₂CH₂R_F)I(L)], but they

would also initiate a faster radical chain reaction that, in the

presence of an excess of IR_Fand ethene, would become the

dominant reaction pathway.

Radical addition of iodoperﬂuorolkanes to alkenes initiated

by metal salts or complexes has been reported.^10,13,17,34In this

reaction, the main role of the metal species is to transfer one

electron to IR_F, to give I⁻and a perﬂuoroalkyl radical, which

reacts with the alkene, initiating a radical chain reacion. To test

if the investigated reactions follow a radical mechanism, we

carried out the reaction of I-i-C₃F₇, ethene, and [Rh(η⁵-

Cp*)(η²-C₂H₄)₂] in the presence of TEMPO ([TEMPO]:[Rh]

= 2 equiv). The radical scavenger TEMPO is expected to react

with the generated perﬂuoroalkyl radical, disrupting the radical

chain to form the stable adduct TEMPO-R_F.³⁵In agreement

with this expectation, no ethene perﬂuoroalkylation was

observed, and signals corresponding to the TEMPO−i-C₃F₇

adduct were detected in the H and ¹⁹F NMR spectra of the

reaction mixture (see the Supporting Information), suggesting

that a radical mechanism is operating.

CONCLUSIONS

■

Complexes [Ir(η⁵-Cp*)(η²-C₂H₄)₂] and [Ir(η⁵-Cp*)(η²-

C₂H₄)(PPh₃)] react with secondary or tertiary iodoperﬂuor-

oalkanes to give complexes of the types [Ir(η⁵-Cp*)-

(CH₂CH₂R_F)(μ-I)]₂and [Ir(η⁵-Cp*)(CH₂CH₂R_F)I(PPh₃)],

respectively. Evidence for the generation of a perﬂuoroalkyl

anion in the reaction of [Ir(η⁵-Cp*)(η²-C₂H₄)(PPh₃)] with I-i-

To further test the radical nature of these reactions, I-i-C₃F₇

was reacted with norbornene and [Rh(η⁵-Cp*)(η²-C₂H₄)₂] in a

20:5:1 molar proportion, respectively. A sluggish reaction was

observed at room temperature, but when the mixture was

heated at 80 °C for 2 h, norbornene was quantitatively

transformed into endo-2-iodo-exo-3-(heptaﬂuoroprop-2-yl)-

DOI: 10.1021/acs.organomet.6b00929

Organometallics XXXX, XXX, XXX−XXX

Organometallics

Article

²J_FF= 295.7 Hz, F_ax, 2), −139.2 (d, 2 F, J_FF= 272.5 Hz, F_ax, 2),

C₃F₇was obtained, which suggests that the reaction is initiated

by the transfer of two electrons from the Ir(I) complex to the

iodoperﬂuoroalkane. Hydrido alkene complexes of the type

[Ir(η⁵-Cp*)H(η²-CH₂CHR_F)(PPh₃)]OTf were isolated in

the reactions of [Ir(η⁵-Cp*)(CH₂CH₂R_F)I(PR₃)] with AgOTf.

The Ir-coordinated alkenes can be liberated by reaction with

PPh₃, although a competitive C−H activation reaction, leading

to [Ir(η⁵-Cp*)(η²-o-C₆H₄PPh₂)(PPh₃)]OTf and CH₃CH₂R_F,

takes place. Stable derivatives of the type [M(η⁵-Cp*)-

(CH₂CH₂R_F)(PR₃)L]OTf (L = phosphine, CO) were isolated

in these reactions. Alkenes of the type CH₂CHR_Fwere

detected in the reactions of the complexes [Rh(η⁵-Cp*)-

(CH₂CH₂R_F)I(PR₃)] with AgOTf, probably resulting from β-

hydride elimination reactions, although the intermediate

hydrido alkene complexes were not observed. Finally,

complexes of the types [M(η⁵-Cp*)(η²-C₂H₄)₂] and [M(η⁵-

Cp*)(CH₂CH₂R_F)I(L)] are able to initiate the addition

reaction of IR_Fto ethene. However, although formation of

alkenes CH₂CHR_Fwas detected in some of these reactions, a

metal-initiated radical addition to give ICH₂CH₂R_Fis the

dominant pathway.

−141.9 (d, 1 F, J_FF= 289.5 Hz, F_ax, 2), −184.1 (m, 1F, CH₂CF, 2);

the ¹⁹F signals of 2_Ioverlap with those of 2. (+)ESI-MS: m/z 455

([Ir(C₅Me₅)I]⁺), 701, 783 ([Ir₂(C₅Me₅)₂H₂I]⁺), 909

([Ir₂(C₅Me₅)₂I₂H]⁺), 965, 1217 ([Ir₂(C₅Me₅)₂I₂(CH₂CH₂C₆F₁₁)]⁺),

1571.

[Rh(η⁵-Cp*)(CH₂CH₂-c-C₆F₁₁)(μ-I)]₂(3) and [(η⁵-Cp*)IRh(μ-

I)₂Rh(η⁵-Cp*)(CH₂CH₂-c-C₆F₁₁)] (3_I). I-c-C₆F₁₁(100 μL, 0.532

mmol) was added to a solution of [Rh(η⁵-Cp*)(η²-C₂H₄)₂] (128

mg, 0.435 mmol) in n-pentane (5 mL), and the mixture was stirred for

22 h at room temperature. The red precipitate that formed was

separated by centrifugation, washed with n-pentane (2 × 1 mL), and

dried under vacuum (268 mg). The isolated solid was a mixture

containing mainly 3 (ca. 80%, as determined by integration of the

C₅Me₅signals in the ¹H NMR spectrum of the mixture), together with

small amounts of 3_I(7%) and minor amounts of unidentiﬁed

complexes containing the Rh(η⁵-Cp*) unit. This material was used for

further reactions. A dark red crystalline sample containing 3 and 3_Iin a

ca. 93:7 molar ratio (determined by integration of the ¹H NMR

spectrum) was obtained by recrystallization from Et₂O at −32 °C (45

m g , 1 5 % ) . M p : 1 7 5 ° C d e c . A n a l . C a l c d f o r

(C₃₆H₃₈F₂₂I₂Rh₂)_0.93(C₂₈H₃₄F₁₁I₃Rh₂)_0.07: C, 31.87; H, 2.85. Found:

C, 31.59; H, 2.84. H NMR (400.9 MHz, C₆D₆): δ 3.21−3.04 (m,

CH₂of 3 and 3_I), 1.53 (s, 15 H, C₅Me₅, 3_I), 1.48 (s, 15 H, C₅Me₅, 3_I),

1.39 (s, 30 H, C₅Me₅, 3). ¹³C{¹H} NMR (100.8 MHz, C₆D₆): δ 95.6

(d, ¹J_RhC= 6.6 Hz, C₅Me₅, 3_I), 94.9 (d, ¹J_RhC= 6.6 Hz, C₅Me₅, 3_I), 95.0

(d, ¹J_RhC= 7.5 Hz, C₅Me₅, 3), 35.2 (d, ²J_FC= 22.2 Hz, RhCH₂CH₂, 3),

EXPERIMENTAL SECTION

■

General Considerations. Complexes [M(η⁵-Cp*)(η²-C₂H₄)₂]

(M = Rh, Ir)³⁷and [Ir(η⁵−C₅Me₅)(Cl)(Me)(PPh₃)]³⁸were prepared

as previously reported. Solutions of [Rh(η⁵-Cp*)(η²-C₂H₄)(PR₃)] (R

= Me,³⁹Ph⁴⁰) were prepared by the reaction of [Rh(η⁵-Cp*)(η²-

C₂H₄)₂] with a stoichiometric amount of PMe₃or PPh₃in toluene.

[Ir(η⁵-C₅Me₅)(η²-C₂H₄)(PPh₃)] was prepared as reported by Berg-

man and co-workers²⁵and used immediately. Other reagents were

obtained from commercial sources and used without further

puriﬁcation. The purity of all new compounds was established by

elemental analyses and NMR spectroscopy. Additional experimental

details are included in the Supporting Information.

10.8 (s, C₅Me₅, 3_I), 9.5 (s, C₅Me₅, 3_I), 9.4 (s, C₅Me₅, 3), 6.4 (d, ¹J_RhC

24.2 Hz, RhCH₂CH₂, 3); the signals of the C₆F₁₁groups and the CH₂

signals of 3_Iwere not observed. ¹⁹F NMR (282.4 MHz, C₆D₆): δ

−117.9 (d, 2 F, J_FF= 299.6 Hz, F_eq, 3), −122.0 (d, 2 F, J_FF= 282.9

Hz, F_eq, 3), −123.7 (d, 1 F, J_FF= 289.2 Hz, F_eq, 3), −131.1 (d, 2 F,

²J_FF= 291.1 Hz, F_ax, 3), −139.0 (d, 2 F, J_FF= 285.5 Hz, F_ax, 3),

−141.7 (d, 1 F, J_FF= 277.8 Hz, F_ax, 3), −183.7 (m, 1 F, CH₂CF, 3);

all the ¹⁹F NMR signals of 3_Ioverlap with those of 3. (+)ESI-MS: m/z

365 ([Rh(C₅Me₅)I]⁺), 635, 731 ([Rh₂(C₅Me₅)₂I₂H]⁺), 857

([Rh₂(C₅Me₅)₂I₃^]+), 1039 ([Rh₂(C₅Me₅)₂I₂(CH₂CH₂C₆F₁₁)]⁺), 1387

(M + K⁺).

[Ir(η⁵-Cp*)(CH₂CH₂-t-C₄F₉)(μ-I)]₂(1). I-t-C₄F₉(170 mg, 0.491

mmol) was added to a solution of [Ir(η⁵-Cp*)(η²-C₂H₄)₂] (109 mg,

0.284 mmol) in n-pentane (6 mL), and the mixture was stirred for 22

h at room temperature. The red precipitate was ﬁltered, washed with

n-pentane (5 mL), and dried under vacuum (128 mg, 0.0912 mmol,

64.2%). Mp: 163 °C dec. Anal. Calcd for C₃₂H₃₈F₁₈I₂Ir₂: C, 27.40; H,

[Ir(η⁵-Cp*)(CH₂CH₂-t-C₄F₉)I(PPh₃)] (4). I-t-C₄F₉(202 mg, 0.584

mmol) was added to a solution of [Ir(η⁵-C₅Me₅)(η²-C₂H₄)₂] (155 mg,

0.404 mmol) in n-pentane (5 mL), and the mixture was stirred for 18

h at room temperature. The volatiles were removed under vacuum,

and the residue was dissolved in THF (6 mL). PPh₃(115 mg, 0.44

mmol) was added to the resulting solution. After it was stirred for 3 h

at room temperature, the mixture was evaporated to dryness to give a

pale orange residue, which was chromatographed on a silica gel

column using Et₂O/n-hexane (1/2) as eluent. The collected orange

fraction (R_f= 0.58) was concentrated until an orange crystalline solid

precipitated. The solid was washed with cold n-hexane (3 × 2 mL) and

dried under vacuum (302 mg, 0.313 mmol, 77.6%). Mp: 184−186 °C.

