Substituent effect on reactions of ReH5(PMe2Ph)3 with propargyl alcohols

Article abstract of DOI:10.1016/j.ica.2020.120239

Reactions of the rhenium polyhydride ReH₅(PMe₂Ph)₃ with propargyl alcohols in the presence of HCl can produce γ-hydroxycarbyne, vinylcarbyne and η²-vinyl complexes, the relative amounts of which are dependent on the substituents of the propargyl alcohols. The reaction with the bis-alkyl substituted propargyl alcohol HC[tbnd]CC(OH)Me₂ produced only the vinylcarbyne complex ReCl₂(≡CCH=CMe₂)(PMe₂Ph)₃. The reaction with the bis-alkynyl substituted propargyl alcohol HC[tbnd]CC(OH)(C[tbnd]CSiMe₃)₂ produced only the η²-vinyl complex ReCl₂{ η²-CH₂=CC(OH)(C[tbnd]CSiMe₃)₂}(PMe₂Ph)₃. The reactions with the bis-(o-functionalized aryl) substituted propargyl alcohols HC[tbnd]CC(OH)Ar₂ (Ar = o-C₆H₄Br, o,o'-C₆H₃Cl₂) produced only the γ-hydroxycarbyne complexes Re{≡CCH₂C(OH)Ar₂}Cl₂(PMe₂Ph)₃. The reactions with the monoaryl substituted propargyl alcohol HC[tbnd]CC(OH)Ph(C[tbnd]CSiMe₃) produced a mixture of the vinylcarbyne Re{≡CCH=CPh(C[tbnd]CSiMe₃)}Cl₂(PMe₂Ph)₃, the γ-hydroxycarbyne Re{≡CCH₂C(OH)Ph(C[tbnd]CSiMe₃)}Cl₂(PMe₂Ph)₃ and the η ²-vinyl complex Re{η²-CH₂=CC(OH)Ph(C[tbnd]CSiMe₃)}Cl₂(PMe₂Ph)₃. The selectivity for the products can be related to the steric and electronic effect of the substituents of propargyl alcohols. In general, formation of η²-vinyl complexes is favored over carbyne complexes when the substituents are sterically less demanding. Formation of γ-hydroxycarbyne complexes is favored over vinylcarbyne complexes when the substituents are electron withdrawing.

Full text of DOI:10.1016/j.ica.2020.120239

Inorganica Chimica Acta 518 (2021) 120239
Contents lists available at ScienceDirect
Inorganica Chimica Acta
journal homepage: www.elsevier.com/locate/ica
Research paper
Substituent effect on reactions of ReH5(PMe2Ph)3 with propargyl alcohols
Guomei He1, Jiangxi Chen1, Herman Ho-Yung Sung, Ian Duncan Williams, Guochen Jia*
Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong
A R T I C L E I N F O
A B S T R A C T
Reactions of the rhenium polyhydride ReH5(PMe2Ph)3 with propargyl alcohols in the presence of HCl can
Dedicated to Professor Maurizio Peruzzini on
the occasion of his 65th birthdays
produce γ-hydroxycarbyne, vinylcarbyne and
η
2-vinyl complexes, the relative amounts of which are dependent
on the substituents of the propargyl alcohols. The reaction with the bis-alkyl substituted propargyl alcohol
–
–
–
HC CC(OH)Me2 produced only the vinylcarbyne complex ReCl2(≡CCH=CMe2)(PMe2Ph)3. The reaction with
Keywords:
–
–
–
–
CSiMe3)2 produced only the
–
the bis-alkynyl substituted propargyl alcohol HC
–
CC(OH)(C
η
2-vinyl complex
Rhenium
ReCl2{ η2-CH2=CC(OH)(C CSiMe3)2}(PMe2Ph)3. The reactions with the bis-(o-functionalized aryl) substituted
–
–
–
Propargyl alcohol
Carbyne
–
–
–
propargyl alcohols HC CC(OH)Ar2 (Ar = o-C6H4Br, o,o’-C6H3Cl2) produced only the γ-hydroxycarbyne com-
plexes Re{≡CCH2C(OH)Ar2}Cl2(PMe2Ph)3. The reactions with the monoaryl substituted propargyl alcohol
Vinylidene
η
2-vinyl complexes
–
–
–
–
–
CSiMe3)}
–
–
HC
–
CC(OH)Ph(C
–
CSiMe3) produced
a
mixture of the vinylcarbyne Re{≡CCH=CPh(C
–
–
–
Cl2(PMe2Ph)3, the γ-hydroxycarbyne Re{≡CCH2C(OH)Ph(C CSiMe3)}Cl2(PMe2Ph)3 and the
η
2-vinyl complex
Re{η2-CH2=CC(OH)Ph(C
–
CSiMe3)}Cl2(PMe2Ph)3. The selectivity for the products can be related to the steric
–
–
and electronic effect of the substituents of propargyl alcohols. In general, formation of
η
2-vinyl complexes is
favored over carbyne complexes when the substituents are sterically less demanding. Formation of γ-hydrox-
ycarbyne complexes is favored over vinylcarbyne complexes when the substituents are electron withdrawing.