Anal. Calcd for C₃₄H₃₄F₉IPIr: C, 42.37; H, 3.56. Found: C, 42.44; H,

3.68. ¹H NMR (300.1 MHz, CDCl₃): δ 7.47 (br m, 6 H, Ph), 7.36 (br

m, 9 H, Ph), 2.86 (m, 1 H, CH₂), 2.22−1.93 (m, 3 H, CH₂), 1.50 (d,

⁴J_PH= 1.5 Hz, 15 H, C₅Me₅). ¹³C{¹H} NMR (100.8 MHz, CDCl₃): δ

135.4−132.6 (br m, Ph), 130.2 (s, C4, Ph), 127.8 (d, J_PC= 9.9 Hz,

2.73. Found: C, 27.20; H, 2.53. H NMR (400.9 MHz, C₆D₆): δ 3.81

(m, 4 H, CH₂), 2.90 (m, 4 H, CH₂), 1.37 (s, 30 H, C₅Me₅). ¹³C{¹H}

NMR (100.8 MHz, C₆D₆): δ 123.4 (q, ¹J_CF= 287.4 Hz, CF₃), 87.7 (s,

C₅Me₅), 61.7 (decaplet, J_CF= 24.7 Hz, CCF₃), 37.7 (s, IrCH₂CH₂),

8.9 (s, C₅Me₅), −5.1 (s, IrCH₂CH₂). ¹⁹F NMR (188.3 MHz, C₆D₆): δ

−65.2 (s, CF₃). (+)ESI-MS: m/z 454 ([Ir(C₅Me₅)I]⁺), 783

([Ir₂(C₅Me₅)₂H₂I]⁺), 903 ([Ir₂(C₅Me₅)₂(CH₂CH₂C₄F₉)H₂]⁺), 1155

([Ir₂(C₅Me₅)₂I₂(CH₂CH₂C₄F₉)]⁺).

[Ir(η⁵-Cp*)(CH₂CH₂-c-C₆F₁₁)(μ-I)]₂(2) and [(η⁵-Cp*)IIr(μ-I)₂Ir-

(η⁵-Cp*)(CH₂CH₂-c-C₆F₁₁)] (2_I). I-c-C₆F₁₁(45 μL, 0.24 mmol) was

added to a solution of [Ir(η⁵-Cp*)(η²-C₂H₄)₂] (91 mg, 0.24 mmol) in

n-pentane (6 mL), and the mixture was stirred for 20 h at room

temperature. The orange precipitate was ﬁltered, washed with n-

pentane (7 mL), and dried under vacuum. The isolated solid was a

mixture of 2 and 2_Iin a ca. 2:1 molar ratio, as determined by

integration of the ¹H NMR spectrum (112 mg, 64%). Mp: 168 °C dec.

Anal. Calcd for (C₃₆H₃₈F₂₂I₂Ir₂)₂(C₂₈H₃₄F₁₁I₃Ir₂): C, 27.31; H, 2.52.

Found: C, 27.11; H, 2.24. ¹H NMR (400.9 MHz, C₆D₆): δ 3.75 (m, 4

H, CH₂, 2), 3.65 (m, 4 H, CH₂, 2_I), 3.04−2.91 (m, 4 H, CH₂, 2 and

2_I), 1.47 (s, 15 H, C₅Me₅, 2_I), 1.38 (s, 15 H, C₅Me₅, 2_I), 1.37 (s, 15 H,

C₅Me₅, 2). ¹³C{¹H} NMR (100.8 MHz, C₆D₆): δ 88.3 (s, C₅Me₅, 2_I),

Ph), 122.3 (q, J_CF= 288.3 Hz, CF₃), 93.7 (d, ²J_PC= 2.8 Hz, C₅Me₅),

60.9 (decaplet, J_CF= 24.1 Hz, CCF₃), 37.8 (d, J_PC= 4.2 Hz,

IrCH₂CH₂), 9.2 (s, C₅Me₅), −15.0 (d, J_PC= 7.6 Hz, IrCH₂CH₂). ¹⁹F

NMR (282.4 MHz, CDCl₃): δ −65.8 (s). ³¹P{¹H} NMR (121.5 MHz,

CDCl₃): δ 0.3 (s). (+)ESI-MS: m/z 589 ([Ir(C₅Me₄CH₂)(PPh₃)]⁺),

717 ([Ir(C₅Me₅)I(PPh₃)]⁺), 982 (M + NH₄), 1003 (M + K⁺).

[Ir(η⁵-Cp*)(CH₂CH₂-c-C₆F₁₁)I(PPh₃)] (5). PPh₃(20 mg, 0.076

mmol) was added to a solution of 2 and 2_I(58 mg, molar ratio 4:1, ca.

0.08 mmol of Ir) in THF (5 mL). The mixture was stirred for 4.5 h at

room temperature and evaporated to dryness under vacuum. The

residue was puriﬁed by chromatography on a silica gel column using

Et₂O/n-hexane (1/3) as eluent. The collected orange fraction (R_f=

0.55) was concentrated until a pale orange crystalline precipitate

formed, which was ﬁltered, washed with cold n-hexane (3 mL), and

dried under vacuum (34 mg, 0.033 mmol, 43%). Mp: 204−206 °C.

87.8 (s, C₅Me₅, 2_I), 87.7 (s, C₅Me₅, 2), 35.2 (d, J_FC= 21.8 Hz,

IrCH₂CH₂, 2), 10.2 (s, C₅Me₅, 2_I), 9.4 (s, C₅Me₅, 2_I), 9.0 (s, C₅Me₅,

2), −7.6 (s, IrCH₂CH₂, 2); the signals of the C₆F₁₁group and the CH₂

signals of 2_Iwere not observed. ¹⁹F NMR (282.4 MHz, C₆D₆): δ

−118.2 (d, 2 F, J_FF= 286.6 Hz, F_eq, 2), −122.3 (d, 2 F, J_FF= 286.9

Hz, F_eq, 2), −124.0 (d, 1 F, J_FF= 283.5 Hz, F_eq, 2), −131.5 (d, 2 F,

DOI: 10.1021/acs.organomet.6b00929

Organometallics XXXX, XXX, XXX−XXX

Organometallics

Article

Anal. Calcd for C₃₆H₃₄F₁₁IPIr: C, 42.15; H, 3.34. Found: C, 42.32; H,

[Rh(η⁵-Cp*)(CH₂CH₂-t-C₄F₉)I(PPh₃)] (8). Method A. [Rh(η⁵-

Cp*)(η²-C₂H₄)(PPh₃)] was prepared in situ by heating a solution of

[Rh(η⁵-Cp*)(η²-C₂H₄)₂] (104 mg, 0.353 mmol) and PPh₃(102 mg,

0.389 mmol) in toluene (5 mL) at 120 °C for 4 h in a Carius tube.

The resulting solution was cooled to room temperature, and I-t-C₄F₉

(130 mg, 0.376 mmol) was added. After the mixture was stirred for 1.5

h at room temperature, the volatiles were removed under vacuum. The

residue was chromatographed on a silica gel column using Et₂O/n-

hexane (1/2) as eluent. The collected orange fraction (R_f= 0.53) was

concentrated to ca. 2 mL, and n-hexane (2 mL) was added. The

orange crystalline precipitate was ﬁltered, washed with cold n-hexane

(3 × 2 mL), and dried under vacuum (186 mg, 0.213 mmol, 60.3%).

Method B. I-t-C₄F₉(230 mg, 0.665 mmol) was added to a solution

of [Rh(η⁵-C₅Me₅)(η²-C₂H₄)₂] (135 mg, 0.459 mmol) in n-pentane (4

mL), and the mixture was stirred for 20 h at room temperature. The

volatiles were removed under vacuum, the residue was dissolved in

THF (7 mL), and PPh₃(138 mg, 0.526 mmol) was added. The

resulting solution was stirred for 5 h more at room temperature, and it

was ﬁnally evaporated to dryness. The dark orange residue was

chromatographed on a silica gel column using Et₂O/n-hexane (1/2) as

eluent. The collected orange fraction (R_f= 0.53) was concentrated to

give an orange crystalline solid which was ﬁltered, washed with cold n-

hexane (2 × 2 mL), and dried under vacuum (138 mg, 0.158 mmol,

34.4%). Mp: 171 °C dec. Anal. Calcd for C₃₄H₃₄F₉IPRh: C, 46.70; H,

3.20. H NMR (300.1 MHz, CDCl₃): δ 7.37 (br m, 15 H, Ph), 2.77

(m, 1 H, CH₂), 2.17−1.98 (m, 3 H, CH₂), 1.52 (d, J_PH= 1.5 Hz, 15

H, C₅Me₅). ¹³C{¹H} NMR (100.8 MHz, CDCl₃): δ 134.5 (br m, Ph),

130.2 (s, C4 of Ph), 127.8 (d, J_PC= 9.9 Hz, Ph), 93.9 (d, ²J_PC= 2.9 Hz,

C₅Me₅), 36.2 (dd, J_FC= 21.2 Hz, J_PC= 3.2 Hz, IrCH₂CH₂), 9.0 (s,

C₅Me₅), −17.2 (d, J_PC= 8.5 Hz, IrCH₂CH₂); the C₆F₁₁signals were

not observed. ¹⁹F NMR (282.4 MHz, CDCl₃): δ −118.7 (d, J_FF

303.6 Hz, 2 F, F_eq), −122.6 (d, ²J_FF= 290.3 Hz, 1 F, F_eq), −122.9 (d,

²J_FF= 281.0 Hz, 1 F, F_eq), −124.3 (d, J_FF= 282.4 Hz, 1 F, F_eq),

−131.0 (d, ²J_FF= 301.0 Hz, 1 F, F_ax), −133.0 (d, ²J_FF= 296.5 Hz, 1 F,

F_ax), −139.6 (d, ²J_FF= 274.5 Hz, 2 F, F_ax), −142.3 (d, ²J_FF= 277.6 Hz,

1F, F_ax), −184.7 (s, 1 F, CH₂CF). ³¹P{¹H} NMR (121.5 MHz,

CDCl₃): δ 1.1 (s). (+)ESI-MS: m/z 589 ([Ir(C₅Me₄CH₂)(PPh₃)]⁺),

717 ([Ir(C₅Me₅)I(PPh₃)]⁺), 899 (M − I⁻), 1044 (M + NH₄), 1065

(M + K⁺).

[Rh(η⁵-Cp*)(CH₂CH₂-c-C₆F₁₁)I(PPh₃)] (6). A solution of [Rh(η⁵-

C₅Me₅)(η²-C₂H₄)₂] (75 mg, 0.25 mmol) in n-pentane (6 mL) was

treated witch I-c-C₆F₁₁(50 μL, 0.27 mmol). After the mixture was

stirred for 19 h at room temperature, the volatiles were removed under

vacuum. The residue was dissolved in THF (9 mL), and PPh₃(68 mg,

0.26 mmol) was added. After it was stirred for 8 h at room

temperature, the mixture was evaporated to dryness to give a dark

orange residue. The residue was chromatographed on a silica gel

column using Et₂O/n-hexane (1/2) as eluent. The collected orange

fraction (R_f= 0.54) was concentrated to give an orange crystalline

precipitate, which was washed with cold n-hexane (2 × 3 mL) and

dried under vacuum (101 mg, 0.108 mmol, 43%). Mp: 173 °C dec.

Anal. Calcd for C₃₆H₃₄F₁₁IPRh: C, 46.17; H, 3.66. Found: C, 45.93; H,

3.92. Found: C, 46.78; H, 3.93. H NMR (300.1 MHz, C₆D₆): δ 7.70

(br m, 6 H, H2 of Ph), 7.00 (m, 9 H, H3 and H4 of Ph), 3.74 (m, 1 H,

RhCH₂CH₂), 2.39 (m, 1 H, RhCH₂CH₂), 2.19−2.06 (m, 2 H,

RhCH₂CH₂), 1.32 (d, J_PH= 2.7 Hz, 15 H, Me). ¹³C{¹H} NMR

(100.8 MHz, CDCl₃): δ 134.9 (br m, Ph), 132.7 (br m, Ph), 130.2 (s,

C4 of Ph), 128.0 (d, J_PC= 9.6 Hz, Ph), 122.2 (q, J_CF= 288.2 Hz,

3.59. H NMR (300.1 MHz, CDCl₃): δ 7.60−7.25 (br m, 15 H, Ph),

CF₃), 99.7 (dd, ¹J_RhC= 4.7 Hz, ²J_PC= 3.2 Hz, C₅Me₅), 60.6 (decaplet,

3.01 (m, 1 H, RhCH₂CH₂), 2.12 (m, 1 H, RhCH₂CH₂), 1.74 (m, 2 H,

²J_CF= 24.4 Hz, CCF₃), 37.5 (s, RhCH₂CH₂), 9.6 (d, J_RhC= 1.0 Hz,

RhCH₂CH₂), 1.51 (d, J_PH= 2.4 Hz, 15 H, C₅Me₅). ¹³C{¹H} NMR

C₅Me₅), 4.3 (dd, J_RhC= 24.4 Hz, J_PC= 12.2 Hz, RhCH₂CH₂). ¹⁹F

NMR (282.4 MHz, C₆₁D₆): δ −64.8 (s). ³¹P{¹H} NMR (121.5 MHz,

C₆D₆): δ 40.7 (d, J_RhP= 161.5 Hz). (+)ESI-MS: m/z 499

([Rh(C₅Me₄CH₂)(PPh₃)]⁺), 627 ([Rh(C₅Me₅)I(PPh₃)]⁺), 897 (M

+ Na⁺), 913 (M + K⁺).

(75.5 MHz, CDCl₃): δ 135.9−132.6 (br m, Ph), 130.3 (br s, C4, Ph),

128.0 (d, J_PC= 9.3 Hz, Ph), 99.8 (dd, J_RhC= 4.6 Hz, J_PC= 3.1 Hz,

C₅Me₅), 35.9 (d, J_FC= 21.3 Hz, RhCH₂CH₂), 9.5 (d, J_RhC= 1.4 Hz,

C₅Me₅), 2.3 (dd, J_RhC= 24.8 Hz, J_PC= 13.5 Hz, RhCH₂CH₂); the

C₆F₁₁signals were not observed. ¹⁹F NMR (282.4 MHz, CDCl₃): δ

−118.9 (d, 1 F, ²J_FF= 295.4 Hz, F_eq), −119.1 (d, 1 F, ²J_FF= 294.6 Hz,

F_eq), −123.0 (d, 1 F, ²J_FF= 274.7 Hz, F_eq), −123.3 (d, 1 F, ²J_FF= 288.9

[Rh(η⁵-Cp*)(CH₂CH₂-n-C₄F₉)I(PMe₃)] (9). PMe₃(0.52 mL of a 1

M toluene solution, 0.52 mmol) was added to a solution of [Rh(η⁵-

Cp*)(η²-C₂H₄)₂] (153 mg, 0.520 mmol) in toluene (5 mL). The

mixture was heated at 120 °C for 17 h in a Carius tube. The resulting

solution of [Rh(η⁵-Cp*)(η²-C₂H₄)(PMe₃)] was cooled to room

temperature, and ICH₂CH₂-n-C₄F₉(195 mg, 0.521 mmol) was added.

After the mixture was stirred for 7 h at room temperature, the volatiles

were removed under vacuum. The residue was chromatographed on a

silica gel column using Et₂O/n-hexane (1/1) as eluent. The collected

fraction (R_f= 0.54) was evaporated to dryness, and the residue was

stirred with Et₂O (3 mL) to give an orange solid, which was washed

with n-pentane (2 mL) and dried under vacuum (94 mg, 0.14 mmol,

26%). Mp: 101−103 °C. Anal. Calcd for C₁₉H₂₈F₉IPRh: C, 33.16; H,

4.10. Found: C, 32.94; H, 4.01. ¹H NMR (300.1 MHz, CDCl₃): δ 2.47

(m, 1 H, RhCH₂CH₂), 1.94 (m, 1 H, RhCH₂CH₂), 1.79 (d, ⁴J_PH= 2.7

Hz, 15 H, C₅Me₅), 1.56 (m, 1 H, RhCH₂CH₂), 1.55 (d, ²J_PH= 9.9 Hz,

9 H, PMe₃), 1.32 (m, 1 H, RhCH₂CH₂). ¹³C{¹H} NMR (75.5 MHz,

Hz, F_eq), −124.7 (d, 1 F, ²J_FF= 288.6 Hz, F_eq), −130.8 (d, 1 F, ²J_FF

302.2 Hz, F_ax), −133.5 (d, 1 F, J_FF= 294.2 Hz, F_ax), −140.0 (d, 2 F,

²J_FF= 280.4 Hz, F_ax), −142.7 (d, 1 F, ²J_FF= 287.5 Hz, F_ax), −184.8 (s,

1 F, CH₂CF). ³¹P{¹H} NMR (121.5 MHz, CDCl₃): δ 40.9 (d, ¹J_RhP

162.2 Hz). (+)ESI-MS: m/z 499 ([Rh(C₅Me₄CH₂)(PPh₃)]⁺), 627

([Rh(C₅Me₅)I(PPh₃)]⁺), 959 (M + Na⁺), 975 (M + K⁺).

[Ir(η⁵-Cp*)(CH₂CH₂-i-C₃F₇)I(PPh₃)] (7). I-i-C₃F₇(35 μL, 0.25

mmol) was added to a solution of [Ir(η⁵-C₅Me₅)(η²-C₂H₄)(PPh₃)]

(153 mg, 0.248 mmol) in toluene (7 mL), and the mixture was stirred

for 7 h at room temperature. The volatiles were removed under

vacuum, and the residue was puriﬁed by chromatography on a silica gel

column using Et₂O/n-hexane (1/3) as eluent. The collected orange

fraction (R_f= 0.45) was concentrated under vacuum until a pale

orange microcrystalline precipitate formed, which was washed with

cold n-hexane (3 × 1 mL) and dried under vacuum (53 mg, 0.058

mmol, 23%). Mp: 147−149 °C dec. Anal. Calcd for C₃₃H₃₄F₇IPIr: C,

CDCl₃): δ 98.6 (dd, J_RhC= 4.6 Hz, J_PC= 3.2 Hz, C₅Me₅), 38.6 (t,

²J_FC= 22.5 Hz, RhCH₂CH₂), 17.5 (d, ¹J_PC= 32.4 Hz, PMe₃), 10.0 (d,

43.38; H, 3.75. Found: C, 43.41; H, 3.64. H NMR (400.9 MHz,

²J_RhC= 1.0 Hz, C₅Me₅), −2.1 (dd, J_RhC= 25.9 Hz, J_PC= 15.1 Hz,

CDCl₃): δ 7.37 (br m, 15 H, Ph), 2.66 (m, 1 H, CH₂), 2.09−1.86 (m,

3 H, CH₂), 1.51 (d, ⁴J_PH= 1.5 Hz, 15 H, C₅Me₅). ¹³C{¹H} NMR (75.5

MHz, CDCl₃): δ 134.8 (br m, Ph), 132.6 (br m, Ph), 130.2 (s, C4 of

RhCH₂CH₂); the C₄F₉signals were not observed. ¹⁹F NMR (188.3

MHz, CDCl₃): δ −81.8 (t, J_F₂_F= 9.3, CF₃), −115.2 (dm, J_FAFB

272.8, CF₂CH₂), −116.9 (dm, J_FAFB= 265.8, CF₂CH₂), −125.0 (m,

CF₂), −126.7 (m, CF₂). ³¹P{¹H} NMR (81.0 MHz, CDCl₃): δ 3.5 (d,

¹J_RhP= 157.3 Hz). (+)ESI-MS: m/z 441 ([Rh(C₅Me₅)I(PMe₃)]⁺), 561

Ph), 127.8 (d, J_PC= 9.9 Hz, Ph), 121.3 (qd, J_FC= 286.9 Hz, J_FC

28.2 Hz, CF₃), 93.9 (d, J_PC= 2.7 Hz, C₅Me₅), 39.3 (dd, J_FC= 20.6

Hz, ³J_PC= 3.4 Hz, IrCH₂CH₂), 8.9 (s, C₅Me₅), −17.7 (d, ²J_PC= 8.4 Hz,

IrCH₂CH₂); the CF signal was observed in a separate measurement

(M − I⁻), 706 (M + NH₄).

(100.8 MHz, CDCl₃), 93.4 (d(sept), J_FC= 198.6 Hz, J_FC= 30.0 Hz,

[Ir(η⁵-Cp*)(η²-CH₂CH-c-C₆F₁₁)H(PPh₃)]OTf (10). AgOTf (9

mg, 0.04 mmol) was added to a solution of 5 (30 mg, 0.029 mmol)

in CH₂Cl₂(4 mL). The suspension was stirred at room temperature

for 2 h and ﬁltered. The ﬁltrate was evaporated to dryness under

vacuum. The residue was cooled to 0 °C and stirred with Et₂O (5

mL). An oﬀ-white solid precipitated, which was washed with cold Et₂O

CF). ¹⁹F NMR (188.3 MHz, CDCl₃): δ −75.4 (dq, J_FF= J_FF= 8.4

Hz, 3 F, CF₃), −76.8 (dq, ³J_FF= ⁴J_FF= 8.6 Hz, 3 F, CF₃), −183.7 (m, 1

F, CF). ³¹P{¹H} NMR (81.0 MHz, CDCl₃): δ 1.2 (s). (+)ESI-MS: m/

z 589 ([Ir(C₅Me₄CH₂)(PPh₃)]⁺), 717 ([Ir(C₅Me₅)I(PPh₃)]⁺), 787

(M − I⁻), 932 (M + NH₄), 953 (M + K⁺).

DOI: 10.1021/acs.organomet.6b00929

Organometallics XXXX, XXX, XXX−XXX

Organometallics

Article

(3 × 0.5 mL) and dried under vacuum (22 mg, 0.021 mmol, 72%).