–
–
OTf (Re-3) [3], the reaction with HC CC(OH)Me2 gives the dinuclear
–
1. Introduction
vinylidene-carbene complex [{(triphos)(CO)2Re}2{μ-(C10H12)}](OTf)2
–
–
Reactions of propargyl alcohols HC CC(OH)RR’ with transition
(Re-5) [4], while the reaction with the secondary propargyl alcohol
–
–
–
metal complexes are of interest because of their relevance to catalysis
and organometallic synthesis. In the area of rhenium chemistry, re-
actions of propargyl alcohols have been reported for several hydride-
free d6 rhenium(I) complexes including Re(OTf)(CO)2(triphos) (tri-
phos = MeC(CH2PPh2)3) [1–11], ReCl(CO)2{12[ane]P3iBu3}/CF3SO3Ag
(12[ane]P3iBu3 = the macrocyclic phosphine ligand 1,5,9-tri(isobutyl)-
1,5,9-triphosphacyclododecane) [12], [Re(CO)2(P)3]+ (P = PPh(OEt)2,
PPh2OEt) [13], [CpRe(NO)(PPh3)(CH2Cl2)]BF4 [14], trans-ReCl(N2)
(dppe)2 [15] and [Re(dppm)3]I [16,17]. The reactions often give
interesting organometallic compounds such as hydroxyvinylidenes or
allenylidenes or their derivatives, depending on the propargyl alcohol
substituents as well as reaction conditions. For example, Peruzzini and
his coworkers have shown that the reactions of Re(OTf)(CO)2(triphos)
HC CC(OH)H(Me) in the presence of MeOH gives the methoxyalkenyl
–
Fischer-type carbene complex [Re{C(OMe)CH=CHMe}(CO)2(triphos)]
OTf (Re-4) [4].
Rhenium forms a large number of hydride/dihydrogen complexes
with the number of H atoms in the hydride or dihydrogen ligands
ranging from 1 to 9. Their reactions with propargyl alcohols are
appealing as they can potentially give products derived from reactions
associated with the hydride functionality. However, such reactions have
rarely been investigated, although reactions of rhenium hydride com-
–
–
plexes with terminal alkynes (HC CR) [18–20] and reactions of prop-
–
argyl alcohols with hydrides of other metals (e.g. osmium [21]) are well-
documented. As a rare example, Albertin et al reported that the com-
plexes [Re(
η
2-H2)(CO)2(P)3] (P = PPh(OEt)2, PPh2OEt) can react with
–
–
–
–
(Re-1) with HC CC(OH)Ph(R) (R = Me, Ph, p-C6H4NO2) give the
HC C(OH)CPh2 at room temperature to give the allenylidene com-
–
–
–
–
–
–
allenylidene complexes [Re{=C C = CPh(R)}(CO) (triphos)]OTf (Re-
plexes [Re(=C C=CPh )(CO) P ]BF [12].
2
2 3 4
2, Scheme 1) [1,4], the reaction with 1-ethynyl-1-cyclohexanol gives the
Rhenium carbyne c2omplexes are potentially useful for catalysis,
material science and organometallic synthesis [22]. In our efforts in
hydroxyvinylidene complex [Re{=C=CH(c-C6H10OH)}(CO)2(triphos)]
* Corresponding author.
E-mail address: chjiag@ust.hk (G. Jia).
1
Present address: Department of Materials Science and Engineering, College of Materials, Xiamen University, Xiamen 361005, P. R. China
https://doi.org/10.1016/j.ica.2020.120239
Received 22 August 2020; Received in revised form 20 December 2020; Accepted 21 December 2020
Available online 29 December 2020
0020-1693/© 2020 Published by Elsevier B.V.

G. He et al.
Inorganica Chimica Acta 518 (2021) 120239
–
–
developing synthetic methods for the synthesis of rhenium carbyne
Similarly, the reaction of HC CC(OH)(o,o’-C6H3Cl2)2 (2c) with 1 in the
–
complexes, we have studied the reactions of ReH5(PMe2Ph)3 (1) with
presence of HCl produced the γ-hydroxycarbyne complex Re{≡CCH2C
–
–
–
–
–
–
the propargyl alcohols HC CC(OH)Ph2 and HC CC(R)(OH)C CSiMe3
(OH)(o,o’-C6H3Cl2)2}Cl2(PMe2Ph)3 (7). Again, vinylcarbyne and η2
vinyl complexes were also not detectable by in situ NMR experiments.
-
–
–
–
(R = CMe, adamantyl, iPr) in the presence of two equivalents of HCl
[23–26]. The reactions were found to give a mixture of products
The carbyne complexes 6 and 7 have been characterized by NMR,
elemental analysis as well as X-ray diffraction. The molecular structures
of 6 and 7 are shown in Figs. 1 and 2, respectively. The selected bond
distances and angles are given in Table 1. Both the complexes contain
three meridionally bound PMe2Ph ligands, two mutually cis chloride
ligands and a carbyne ligand trans to one of the chloride ligands. The
Re≡C bond distances are 1.761(8) Å for 6 and 1.764(5) Å for 7; the Re-C
(1)-C(2) angles are 172.6(6)◦ for 6 and 168.7(4)◦ for 7. The structural
data are similar to those of complex 4 [22]. The solid state structures are
supported by the solution NMR data. For example, the 13C{1H} NMR
spectra show the carbyne signals at 267.2 ppm for 6 and 267.5 ppm for 7
and those of CH2 at 56.9 ppm for 6 and 61.0 ppm for 7.
including vinylcarbyne, γ -hydroxycarbyne and
η
2-vinyl complexes. To
extend the application of the chemistry, it is desirable to know how the
substituents of propargyl alcohols might influence the selectivity of the
products. To this end, we have recently studied the reactions of
ReH5(PMe2Ph)3 (1) with several propargyl alcohols bearing substituents
with different electronic and steric properties. Herein we report the
results of this study.
2. Results and discussion
–
–
2.1. Reactions of ReH5(PMe2Ph)3 (1) with HC CC(OH)Ar2 (Ar = o-
–
–
–
C6H4Br, o,o’-C6H3Cl2)
The results from the reactions of 1 with HC CC(OH)Ar2 (Ar = Ph, o-
–
C6H4Br, o,o’-C6H3Cl2) indicate that presence of sterically demanding
–
–
We have previously reported that the reaction of HC CC(OH)Ph2
and electronically poor aryl groups at the C-OH carbon of propargyl
–
(2a) with ReH5(PMe2Ph)3 in the presence of HCl gave a mixture of the
alcohols disfavors the formation of
η
2-vinyl and vinylcarbyne com-
–
–
vinylcarbyne complex Re(≡CCH
=
CPh2)Cl2(PMe2Ph)3 (3), the
plexes. Previous study on reactions of HC CAr with ReH5(PMe2Ph)3
–
γ-hydroxycarbyne Re{≡CCH2C(OH)Ph2}Cl2(PMe2Ph)3 (4) and the η2
-
reveals that, due to steric effect, an increase in the steric bulkiness of the
vinyl complex Re{
η
2-CH2=CC(OH)Ph2}Cl2(PMe2Ph)3 (5) in a molar
–
–
aryl group Ar of HC CAr can increases the selectivity for the formation
–
ratio of 0.59:1:0.94 (Scheme 2) [22]. As a starting point to study the
effect of substituents of propargyl alcohols on the pathways for the
of carbyne complexes over that of
η
2-vinyl complexes.20 By analogy, the
lack of η2-vinyl products in the reactions with HC CC(OH)Ar2 (Ar = o-
–
–
–
formation of vinylcarbyne, γ-hydroxycarbyne, and
η
2-vinyl complexes,
C6H4Br, o,o’-C6H3Cl2) may also be attributed to steric effect, as will be
described in more detail in the section dealing with the mechanism of
the reactions. The lack of vinylcarbyne products in the reactions with
–
–
we have carried out the reactions of ReH5(PMe2Ph)3 (1) with HC CC
–
(OH)Ar2 (Ar = o-C6H4Br (2b), o,o’-C6H3Cl2 (2c)). Compared with
–
–
–
–
HC CC(OH)Ph2, the aryl groups of 2b and 2c are sterically more
HC CC(OH)Ar2 (Ar = Ph, o-C6H4Br, o,o’-C6H3Cl2) might be related to
–
–
demanding and electronically poorer.
the electron withdrawing property of the aryl groups.