Mp: 95 °C dec. Anal. Calcd for C₃₇H₃₄F₁₄PSO₃Ir: C, 42.41; H, 3.27; S,

3.06. Found: C, 42.41; H, 3.33; S, 2.78. ¹H NMR (400.9 MHz,

CD₂Cl₂, 21 °C): δ 7.64−7.45 (m, Ph), 2.98 (m, CHCH₂), 2.72 (dd,

J₁= 9.5 Hz, J₂= 2.0 Hz, CHCH₂), 2.49 (m, CHCH₂), 2.40−2.22

for 2 h at room temperature, ﬁltered, and heated at 60 °C for 50 h in a

Carius tube. The compound was isolated in the same way as in

method A to give yellow crystals (104 mg, 0.104 mmol, 24.8%). Mp:

270−272 °C. Anal. Calcd for C₄₇H₄₄F₃P₂SO₃Ir: C, 56.45; H, 4.43; S,

3.21. Found: C, 56.56; H, 4.28; S, 3.50. ¹H NMR (400.9 MHz,

CD₂Cl₂, 25 °C): δ 7.61−7.25 (several m, 21 H, Ph), 6.99 (br s, 1 H,

Ph), 6.89 (m, 3 H, Ph), 6.54 (br m, 2 H), 5.69 (br m, 2 H), 1.41 (t,

⁴J_PH= 2.3 Hz, 15 H, C₅Me₅); (−90 °C) δ 7.80−7.06 (several m, 20 H,

(br m, CHCH₂), 1.77 (dd, J_PH= 2.3 Hz, J_HH= 1.2 Hz, C₅Me₅,

major diastereomer), 1.64 (d, J_PH= 1.8 Hz, C₅Me₅, minor

diastereomer), −14.64 (br s, Ir−H, major), −15.84 (br d, J_PH

29.3 Hz, Ir−H, minor); (−20 °C, only hydride region) −14.67 (d, ²J_PH

= 26.5 Hz, Ir−H, major), −15.88 (dd, ²J_PH= 29.1 Hz, J = 3.5 Hz, Ir−

H, minor). A reliable ¹³C{¹H} NMR spectrum could not be obtained

because of decomposition. ¹⁹F NMR (188.3 MHz, CD₂Cl₂, −40 °C):

Ph), 6.92 (m, 2 H, Ph), 6.85 (m, 1 H, Ph), 6.67 (dd, J_HH= 12.3 Hz,

²J_HH= 7.8 Hz, 1 H, Ph), 6.54 (m, 2 H, Ph), 6.34 (m, 1 H, Ph), 6.06

(m, 1 H, Ph), 4.89 (m, 1 H, Ph), 1.29 (br s, 15 H, C₅Me₅). ¹³C{¹H}

NMR (75.5 MHz, CD₂Cl₂, 25 °C): δ 152.1 (d, ²J_PC= 64.0 Hz, IrC_Ar),

135.4−125.3 (several overlapped broad m, Ar), 98.6 (s, C₅Me₅), 9.3 (s,

C₅Me₅); (100.8 MHz, (CD₃)₂SO, 85 °C): δ 151.1 (d, J_PC= 64.2 Hz,

IrC_Ar), 133.4 (br m, Ar), 131.8 (d, J_PC= 41.5 Hz, P−C), 131.8 (d, J_PC

= 9.5 Hz, Ar), 131.6 (s, Ar), 131.0 (d, J_PC= 10.1 Hz, Ar), 130.4 (d, J_PC

= 2.8 Hz, Ar), 130.2 (d, J_PC= 2.2 Hz, Ar), 130.1 (br m, Ar) 128.2 (d,

J_PC= 10.7 Hz, Ar), 128.0 (d, J_PC= 10.9 Hz, Ar), 127.8 (d, J_PC= 52.4

Hz, C−P), 127.4 (d, J_PC= 10.2 Hz, Ar), 125.8 (d, J_PC= 41.5 Hz, C−

P), 124.2 (d, J_PC= 10.2 Hz, Ar), 97.7 (t, ²J_PC= 2.1 Hz, C₅Me₅), 7.9 (s,

C₅Me₅); the CF₃signal was not observed. ¹⁹F NMR (282.4 MHz,

CD₂Cl₂): δ −78.7 (s, CF₃SO₃). ³¹P{¹H} NMR (121.5 MHz, CD₂Cl₂,

δ −79.6 (s, CF₃SO₃), −116.7 (dm, J_FF= 279.2 Hz, F_eq, minor

diastereomer), −117.8 (dm, ²J_FF= 295.1 Hz, F_eq, major diastereomer),

−119.4 (dm, J_FF= 244.4 Hz, F_eq, minor), −121.3 (dm, J_FF= 297.3

Hz, F_eq, major), −123.5 (two overlapped dm, J_FF= 291.5 Hz, 2 F_eq,

major), −124.3 (dm, ²J_FF= 283.7 Hz, F_eq, minor), −124.9 (dm, ²J_FF

292.7 Hz, F_eq, major), −130.5 (dm, J_FF= 300.6 Hz, F_ax, major),

−133.8 (d, ²J_FF= 301.3 Hz, F_ax, minor), −134.4 (dm, ²J_FF= 310.5 Hz,

F_ax, major), −139.7 (d, ²J_FF= 277.8 Hz, F_ax, major), −140.4 (d, ²J_FF

288.9 Hz, F_ax, major), −142.8 (d, ²J_FF= 285.3 Hz, F_ax, major), −180.1

(m, CH₂CF minor), −182.9 (m, CH₂CF major); six signals of the

minor diastereomer were overlapped with those of the major one.

³¹P{¹H} NMR (162.2 MHz, CD₂Cl₂): δ 12.4 (s, major), 7.2 (s,

minor). (+)ESI-MS: m/z 589 ([Ir(C₅Me₄CH₂)(PPh₃)]⁺), 899 (M −

OTf⁻). HRMS (+ESI): calcd for M − OTf⁻(C₃₆H₃₄F₁₁IrP)⁺,

899.1846; found, 899.1886; Δ = 4.4 ppm.

25 °C): δ 4.8 (d, J_PP= 17.7 Hz, PPh₃), −77.9 (d, J_PP= 17.7 Hz,

Ph₂PC₆H₄). (+)ESI-MS: m/z 589 ([Ir(C₅Me₄CH₂)(PPh₃)]⁺), 851 (M

− OTf⁻). HRMS (+ESI): calcd for M − OTf⁻(C₄₆H₄₄IrP₂)⁺,

851.2542; found, 851.2551; Δ = 1.1 ppm.

[Ir(η⁵-Cp*)(CH₂CH₂-c-C₆F₁₁)(CO)(PPh₃)]OTf (15). CO was

bubbled through a solution of 10 (23 mg, 0.022 mmol, overall) in

CH₂Cl₂(6 mL) for 3 min. The solution was stirred for 2 h at room

temperature under a CO atmosphere and ﬁnally evaporated to dryness

under vacuum. Addition of Et₂O (5 mL) gave rise to a white solid,

which was washed with Et₂O (3 × 5 mL) and dried under vacuum (18

mg, 0.017 mmol, 76%). Mp: 214−216 °C. Anal. Calcd for

C₃₈H₃₄F₁₄PSO₄Ir: C, 42.42; H, 3.19; S, 2.98. Found: C, 42.40; H,

[Ir(η⁵-Cp*)H(η²-CH₂CH-i-C₃F₇)(PPh₃)]OTf (11). AgOTf (38

mg, 0.15 mmol) was added to a solution of 7 (114 mg, 0.125

mmol) in CH₂Cl₂(4 mL). The suspension was stirred at room

temperature for 2 h and ﬁltered. The ﬁltrate was concentrated to ca. 1

mL under vacuum and cooled to 0 °C. By addition of Et₂O (15 mL)

an oﬀ-white solid precipitated, which was washed with cold Et₂O (0

°C, 3 × 2 mL) and dried under vacuum (104 mg, 0.111 mmol, 88.9%).

Mp: 145 °C dec. Anal. Calcd for C₃₄H₃₄F₁₀PSO₃Ir: C, 43.64; H, 3.66;

3.30; S, 3.27. IR (Nujol, cm⁻¹): ν(CO) 2032. H NMR (400.9 MHz,

S, 3.43. Found: C, 43.57; H, 3.56; S, 3.40. H NMR (400.9 MHz,

CDCl₃): δ 7.63−7.54 (m, 9 H, Ph), 7.29−7.24 (m, 6 H, Ph), 2.14 (m,

2 H, IrCH₂CH₂), 1.96 (m, 1 H, IrCH₂CH₂), 1.80 (d, ⁴J_PH= 2.2 Hz, 15

H, C₅Me₅), 1.49 (m, 1 H, IrCH₂CH₂). ¹³C{¹H} NMR (100.8 MHz,

CDCl₃): δ 169.1 (d, ²J_PC= 12.3 Hz, CO), 133.3 (d, ²J_PC= 10.3 Hz, C2

or C3, Ph), 132.8 (d, ⁴J_PC= 2.6 Hz, C4, Ph), 129.8 (d, ³J_PC= 11.4 Hz,

CD₂Cl₂, 25 °C): δ 7.65−7.44 (several m, Ph), 2.88 (m, CHCH₂),

2.67 (dd, J₁= 9.4 Hz, J₂= 1.9 Hz, CHCH₂), 2.47 (m, CHCH₂),

2.19 (br m, CHCH₂), 1.78 (dd, J_PH= 2.1 Hz, J_HH= 1.2 Hz,

C₅Me₅, major diastereomer), 1.62 (d, J_PH= 1.4 Hz, C₅Me₅, minor

diastereomer), −14.65 (br s, Ir−H, major), −15.92 (d d, J_PH= 28.0

C3 or C2, Ph), 127.7 (d, J_CP= 57.8 Hz, C1, Ph), 121.1 (q, J_CF

Hz, Ir−H, minor); (−10 °C, 200.1 MHz, only hydride region) −14.73

320.1 Hz, CF₃S), 104.7 (d, ²J_PC= 1.3 Hz, C₅Me₅), 33.0 (d, ²J_FC= 20.5

Hz, IrCH₂CH₂), 9.0 (s, C₅Me₅), −13.1 (s, IrCH₂CH₂); the C₆F₁₁

signals were not observed. ¹⁹F NMR (188.3 MHz, CD₂Cl₂): δ −79.1

(s, CF₃SO₃), −119.3 (d, 2 F, ²J_FF= 286.9 Hz, F_eq), −123.4 (d, 2 F, ²J_FF

= 293.9 Hz, F_eq), −124.9 (d, 1 F, ²J_FF= 283.7 Hz, F_eq), −131.9 (d, 1 F,

²J_FF= 264.5 Hz, F_ax), −133.3 (d, 1 F, ²J_FF= 283.8 Hz, F_ax), −140.2 (d,

2 F, ²J_FF= 288.6 Hz, F_ax), −142.8 (d, 1 F, ²J_FF= 285.5 Hz, F_ax), −186.5

(s, 1 F, CH₂CF). ³¹P{¹H} NMR (162.3 MHz, CDCl₃): δ 2.6 (s).

(+)ESI-MS: m/z 379, 927 (M − OTf⁻). HRMS (+ESI): calcd for M −

OTf⁻(C₃₇H₃₄F₁₁IrOP)⁺, 927.1795; found, 927.1809; Δ = 1.5 ppm.