–
–
The propargyl alcohol HC CC(OH)(o-C6H4Br)2 (2b) bearing two
–
aromatic rings with a bromo substituenet at the ortho position behaved
–
–
–
–
–
–
2.2. Reactions of 1 with HC CC(OH)Ph(C CSiMe3) and HC CC
–
–
–
–
–
differently compared with HC CC(OH)Ph2. As indicated by an in situ
–
–
–
(OH)(C CSiMe3)2
–
–
–
NMR experiment, HC CC(OH)(o-C6H4Br)2 reacted with 1 in the pres-
–
ence of HCl at room temperature to give the γ -hydroxycarbyne complex
Re{≡CCH2C(OH)(o-C6H4Br)2}Cl2(PMe2Ph)3 (6) as the major product
To further study steric effect of substituents of propargyl alcohols, we
–
–
–
–
have studied the reactions of 1 with HC CC(OH)Ph(C CSiMe3). As a
–
–
(Scheme 3). Vinylcarbyne and
η
2-vinyl complexes were either not
–
tion of
–
C
CSiMe3 group is sterically less demanding than a Ph group, forma-
–
produced or produced in an insignificant amount to be detectable by in
situ NMR. The γ -hydroxycarbyne complex 6 can be isolated as a
greenish-yellow solid in 82% yield with a preparative scale reaction.
η
2-vinyl complex might become more favorable for the reaction
–
–
–
–
–
–
with HC CC(OH)Ph(C CSiMe3) compared with that with HC CC
–
–
–
(OH)Ph2. The expectation has been confirmed experimentally. An in situ
Scheme 1. Selected reactions of Re(OTf)(CO)2(triphos) with propargyl alcohols.
2

G. He et al.
Inorganica Chimica Acta 518 (2021) 120239
–
–
Scheme 2. Reactions of ReH5(PMe2Ph)3 (1) with propargyl alcohols HC CC(OH)Ph2 (2a).
–
–
–
Scheme 3. Reactions of ReH5(PMe2Ph)3 (1) with propargyl alcohols HC CC(OH)Ar2 (Ar = o-C6H4Br, o,o’-C6H3Cl2).
–
–
–
NMR experiment shows that the reaction of 1 with HC CC(OH)Ph
vinylcarbyne complex Re(≡CCH
=
CPh2)Cl2(PMe2Ph)3 (3), the
–
2
–
–
(C CSiMe3) (2d) in the presence of HCl produced the vinylcarbyne
γ-hydroxycarbyne Re{≡CCH2C(OH)Ph2}Cl2(PMe2Ph)3 (4) and the
η
-
–
complex
γ-hydroxycarbyne
(PMe2Ph)3 (9), and the
ReCl2{≡CCH=C(Ph)(C CSiMe3)}(PMe2Ph)3
(8),
the
vinyl complex Re{η
2-CH2 = CC(OH)Ph2}Cl2(PMe2Ph)3 (5) in a molar
–
–
–
–
–
complex
ReCl2{≡CCH2C(OH)Ph(C CSiMe3)}
ratio of 0.59:1:0.94 (Scheme 2).
–
η
2-vinyl complex ReCl2{
η
2-CH2=CC(OH)Ph
It was noted that γ -hydroxycarbyne complexes 4 and 9 do not evolve
to the corresponding vinylcarbyne complexes on heating or treatment
with HCl. Thus the vinylcarbyne complexes are not formed by
–
–
(C CSiMe3)}(PMe2Ph)3 (10) in a molar ratio of 0.25:1:1.44 (Scheme 4).
–
–
–
For comparison, the reaction with HC CC(OH)Ph2 (2a) gave the
–
3

G. He et al.
Inorganica Chimica Acta 518 (2021) 120239
Fig. 1. ORTEP drawing of 6 with ellipsoids at 35% probability level. The hydrogen atoms on PMe2Ph ligands and phenyl groups are omitted for clarity.
dehydration of the γ -hydroxycarbyne complexes.
with the solid state structure, the 13C{1H} NMR spectrum of 11 shows
The structures of complexes 8–10 can be readily assigned by their
NMR data. In particular, the 31P{1H} NMR spectrum of 8 showed a
doublet at ꢀ 18.6 and a triplet at ꢀ 28.3 ppm. The 1H NMR spectrum
showed a characteristic Re≡CCH=C signal at 4.86 ppm. The 31P{1H}
NMR spectrum of 9 showed a doublet at ꢀ 20.3 and a triplet at –22.7
ppm. The 1H NMR spectrum showed a characteristic Re≡CCH2 signal at
2.65 ppm. The 31P{1H} NMR spectrum of 10 showed a triplet at ꢀ 27.1
ppm, and two doublet of doublets at ꢀ 29.0 and ꢀ 31.4 ppm. The 1H NMR
the Re=C signal at 248.1 ppm and that of Re-CH2 at 12.5 ppm. The 31
P
{1H} NMR spectrum shows a triplet at ꢀ 26.6 ppm and a doublet at
ꢀ 31.8 ppm with a coupling constant of 17.3 Hz.
The
η
2-vinyl complexes 10–11 are interesting as well characterized
rhenium
η
2-vinyl complexes are still rare. Reported examples of rhenium
η
2-vinyl complexes include trans-[ReCl(
η
2-CH2=CCH2Ph)(dppe)2]BF4
generated by the protonation of the allene complex trans-ReCl(
η
2-PhCH
=C=CH2)(dppe)2 with HBF4 [27], CpReBr(
η
2-CHPh = CPh)(PPh3)
2
spectrum showed a characteristic Re(
η
2-CH2C) signal at 2.37 ppm. These
generated by addition of H- to the alkyne complex [CpReBr(
η
-
2-RCH=CR)]BF4 (R =
–
–
NMR data are similar to those of the analogous complexes 3, 4, and 5,
respectively [22].
PhC CPh)(PPh3)]PF6 [28], and [Cp*Re(CO)2(
η
–
–
–
Ph, Me) generated by protonation of Cp*Re(CO)2(RC CR) with HBF4
–
Further support to the expectation that propargyl alcohols with the
[29].
–
–
sterically less demanding C CSiMe3 substituent favors the formation of
–
2
–
–
–
–
-vinyl complex comes from the reaction of 1 with HC CC(OH)
–
η
–
–
2.3. The reaction of 1 with HC CC(OH)Me2
–
–
–
–
(C CSiMe3)2 (2e). Treatment of 1 with 1.2 equivalents HC CC(OH)
–
–
–
(C CSiMe3)2 (2e) in the presence of 2.2 equiv. of HCl produced a brown
–
To further study the influence of the substituents at the C-OH carbon
solution. An in situ NMR experiment shows that the reaction produced
atom of the propargyl alcohols on the formation of vinylcarbyne, γ
2-vinyl complex ReCl2{ η 2-CH2 = CC(OH)(C CSiMe3)2}(PMe2Ph)3
–
the η
–
–
-hydroxycarbyne, and
η
2-vinyl complexes in our system, we have carried
(11) as the only 31P{1H} NMR active product (Scheme 4). Neither the
–
–
out the reactions of 1 with HC CC(OH)Me2. In situ NMR experiments
–
–
–
vinylcarbyne complex ReCl2{≡CCH = C(C CSiMe3)2}(PMe2Ph)3 nor
–
–
–
show that the reaction of 1 with HC CC(OH)Me2 produced the vinyl-
–
–
–
the γ-hydroxycarbyne complex ReCl2{≡CCH2C(OH)(C CSiMe3)2}
–
carbyne complex ReCl2(≡CCH=CMe2)(PMe2Ph)3 (12) only (Scheme 5).
(PMe2Ph)3 was detected in the in situ NMR experiment.
Neither the γ-hydroxycarbyne nor
the in situ NMR experiment.
η
2-vinyl complexes were detected in
Pure sample of the
η
2-vinyl complex 11 can be obtained in 86% yield
as purple crystals by recrystallization. Complex 11 has been character-
ized by NMR, elemental analysis as well as X-ray diffraction. The mo-
lecular structure of 11 is shown in Fig. 3. The complex 11 contains three
meridionally bound PMe2Ph ligands, two mutually cis chloride ligands
–
–
It is noted that reaction of HC CC(OH)Ph2 (2a) gave the vinyl-
–
carbyne complex Re(≡CCH=CPh2)Cl2(PMe2Ph)3 (3) and the γ-hydrox-
ycarbyne Re{≡CCH2C(OH)Ph2}Cl2(PMe2Ph)3 (4) in a molar ratio of
0.59:1. It appears that formation of vinylcarbyne complexes is more
favorable for reactions of propargyl alcohols with an alkyl group than
and a
η
2-vinyl ligand trans to one of the chloride ligands. The Re=C and
Re-C bond distances are 1.890(5) Å and 2.176(5) Å, respectively. The C
(1)-Re-C(2), Re-C(1)-C(2), Re-C(2)-C(1) and Re-C(2)-C(3) angles are
39.81(19)◦, 59.1(3)◦, 81.1(3)◦ and 150.6(4)◦, respectively. Consistent
–
–
–
–
that with an aryl group. The reactions with HC CC(OH)(R)C CSiMe3
–
–
(R = CMe3, Ph) follows that same trend. The reaction of the alkyl
–
–
–
–
substituted propargyl alcohol HC CC(OH)(CMe3)C CSiMe3 produced
–
–
4