[Ir(η⁵-Cp*)(CH₂CH₂-i-C₃F₇)(CO)(PPh₃)]OTf (16). This compound

was prepared in the same way as for 15 from 11 (25 mg, 0.027 mmol

overall) and CO. Oﬀ-white solid (21 mg, 0.022 mmol, 81%). Colorless

analytically pure crystals were obtained by liquid diﬀusion of n-hexane

into a CH₂Cl₂solution. Mp: 195−197 °C. Anal. Calcd for

C₃₅H₃₄F₁₀PSO₄Ir: C, 43.61; H, 3.56; S, 3.33. Found: C, 43.40; H,

(d, J_PH= 25.6 Hz, Ir−H, major), −15.87 (dd, J_PH= 30.4 Hz, J_FH

4.1 Hz, Ir−H, minor). A reliable ¹³C{¹H} NMR spectrum could not be

obtained because of decomposition. ¹⁹F NMR (188.3 MHz, CD₂Cl₂,

21 °C): δ −75.0 (dq, J_FF= J_FF= 10.0 Hz, 3 F, CF₃, minor), −75.8

(br m, 3 F, CF₃, major), −76.8 (dq, J_FF= J_FF= 9.8 Hz, 3 F, CF₃,

minor), −77.1 (br m, 3 F, CF₃, major), −79.4 (s, 3 F, CF₃SO₃),

−181.5 (br m, 1 F, CF, minor and major); (188.3 MHz, CD₂Cl₂, −10

°C): δ −75.0 (dq, J_FF= J_FF= 9.6 Hz, 3 F, CF₃, minor), −75.8 (dq,

³J_FF= ⁴J_FF= 9.3 Hz, 3 F, CF₃, major), −76.8 (dq, ³J_FF= ⁴J_FF= 9.2 Hz,

3 F, CF₃, minor), −76.6 (dq, J_FF= J_FF= 9.1 Hz, 3 F, CF₃, major),

−79.2 (s, 3 F, CF₃SO₃), −182.4 (br m, 1 F, CF, minor and major).

³¹P{¹H} NMR (121.5 MHz, CDCl₃, 20 °C): δ 12.6 (s, major), 7.5 (s,

minor). (+)ESI-MS: m/z 268, 400, 589 ([Ir(C₅Me₄CH₂)(PPh₃)]⁺),

787 (M − OTf⁻). HRMS (+ESI): calcd for M − OTf⁻

(C₃₃H₃₄F₇IrP)⁺, 787.1910; found, 787.1917; Δ = 1.8 ppm.

[Ir(η⁵-Cp*){κ²-C,P-C₆H₄(PPh₂)}(PPh₃)]OTf (13). Method A.

AgOTf (34 mg, 0.13 mmol) was added to a solution of 4 (102 mg,

0.106 mmol) in CH₂Cl₂(4 mL). The suspension was stirred for 2 h at

room temperature and ﬁltered. PPh₃(32 mg, 0.12 mmol) was added

to the ﬁltrate. The mixture was stirred for 7 h at room temperature,

concentrated to ca. 2 mL under vacuum, and cooled to 0 °C. By

addition of Et₂O (8 mL) a greenish yellow solid precipitated, which

was ﬁltered and washed with cold Et₂O (2 × 2 mL). The obtained

solid was further puriﬁed by slow diﬀusion of n-hexane into a CH₂Cl₂

solution to aﬀord yellow crystals (43 mg, 0.043 mmol, 39%).

3.42; S, 3.28. IR (Nujol, cm⁻¹): ν(CO) 2015. H NMR (400.9 MHz,

CD₂Cl₂): δ 7.64−7.56 (m, 9 H, Ph), 7.30−7.25 (m, 6 H, Ph), 2.10−

1.94 (m, 3 H, IrCH₂CH₂), 1.76 (d, ⁴J_PH= 2.3 Hz, 15 H, C₅Me₅), 1.48

(m, 1 H, IrCH₂). ¹³C{¹H} NMR (100.8 MHz, CD₂Cl₂): δ 168.5 (d,

²J_PC= 12.8 Hz, CO), 133.5 (br d, ²J_PC= 9.7 Hz, C2 or C3, Ph), 133.1

(d, J_PC= 2.6 Hz, C4, Ph), 129.9 (d, J_PC= 11.3 Hz, C3 or C2, Ph),

127.5 (d, J_CP₁= 61.7 Hz, C1, Ph), 121.3 (q, J_FC= 321.5 Hz, CF₃S),

120.9 (qdq, J_FC= 286.8 Hz, J_FC= 6.5 Hz, J_FC= 29.1 Hz, CF₃C),

104.5 (d, ²J_PC= 1.8 Hz, C₅Me₅), 36.3 (d, ²J_FC= 21.1 Hz, IrCH₂CH₂),

8.9 (s, C₅Me₅), −12.5 (s, IrCH₂CH₂); the CF signal was not observed.

Method B. AgOTf (115 mg, 0.448 mmol) and PPh₃(112 mg, 0.427

mmol) were added to a solution of [Ir(η⁵-C₅Me₅)Cl(Me)(PPh₃)]

(268 mg, 0.419 mmol) in CH₂Cl₂(7 mL). The suspension was stirred

¹⁹F NMR (282.4 MHz, CD₂Cl₂): δ −75.1 (dq, J_FF= ⁴J_FF= 8.2 Hz, 3

F, CF₃), −76.4 (dq, ³J_FF= ⁴J_FF= 8.2 Hz, 3 F, CF₃), −78.7 (s, CF₃SO₃),

DOI: 10.1021/acs.organomet.6b00929

Organometallics XXXX, XXX, XXX−XXX

Organometallics

Article

−184.2 (m, 1 F, CF). ³¹P{¹H} NMR (121.5 MHz, CD₂Cl₂): δ 3.6 (s).

(+)ESI-MS: m/z 379, 815 (M −OTf⁻). HRMS (+ESI): calcd for M −

OTf⁻(C₃₄H₃₄F₇IrOP)⁺, 815.1859; found, 815.1869; Δ = 1.2 ppm.

[Ir(η⁵-Cp*)(CH₂CH₂-i-C₃F₇)(PPh₃)₂]OTf (17). PPh₃(23 mg, 0.088

mmol) was added to a solution of 11 (79 mg, 0.084 mmol overall) in

CH₂Cl₂(5 mL). The mixture was stirred for 2 h at room temperature

and evaporated to dryness. The residue was stirred with Et₂O (10 mL)

at 0 °C for 30 min to give a pale yellow solid, which was washed with

Et₂O (2 × 2 mL) and dried under vacuum (49 mg, 0.041 mmol, 49%).

Mp: 103−105 °C. Anal. Calcd for C₅₂H₄₉F₁₀P₂SO₃Ir: C, 52.13; H,

4.12; S, 2.68. Found: C, 52.07; H, 4.18; S, 2.76. ¹H NMR (300.1 MHz,

CD₂Cl₂): δ 7.58−6.95 (several m, 30 H, Ph), 2.66 (m, 2 H, CH₂), 2.21

2.39−2.15 (m, 4 H, CH₂), 1.34 (d, J_PH= 2.3 Hz, 15 H, Me). ¹⁹F

NMR (282.4 MHz, CD₂Cl₂): δ −78.8 (br s, CF₃SO₃), −119.1 (d, 2 F,

²J_FF= 287.6 Hz, F_eq), −123.3 (d, 2 F, ²J_FF= 282.9 Hz, F_eq), −124.8 (d,

1 F, J_FF= 282.9 Hz, F_eq), −132.3 (br d, 2 F, J_FF= 197 Hz, F_ax),

−140.1 (d, 2 F, ²J_FF= 279.4 Hz, F_ax), −142.9 (d, 1 F, ²J_FF= 277.0 Hz,

F_ax), −185.5 (m, 1 F, CH₂CF). ³¹P{¹H} NMR (121.5 MHz, CD₂Cl₂):

δ 40.3 (d, J_RhP= 166.1 Hz).

NMR Data of [Rh(η⁵-Cp*)(CH₂CH₂-i-C₃F₇)(OTf)(PPh₃)] (21).

This compound was generated in situ from [Rh(η⁵-Cp*)(CH₂CH₂-i-

C₃F₇)I(PPh₃)]²⁰in a way similar to that for 19. ¹H NMR (300.1 MHz,

CD₂Cl₂): δ 7.58−7.36 (m, 15 H, Ph), 2.36−2.02 (m, 4 H, CH₂), 1.33

(d, J_PH= 2.9 Hz, 15 H, Me). ¹⁹F NMR (282.4 MHz, CD₂Cl₂): δ

(m, 2 H, CH₂), 1.27 (t, J_PH= 2.3 Hz, 15 H, C₅Me₅). ¹³C{¹H} NMR

−75.8 (br m, CF(CF₃)₂), −78.8 (s, CF₃SO₃), −184.2 (m, CF).

³¹P{¹H} NMR (121.5 MHz, CD₂Cl₂): δ 40.1 (d, J_RhP= 166.0 Hz).

(75.5 MHz, CD₂Cl₂): δ 134.7 (m, C2 or C3, Ph), 131.8 (s, C4, Ph),

128.7 (m, C3 or C2, Ph), 121.3 (qd, J_FC= 287.2 Hz, ²J_FC= 28.3 Hz,

NMR Data of [Rh(η⁵-Cp*)(CH₂CH₂-n-C₄F₉)(OTf)(PMe₃)] (22).

This compound was generated in situ from 9 in a way similar to that

CF₃C), 102.1 (t, J_PC= 2.2 Hz, C₅Me₅), 33.8 (dt, ²J_FC= 20.5 Hz, ³J_PC

= 3.4 Hz, IrCH₂CH₂), 9.8 (s, C₅Me₅), −24.7 (t, J_PC= 8.8 Hz,

for 19. H NMR (200.1 MHz, CD₂Cl₂): δ 1.62 (d, J_PH= 2.8 Hz, 15

H, C₅Me₅), 1.50 (d, J_PH= 10.2 Hz, PMe); the CH₂multiplet

IrCH₂CH₂); owing to partial decomposition of the complex during the

measurement the signals of C1-Ph, CF and CF₃S could not be located.

overlapped with the Cp* signal and the signals of decomposition

products. ¹⁹F NMR (188.3 MHz, CD₂Cl₂): δ −78.9 (br s, CF₃SO₃),

−81.6 (m, CF₂CF₃), −115.8 (br m, CF₂), −125.0 (m, CF₂), −126.4

(m, CF₂). ³¹P{¹H} NMR (81.0 MHz, CD₂Cl₂): δ 7.5 (d, ¹J_RhP= 163.4

Hz).

¹⁹F NMR (282.4 MHz, CD₂Cl₂): δ −75.3 (d, 6 F, J_FF= 6.5 Hz,

CF(CF₃)₂), −78.9 (s, 3 F, CF₃SO₃), −185.0 (m, 1 F, CF). ³¹P{¹H}

NMR (121.5 MHz, CD₂Cl₂): δ −13.1 (s). (+)ESI-MS: m/z 118, 379,

589 ([Ir(C₅Me₄CH₂)(PPh₃)]⁺), 787 (M − OTf⁻− PPh₃), 980 (M −

OTf⁻− CF₃).

NMR Data of [Rh(η⁵-Cp*)(CH₂CH₂-t-C₄F₉)(OTf)(PMe₃)] (23).

This compound was generated in situ from [Rh(η⁵-Cp*)(CH₂CH₂-t-

[Ir(η⁵-Cp*){κ²-C,P-C₆H₄(PPh₂)}(P(p-Tol)₃)]OTf (18). AgOTf (100

mg, 0.389 mmol) was added to a solution of [Ir(η⁵-C₅Me₅)(Cl)-

(Me)(PPh₃)] (100 mg, 0.156 mmol) in CH₂Cl₂(13 mL). The

suspension was stirred for 40 min at room temperature and ﬁltered.

P(p-Tol)₃(48 mg, 0.16 mmol) was added to the ﬁltrate, and the

mixture was stirred for 2 h at room temperature. It was evaporated to

dryness under vacuum, and the residue was stirred with n-pentane (10

mL) to give a pale brown solid, which was washed with n-pentane (15

mL). Slow diﬀusion of n-hexane into a CH₂Cl₂solution of the

obtained solid aﬀorded yellow crystals (52 mg, 0.047 mmol, 30%).

Mp: 275−277 °C. Anal. Calcd for C₅₀H₅₀F₃P₂SO₃Ir·0.7CH₂Cl₂: C,

C₄F₉)I(PMe₃)]²⁰in a way similar to that for 19. H NMR (200.1

MHz, CD₂Cl₂): δ 2.25 (m, 2 H, CH₂), 1.65 (m, 2 H, CH₂), 1.63 (dd,

⁴J_PH= 3.0 Hz, ³J_RhH= 0.6 Hz, 15 H, C₅Me₅), 1.49 (dd, ²J_PH= 10.4 Hz,

³J_RhH= 0.8 Hz, PMe). ¹⁹F NMR (188.3 MHz, CD₂Cl₂): δ −66.1 (s,

C(CF₃)₃), −79.1 (br s, CF₃SO₃). ³¹P{¹H} NMR (81.0 MHz, CD₂Cl₂):

δ 7.3 (d, J_RhP= 163.1 Hz).

NMR Data of [Rh(η⁵-Cp*)(CH₂CH₂-i-C₃F₇)(OTf)(PMe₃)] (24).

This compound was generated in situ from [Rh(η⁵-Cp*)(CH₂CH₂-i-

C₃F₇)I(PMe₃)]²⁰in a way similar to that for 19. H NMR (200.1

MHz, CD₂Cl₂): δ 1.62 (d, ⁴J_PH= 2.8 Hz, 15 H, C₅Me₅), 1.49 (d, ²J_PH

55.28; H, 4.70; S, 2.91. Found: C, 55.13; H, 4.49; S, 2.90. H MNR

10.4 Hz, PMe); the CH₂multiplet overlapped with the Cp* signal and

the signals of decomposition products. ¹⁹F NMR (188.3 MHz,

CD₂Cl₂): δ −75.9 (br m, CF(CF₃)₂), −79.1 (br s, CF₃SO₃) −183.4

(m, CF). ³¹P{¹H} NMR (81.0 MHz, CD₂Cl₂): δ 7.4 (d, ¹J_RhP= 163.9

Hz).

(400.9 MHz, CD₂Cl₂, 25 °C): 7.53−7.27 (several m, 18 H, Ar), 7.16

(br s, 1 H, Ar), 6.88 (m, 3 H, Ar), 6.31 (br m, 2 H, C₆H₄), 5.51 (br m,

2 H, C₆H₄), 2.47 (br s, 3 H, CH₃), 2.42 (br s, 3 H, CH₃), 2.14 (s, 3 H,

CH₃), 1.40 (t, J_PH= 2.4 Hz, 15 H, C₅Me₅); (−90 °C) δ 7.77−6.86

(several m, 20 H, Ar), 6.70 (m, 1 H, Ar), 6.51 (m, 1 H, Ar), 6.35 (m, 1

H, C₆H₄), 6.05 (m, 1 H, C₆H₄), 5.98 (m, 1 H, C₆H₄), 4.60 (m, 1 H,

C₆H₄), 2.37 (s, 3 H, MeC₆H₄), 2.35 (s, 3 H, MeC₆H₄), 2.07 (s, 3 H,

MeC₆H₄), 1.29 (s, 15 H, C₅Me₅). ¹³C{¹H} NMR (100.8 MHz,

CD₂Cl₂, 25 °C): δ 152.4 (d, ²J_PC= 64.2 Hz, IrC_Ar), 142.6 (br m, Ar),

140.0 (br m, Ar), 135.3 (br m, Ar), 133.1−132.3 (several overlapped

m, Ar), 131.5 (s, Ar), 131.3 (s, Ar), 129.1−128.3 (several overlapped

NMR Data of [Rh(η⁵-Cp*)(CH₂CH₂-t-C₄F₉)(PPh₃)₂]OTf (26).

The signals of this compound were observed in the reaction of in

situ generated 19 with PPh₃in an NMR tube. H NMR (200.1 MHz,

CD₂Cl₂): δ 1.26 (t, J_PH= 3.4 Hz, 15 H, C₅Me₅); the Ph and CH₂

signals were overlapped with those of 19. ¹⁹F NMR (188.3 MHz,

CD₂Cl₂): δ −65.7 (s, C(CF₃)₃). ³¹P{¹H} NMR (81. MHz, CD₂Cl₂): δ

30.9 (d, J_RhP= 147.4 Hz).

m, Ar), 126.8 (d, J_PC= 42.3 Hz, C−P), 126.4 (br s, Ar), 125.3 (d, J_PC

NMR Data of [Rh(η⁵-Cp*)(CH₂CH₂-c-C₆F₁₁)(PPh₃)₂]OTf (27).

The signals of this compound were observed in the reaction of in situ

generated 20 with PPh₃in an NMR tube. H NMR (200.1 MHz,

10.1 Hz, Ar), 124.5 (m, Ar), 121.5 (q, ¹J_FC= 121.5 Hz, CF₃S), 98.4 (s,

C₅Me₅), 21.4 (br s, CH₃), 9.3 (s, C₅Me₅). ¹⁹F NMR (188.3 MHz,

CD₂Cl₂): δ −79.1 (s). ³¹P{¹H} NMR (121.5 MHz, CD₂Cl₂, 25 °C): δ

CD₂Cl₂): δ 1.26 (t, J_PH= 3.2 Hz, 15 H, C₅Me₅); the Ph and CH₂

2.8 (d, J_PP= 17.5 Hz, P(p-Tol)₃), −77.5 (d, J_PP= 17.5 Hz,

PPh₂(C₆H₄)). (+)ESI-MS: m/z 146, 893 (M −OTf⁻). HRMS (+ESI):

calcd for M − OTf⁻(C₄₉H₅₀IrP₂)⁺, 893.3011; found, 893.3015; Δ =

0.4 ppm.

signals were overlapped with those of 20. ¹⁹F NMR (188.3 MHz,

CD₂Cl₂): δ −186.2 (m, CF); the CF₂signals overlapped with those of

20. ³¹P{¹H} NMR (81.0 MHz, CD₂Cl₂): δ 29.9 (d, ¹J_RhP= 147.4 Hz).

NMR Data of [Rh(η⁵-Cp*)(CH₂CH₂-i-C₃F₇)(PPh₃)₂]OTf (28). The

signals of this compound were observed in the reaction of in situ

NMR Data of [Rh(η⁵-Cp*)(CH₂CH₂-t-C₄F₉)(OTf)(PPh₃)] (19). A

solution of 8 (8 mg, 0.009 mmol) in CD₂Cl₂(0.7 mL) was prepared

under a N₂atmosphere in a 1.5 mL vial containing a magnetic stirring

bar. AgOTf (1.5 equiv) was added to this solution, and the vial was

sealed with a screw cap equipped with a PTFE-covered septum. The

suspension was stirred at room temperature for 2 h. It was taken with a

syringe and ﬁltered through a PTFE membrane ﬁlter. The ﬁltrate was

introduced into a NMR tube under N₂. ¹H NMR (300.1 MHz,

CD₂Cl₂): δ 7.55−7.40 (m, 15 H, Ph), 2.48−2.20 (m, 4 H, CH₂), 1.33

generated 21 with PPh₃in an NMR tube. H NMR (200.1 MHz,

CD₂Cl₂): δ 1.24 (t, J_PH= 3.2 Hz, 15 H, C₅Me₅); the Ph and CH₂

signals were overlapped with those of 21. ¹⁹F NMR (188.3 MHz,

CD₂Cl₂): δ −75.5 (d, ³J_FF= 7.3 Hz, CF(CF₃)₂), −184.9 (m, 2 F, CF).

³¹P{¹H} NMR (81.0 MHz, CD₂Cl₂): δ 29.9 (d, J_RhP= 147.4 Hz).

[Rh(η⁵-Cp*)(CH₂CH₂-t-C₄F₉)(PMe₃)₂]OTf (29). AgOTf (42 mg,

0.16 mmol) was added to a solution of [Rh(η⁵-Cp*)(CH₂CH₂-t-

C₄F₉)I(PMe₃)]²⁰(101 mg, 0.146 mmol) in CH₂Cl₂(4 mL). The

suspension was stirred at room temperature for 2 h and ﬁltered. The

ﬁltrate was evaporated to dryness, and the resulting orange residue was

dissolved in Et₂O (3 mL). To this solution was added PMe₃(1 M in

toluene, 0.47 mmol of PMe₃), and the mixture was stirred for 3 h. The

volatiles were removed under vacuum, and the residue was stirred with

(d, J_PH= 3.0 Hz, 15 H, Me). ¹⁹F NMR (282.4 MHz, CD₂Cl₂): δ

−65.7 (s, C(CF₃)₃), −78.6 (br s, CF₃SO₃). ³¹P{¹H} NMR (121.5

MHz, CD₂Cl₂): δ 39.2 (d, J_RhP= 165.8 Hz).

NMR Data of [Rh(η⁵-Cp*)(CH₂CH₂-c-C₆F₁₁)(OTf)(PPh₃)] (20).

This compound was generated in situ from 6 in a way similar to that

for 19. H NMR (300.1 MHz, CD₂Cl₂): δ 7.60−7.42 (m, 15 H, Ph),

DOI: 10.1021/acs.organomet.6b00929

Organometallics XXXX, XXX, XXX−XXX

Organometallics

Article

Et₂O (3 × 5 mL) and dried under vacuum to give a pale yellow solid

(100 mg, 0.127 mmol, 87.1%). Mp: 151−153 °C. Anal. Calcd for

C₂₃H₃₇F₁₂P₂SO₃Rh: C, 35.13; H, 4.74; S, 4.08. Found: C, 35.21; H,

4.70; S, 4.28. ¹H NMR (400.9 MHz, CD₂Cl₂): δ 2.12 (m, 2 H,

RhCH₂CH₂), 1.79 (t, ⁴J_PH= 2.8 Hz, 15 H, C₅Me₅), 1.51 (second order

m, 18 H, PMe₃), 1.17 (m, 2 H, RhCH₂CH₂). ¹³C{¹H} NMR (75.5

Decomposition of 17. A solution of 17 (5 mg, 0.004 mmol) in

CD₂Cl₂(0.5 mL) was heated at 50 °C in a sealed NMR tube for 23 h.

After this time, the NMR spectra of the solution showed quantitative

conversion to 13 and CH₃CH₂-i-C₃F₇(PPh₃cyclometalation

products) and 14 and H₂CCH-i-C₃F₇(β-elimination products).

The (cyclometalation products)/(β-elimination products) molar ratio

was 3, as estimated by integration of the ¹⁹F NMR and ³¹P{¹H} NMR

spectra of the mixture. The data of CH₃CH₂-i-C₃F₇and H₂CCH-i-

C₃F₇are given in the Supporting Information.

Catalytic Reactions. The initiator (0.006 mmol), additive (see

Table 1), C₆D₆(0.5 mL), standard (PhCF₃, 0.081 mmol) and

iodoperﬂuoroalkane (0.12 mmol) were introduced into a J. Young

NMR tube under N₂. The tube was cooled with liquid N₂and freeze−

pump−thawed. Ethene (0.12 mmol) was condensed inside the cold

tube, and it was sealed, thawed, and warmed at the corresponding

temperature. The progress of the reaction was monitored by NMR

spectroscopy. The conversion was determined from the integrals of

the CF₃signals of the standard and the reaction product ICH₂CH₂R_F.

The data of the halogenated organic products are given in the

Supporting Information.

Crystal Structure Determinations. Single crystals were obtained

by liquid diﬀusion of n-hexane in Et₂O (compound 1), Et₂O in

CH₂Cl₂(compound 13), or n-hexane in CH₂Cl₂(compound 16).

Single crystals of [Rh(η⁵-Cp*)Cl(PMe₃)₂]OTf spontaneously grew

after the decomposition of 23 in CD₂Cl₂solution. The compounds

were measured on a Bruker D8 SMART diﬀractometer at 100 K. Data

were collected using a sealed tube with Mo Kα radiation (0.71073 Å)

in w-scan. The structures were solved by direct methods. All were

reﬁned anisotropically on F². The methyl groups were reﬁned using

rigid groups, and the other hydrogens were reﬁned using a riding

mode. Special features of refinement: for compound 1, the CF₃ligands

are disordered over two positions, with a ca. 51:49% distribution.

Crystal data and details of data acquisition and structure reﬁnement

are included in the Supporting Information.

MHz, CD₂Cl₂): δ 122.4 (q, J_CF= 288.3 Hz, CF₃C), 121.4 (q, J_CF

321.4 Hz, CF₃S), 103.4 (s, C₅Me₅), 60.0 (m, J_CF= 26.5 Hz, CF₃C),

33.3 (s, RhCH₂CH₂), 17.3 (second order m, PMe), 10.3 (s, C₅Me₅),

3.0 (dt, J_RhC= 24.7 Hz, J_PC= 11.2 Hz, RhCH₂CH₂). ¹⁹F NMR

(188.3 MHz, CD₂Cl₂): δ −65.7 (s, C(CF₃)₃), −79.1 (s, CF₃SO₃).

³¹P{¹H} NMR (162.3 MHz, CD₂Cl₂): δ 0.3 (d, J_RhP= 143.7 Hz).

(+)ESI-MS: m/z 79, 195, 445, 637 (M − OTf⁻). HRMS (+ESI): calcd

for M − OTf⁻(C₂₂H₃₇F₉P₂Rh)⁺, 637.1276; found, 637.1291; Δ = 2.4

ppm.

[Rh(η⁵-Cp*)(CH₂CH₂-i-C₃F₇)(PMe₃)₂]OTf (30). AgOTf (35 mg,

0.14 mmol) was added to a solution of [Rh(η⁵-Cp*)(CH₂CH₂-i-

C₃F₇)I(PMe₃)]²⁰(80 mg, 0.13 mmol) in CH₂Cl₂(5 mL). The

suspension was stirred at room temperature for 2 h and ﬁltered. The

ﬁltrate was evaporated to dryness to give an orange residue, which was

dissolved in Et₂O (6 mL). To this solution was added PMe₃(1 M in

toluene, 0.13 mmol of PMe₃), and the mixture was stirred for 3 h at

room temperature. The volatiles were removed under vacuum, and the

residue was stirred with Et₂O (2 × 2 mL) and dried under vacuum to

give a pale yellow solid (76 mg, 0.10 mmol, 79%). Mp: 185−187 °C.

Anal. Calcd for C₂₂H₃₇F₁₀P₂SO₃Rh: C, 35.88; H, 5.06; S, 4.35. Found:

C, 35.58; H, 5.16; S, 4.83. ¹H NMR (300.1 MHz, CDCl₃): δ 2.04 (m,

2 H, RhCH₂CH₂), 1.78 (t, ⁴J_PH= 2.9 Hz, 15 H, C₅Me₅), 1.53 (second

order m, 18 H, PMe₃), 0.99 (m, 2 H, RhCH₂CH₂). ¹³C{¹H} NMR

(75.5 MHz, CDCl₃): δ 121.1 (qd, J_CF= 287.5 Hz, J_CF= 28.1 Hz,

CF₃C), 121.0 (q, J_CF= 320.8 Hz, CF₃S), 102.9 (dt, J_RhC= 3.6 Hz,

²J_PC= 2.4 Hz, C₅Me₅), 91.3 (d of m, J_CF= 203.3 Hz, ²J_CF= 31.1 Hz,

CF), 34.0 (dt, J_FC= 21.2 Hz, J_PC= 4.6 Hz, RhCH₂CH₂), 17.0

(second order m, PMe₃), 10.2 (t, ²J_PC= 1.1 Hz, C₅Me₅), 1.1 (dt, ¹J_RhC

= 24.3 Hz, J_PC= 10.6 Hz, RhCH₂CH₂).¹⁹F NMR (188.3 MHz,

ASSOCIATED CONTENT

* Supporting Information

■

CD₂Cl₂): δ −75.6 (d, J_FF= 6.7 Hz, CF(CF₃)₂), −79.1 (s, CF₃SO₃),

−184.4 (m, 1F, CF). ³¹P{¹H} NMR (121.5 MHz, CD₂Cl₂): δ −0.1 (d,

¹J_RhP= 144.1 Hz). (+)ESI-MS: m/z 118, 216, 587 (M − OTf⁻).

The Supporting Information is available free of charge on the

ACS Publications website at DOI: 10.1021/acs.organo-

met.6b00929.

HRMS (+ESI): calcd for M − OTf⁻(C₂₁H₃₇F₇P₂Rh)⁺, 587.1308;

found, 587.1308.

Anion or Radical Trapping Experiments in the Reaction of

Complexes [Ir(η⁵-Cp*)(η²-C₂H₄)(PPh₃)] with I-i-C₃F₇. I-i-C₃F₇(1

equiv) was added to a solution of [Ir(η⁵-Cp*)(η²-C₂H₄)(PPh₃)] (1

equiv) and the corresponding reagent (CH₃OH or CH₃OD; 2 equiv),

in D₈-toluene (0.5 mL), in a NMR tube under N₂. After 1 h, the NMR

spectra of the solution were measured. The corresponding reaction

products (H-i-C₃F₇and D-i-C₃F₇) were unambiguously identiﬁed by

Additional experimental details, NMR spectra, and

crystallographic data (PDF)

Crystallographic data (CIF)

AUTHOR INFORMATION

Corresponding Authors

*E-mail for J.G.-R.: jgr@um.es.

*E-mail for J.V.: jvs1@um.es.

■

20,41

their H and/or ¹⁹F NMR signals.

Reaction of 4 with AgOTf and PPh₃. AgOTf (4 mg, 0.02 mmol)

was added to a solution of complex 4 (11 mg, 0.011 mmol) in CD₂Cl₂.

The mixture was stirred for 2 h at room temperature, ﬁltered, and

transferred to a NMR tube. The NMR spectra of the solution showed

the presence of [Ir(η⁵-Cp*)(η²-o-C₆H₄PPh₂)(OTf)]²⁴and CH₃CH₂-t-

C₄F₉(see the Supporting Information) as the main products, together

with some unidentiﬁed broad signals. Then PPh₃(4 mg, 0.015 mmol)

was added and the solution was heated for 14 h at 70 °C, leading to

complete conversion into 13 and CH₃CH₂-t-C₄F₉.

Notes

The authors declare no competing ﬁnancial interest.

ACKNOWLEDGMENTS

■

We thank the Spanish Ministerio de Economıa y Compet-

itividad (grants CTQ2011-24016 and CTQ2015-69568-P, with

Reaction of 10 with PPh₃. AgOTf (5 mg, 0.02 mmol) was added

to a solution of complex 5 (9 mg, 0.0088 mmol) in CD₂Cl₂. The

mixture was stirred for 2 h at room temperature, ﬁltered, and

transferred to a NMR tube. The NMR spectra of the solution showed

quantitative conversion to 10. Then PPh₃(3 mg, 0.01 mmol) was

added and the solution was heated for 15 h at 50 °C, leading to a

mixture of 13 and CH₃CH₂-c-C₆F₁₁, resulting from PPh₃cyclo-

metalation, and 14 and H₂CCH-c-C₆F₁₁, resulting from alkene

substitution. The (cyclometalation products)/(substitution products)

́ ́

FEDER support) and Fundacion Seneca (grant 19890/GERM/

15) for ﬁnancial support.

REFERENCES

■

(1) Kirsch, P. Modern Fluoroorganic Chemistry; Wiley-VCH:

Weinheim, Germany, 2004. Zhou, Y.; Wang, J.; Gu, Z.; Wang, S.;

Zhu, W.; Acena, J. L.; Soloshonok, V. A.; Izawa, K.; Liu, H. Chem. Rev.

2016, 116, 422−518. Gillis, E. P.; Eastman, K. J.; Hill, M. D.;

molar ratio was 13, as estimated by integration of the H NMR and

Donnelly, D. J.; Meanwell, N. A. J. Med. Chem. 2015, 58, 8315−8359.

³¹P{¹H} spectra. The data of CH₃CH₂-c-C₆F₁₁and H₂CCH-c-C₆F₁₁

́ ́

Wang, J.; Sanchez-Rosello, M.; Acena, J. L.; del Pozo, C.; Sorochinsky,

are given in the Supporting Information.

A. E.; Fustero, S.; Soloshonok, V. A.; Liu, H. Chem. Rev. 2014, 114,

DOI: 10.1021/acs.organomet.6b00929

Organometallics XXXX, XXX, XXX−XXX

Organometallics

Article

2432−2506. Purser, S.; Moore, P. R.; Swallow, S.; Gouverneur, V.

Chem. Soc. Rev. 2008, 37, 320−330.

R.; Klatt, G.; Wadepohl, H.; Koppel, H. Inorg. Chem. 2010, 49, 3289−

3296.

(27) Bell, T. W.; Brough, S. A.; Partridge, M. G.; Perutz, R. N.;

Rooney, A. D. Organometallics 1993, 12, 2933−2941.

(28) Wang, D.; Angelici, R. J. Inorg. Chem. 1996, 35, 1321−1331.

(29) Michael, D.; Mingos, P.; Minshall, P. C.; Hursthouse, M. B.;

Malik, K. M. A.; Willoughby, S. D. J. Organomet. Chem. 1979, 181,

169−182.

(2) Jeschke, P. ChemBioChem 2004, 5, 570−589. Jeschke, P. Pest

Manage. Sci. 2010, 66, 10−27.

(3) Alonso, C.; Martínez de Marigorta, E.; Rubiales, G.; Palacios, F.

Chem. Rev. 2015, 115, 1847−1935.

(4) Neumann, C. N.; Ritter, T. Angew. Chem., Int. Ed. 2015, 54,

3216−3221. Ma, J.-A.; Cahard, D. Chem. Rev. 2004, 104, 6119−6146.

Yang, X.; Wu, T.; Phipps, R. J.; Toste, F. D. Chem. Rev. 2015, 115,

(30) Burger, P.; Bergman, R. G. J. Am. Chem. Soc. 1993, 115, 10462−

10463.

826−870. Zhu, W.; Wang, J.; Wang, S.; Gu, Z.; Acena, J. L.; Izawa, K.;

(31) Hughes, R. P.; Lindner, D. C.; Smith, J. M.; Zhang, D.;

Incarvito, C. D.; Lam, K.-C.; Liable-Sands, L. M.; Sommer, R. D.;

Rheingold, A. L. J. Chem. Soc., Dalton Trans. 2001, 2270−2278.

(32) Werner, H.; Feser, R. J. Organomet. Chem. 1982, 232, 351−370.

Feser, R.; Werner, H. J. Organomet. Chem. 1982, 233, 193−204.

Liu, H.; Soloshonok, V. A. J. Fluorine Chem. 2014, 167, 37−54.

(5) Tomashenko, O. A.; Grushin, V. V. Chem. Rev. 2011, 111, 4475−

4521. Furuya, T.; Kamlet, A. S.; Ritter, T. Nature 2011, 473, 470−477.

Barata-Vallejo, S.; Postigo, A. Coord. Chem. Rev. 2013, 257, 3051−

3069. Lantano, B.; Torviso, M. R.; Bonesi, S. M.; Barata-Vallejo, S.;

(33) Lumbierres, M.; Moreno-Manas, M.; Vallribera, A. Tetrahedron

Postigo, A. Coord. Chem. Rev. 2015, 285, 76−108.

(6) Egami, H.; Sodeoka, M. Angew. Chem., Int. Ed. 2014, 53, 8294−

8308. Besset, T.; Poisson, T.; Pannecoucke, X. Chem. - Eur. J. 2014, 20,

16830−16845.

2002, 58, 4061−4065.

(34) Igumnov, S. M.; Don, V. L.; Vyazkov, V. A.; Narinyan, K. E.

Mendeleev Commun. 2006, 16, 189−190. Xiao, F.; Wu, F.; Yang, X.;

Shen, Y.; Shi, X. J. Fluorine Chem. 2005, 126, 319−323. Sato, K.; Yuki,

T.; Yamaguchi, R.; Hamano, T.; Tarui, A.; Omote, M.; Kumadaki, I.;

Ando, A. J. Org. Chem. 2009, 74, 3815−3819. Iqbal, N.; Choi, S.; Kim,

E.; Cho, E. J. J. Org. Chem. 2012, 77, 11383−11387.

(35) Wang, X.; Ye, Y.; Zhang, S.; Feng, J.; Xu, Y.; Zhang, Y.; Wang, J.

J. Am. Chem. Soc. 2011, 133, 16410−16413. Yajima, T.; Jahan, I.;

Tonoi, T.; Shinmen, M.; Nishikawa, A.; Yamaguchi, K.; Sekine, I.;

Nagano, H. Tetrahedron 2012, 68, 6856−6861.

(7) Kawamura, S.; Egami, H.; Sodeoka, M. J. Am. Chem. Soc. 2015,

137, 4865−4873.

(8) He, Y.-T.; Li, L.-H.; Yang, Y.-F.; Zhou, Z.-Z.; Hua, H.-L.; Liu, X.-

Y.; Liang, Y.-M. Org. Lett. 2014, 16, 270−273. Koike, T.; Akita, M. J.

Fluorine Chem. 2014, 167, 30−36.

(9) Von Werner, K. J. Fluorine Chem. 1985, 28, 229−233.

(10) Dolbier, W. R. Chem. Rev. 1996, 96, 1557−1584.

(11) Cho, E. J. Chem. Rec. 2016, 16, 47−63.

(36) Brace, N. O. J. Org. Chem. 1962, 27, 3027−3032. Wu, F.; Xiao,

F.; Yang, X.; Shen, Y.; Pan, T. Tetrahedron 2006, 62, 10091−10099.

(37) Moseley, K.; Kang, J. W.; Maitlis, P. M. J. Chem. Soc. A 1970,

2875−2883.

(38) Glueck, D. S.; Bergman, R. G. Organometallics 1991, 10, 1479−

1486.

(39) Klingert, B.; Werner, H. Chem. Ber. 1983, 116, 1450−1462.

(40) Diversi, P.; Ingrosso, G.; Lucherini, A.; Martinelli, P.; Benetti,

M.; Pucci, S. J. Organomet. Chem. 1979, 165, 253−263.

(41) Denson, D. D.; Moore, G. J.; Tamborski, C. J. Fluorine Chem.

1975, 5, 475−480.

(12) Parsons, A. T.; Buchwald, S. L. Angew. Chem., Int. Ed. 2011, 50,

9120−9123. Fu, M.; Chen, L.; Jiang, Y.; Jiang, Z.-X.; Yang, Z. Org. Lett.

2016, 18, 348−351. Huang, X.-T.; Chen, Q.-Y. J. Org. Chem. 2001, 66,

4651−4656. Davis, C. R.; Burton, D. J.; Yang, Z.-Y. J. Fluorine Chem.

1995, 70, 135−140. Zhou, Q.-L.; Huang, Y.-Z. J. Fluorine Chem. 1989,

43, 385−392. Hu, C.-M.; Qiu, Y.-L. J. Fluorine Chem. 1991, 55, 109−

111. Chen, Q.-Y.; Yang, Z.-Y. J. Fluorine Chem. 1988, 39, 217−226.

Wang, J.-Y.; Su, Y.-M.; Yin, F.; Bao, Y.; Zhang, X.; Xu, Y.-M.; Wang,

X.-S. Chem. Commun. 2014, 50, 4108−4111. Xu, P.; Xie, J.; Xue, Q.;

Pan, C.; Cheng, Y.; Zhu, C. Chem. - Eur. J. 2013, 19, 14039−14042.

Chen, Q.-Y.; Yang, Z.-Y.; Zhao, C.-X.; Qiu, Z.-M. J. Chem. Soc., Perkin

Trans. 1 1988, 563−567. Kamigata, N.; Fukushima, T.; Terakawa, Y.;

Yoshida, M.; Sawada, H. J. Chem. Soc., Perkin Trans. 1 1991, 627−633.

(13) Choi, W. J.; Choi, S.; Ohkubo, K.; Fukuzumi, S.; Cho, E. J.; You,

Y. Chem. Sci. 2015, 6, 1454−1464.

(14) Caillot, G.; Dufour, J.; Belhomme, M.-C.; Poisson, T.; Grimaud,

L.; Pannecoucke, X.; Gillaizeau, I. Chem. Commun. 2014, 50, 5887−

5890.

(15) Feng, C.; Loh, T.-P. Angew. Chem., Int. Ed. 2013, 52, 12414−

12417.

(16) Surapanich, N.; Kuhakarn, C.; Pohmakotr, M.; Reutrakul, V.

Eur. J. Org. Chem. 2012, 2012, 5943−5952.

(17) Urata, H.; Yugari, H.; Fuchikami, T. Chem. Lett. 1987, 16, 833−

836.

(18) Xu, J.; Fu, Y.; Luo, D.-F.; Jiang, Y.-Y.; Xiao, B.; Liu, Z.-J.; Gong,

T.-J.; Liu, L. J. Am. Chem. Soc. 2011, 133, 15300−15303.

(19) Hughes, R. P.; Maddock, S. M.; Guzei, I. A.; Liable-Sands, L. M.;

Rheingold, A. L. J. Am. Chem. Soc. 2001, 123, 3279−3288.

(20) Gil-Rubio, J.; Guerrero-Leal, J.; Blaya, M.; Vicente, J.; Bautista,

D.; Jones, P. G. Organometallics 2012, 31, 1287−1299.

(21) Brookhart, M.; Lincoln, D. M. J. Am. Chem. Soc. 1988, 110,

8719−8720.

(22) Brookhart, M.; Hauptman, E.; Lincoln, D. M. J. Am. Chem. Soc.

1992, 114, 10394−10401.

(23) In the reaction with CH₃OD, H-i-C₃F₇was also observed,

probably arising from the reaction with residual water.

(24) Luecke, H. F.; Bergman, R. G. J. Am. Chem. Soc. 1997, 119,

11538−11539.

(25) Glueck, D. S.; Winslow, L. J. N.; Bergman, R. G. Organometallics

1991, 10, 1462−1479.

(26) Besora, M.; Vyboishchikov, S. F.; Lledos, A.; Maseras, F.;

Carmona, E.; Poveda, M. L. Organometallics 2010, 29, 2040−2045. Xu,

DOI: 10.1021/acs.organomet.6b00929

Organometallics XXXX, XXX, XXX−XXX

Products guided by the article

Product name:1,1,1,2,2,3,3-heptafluoropentane

Cas No:754-68-7

R&D Labs maybe for 754-68-7

Shanghai AoBo Bio-Pharmaceutical Technology Co., Ltd.

Contact:+86-21-51320130-801, 816

Address:Room 601, No. 1011, Halei Road, Zhangjiang High-Tech Park, Pudong, Shanghai
Shandong Wanda Organosilicon New Material Co., Ltd

Contact:+86-21-54177116;54302881

Address:R1318 Greenland No. 3 Lane 58 Xinjian East Rd., Minhang
ZhangJiaGang YaRui Chemical Co.,Ltd.

Contact:0512-58360968

Address:China JiangSu Province Zhang Jia Gang City YangShe Oriental Plaza Building 10 B307
chengdu firsterchem Pharmaceutical Co., Ltd.

Contact:028-66825849

Address:chengdu
jiangsu senxuan pharmaceutical and chemical co.,ltd

Contact:86-523-87982810

Address:hongqiao industrial zone,taixing,jiangsu china

Relevant to this article

A General and Practicable Synthesis of Polycyclic Heteroaromatic Compounds. Part 4. A Rationale for the Mechanism of the Synthesis

Doi:10.1039/P19810003041
(1981)
Reactions of α-Diazoketones with Phenylselenenyl Chloride. A new Synthesis of α-Chloro- and α-Phenylselenenyl-α,β-unsaturated Ketones

Doi:10.1039/c39800000506
(1980)
SYNTHESIS OF CYCLIC AMINIMINES WITH PERFLUOROALKYL GROUPS

Doi:10.1246/cl.1980.583
(1980)
New tacrine-derived AChE/BuChE inhibitors: Synthesis and biological evaluation of 5-amino-2-phenyl-4H-pyrano[2,3-b]quinoline-3-carboxylates

Doi:10.1016/j.ejmech.2017.01.042
(2017)
THE ABSOLUTE CONFIGURATION OF OPTICALLY ACTIVE ISOVALINE.

Doi:10.1248/cpb.12.1525
(1964)
Evaluation of endo- and exo-aryl-substitutions and central scaffold modifications on diphenyl substituted alkanes as 5-lipoxygenase activating protein inhibitors

Doi:10.1016/j.bmcl.2012.04.064
(2012)

Article Doi

Perfluoroalkylation of coordinated ethene in Rh(I) and Ir(I) complexes. Catalytic addition of iodoperfluoroalkanes to ethene

DOI: 10.1021/acs.organomet.6b00929

Source and publish data:

Authors:

Article abstract of DOI:10.1021/acs.organomet.6b00929

Full text of DOI:10.1021/acs.organomet.6b00929

Products guided by the article

R&D Labs maybe for 754-68-7

Relevant to this article

Hot Product