G. He et al.
Inorganica Chimica Acta 518 (2021) 120239
Fig. 2. ORTEP drawing of 7 with ellipsoids at 35% probability level. The hydrogen atoms on PMe2Ph ligands and phenyl groups are omitted for clarity.
solid state structure found for 12 is supported by the solution NMR data.
Table 1
The 13C{1H} NMR spectrum shows the carbyne signal at 261.7 ppm and
that of CH=C at 134.9 ppm. The 31P{1H} NMR spectrum shows a triplet
at ꢀ 26.2 ppm and a doublet at ꢀ 17.6 ppm with a coupling constant of
12.6 Hz.
Selected bond distances [Å] and angles [◦] for rhenium carbyne complexes
ReCl2(≡C-CH2C(OH)(o-C6H4Br)2)(PMe2Ph)3 (6), ReCl2(≡C-CH2C(OH)(o,o’-
C6H3Cl2)2)(PMe2Ph)3 (7), ReCl2(≡C-CH = CMe2)(PMe2Ph)3 (12).
Compound
6
7
12
Re(1)-P(1)
2.451(2)
2.382(2)
2.458(2)
2.486(2)
2.543(2)
1.761(8)
1.463(10)
1.525(12)
172.6(6)
92.5(2)
2.4289(13)
2.3919(12)
2.4594(13)
2.4756(11)
2.5627(12)
1.764(5)
2.4215(8)
2.3803(8)
2.4212(8)
2.4939(7)
2.5478(8)
1.766(3)
Re(1)-P(2)
2.4. Mechanism for the formation of hydroxycarbyne, vinylcarbyne and
Re(1)-P(3)
η
2-vinyl complexes and comments on the experimental observations
Re(1)-Cl(1)
Re(1)-Cl(2)
Scheme 6 shows a plausible general mechanism for the formation of
Re(1)-C(1)
C(1)-C(2)
1.485(7)
1.433(5)
the γ -hydroxycarbyne complex Re{≡CCH2C(OH)R’2}Cl2(PMe2Ph)3 (G),
the vinylcarbyne complex Re(≡CCH = CR’2)Cl2(PMe2Ph)3 (H) and the
C(2)-C(3)
1.541(7)
1.356(5)
C(2)-C(1)-Re(1)
C(1)-Re(1)-P(1)
C(1)-Re(1)-P(2)
C(1)-Re(1)-P(3)
C(1)-Re(1)-Cl(1)
C(1)-Re(1)-Cl(2)
C(1)-C(2)-C(3)
168.7(4)
176.6(3)
η
2-vinyl complexes Re{
η
2-CH2=CC(OH)R’2}Cl2(PMe2Ph)3 (I) from the
92.58(15)
92.50(15)
93.90(15)
105.93(15)
170.77(15)
114.7(4)
91.57(10)
91.08(10)
90.35(10)
102.63(10)
172.96(10)
123.4(3)
–
–
reaction of 1 with propargyl alcohol HC CC(OH)R’2. Protonation of 1
89.3(3)
–
93.4(2)
with HCl may initially give the cationic hexahydride A which can lose
102.4(3)
171.7(3)
113.6(7)
two molecules of H2 to give the neutral unsaturated hydride complex B.
–
–
The hydride complex B can then react with a molecule of HC CC(OH)
–
R’2 to give the
η
2-alkyne complex C1 or C2, which are isomers arising
from different orientations of the alkyne. The complex C1 can undergo
an insertion reaction by transferring the hydride to the internal carbon
of the alkyne to give the vinyl complex D, which can evolve to the
the corresponding vinylcarbyne and γ-hydroxycarbyne complexes in
about 1:1 molar ratio [23], while that with the aryl substituted prop-
–
–
–
–
argyl alcohol HC CC(OH)Ph(C CSiMe3) produced corresponding
vinylidene complex E via α-hydrogen elimination [30,31]. Protonation
–
–
vinylcarbyne and γ -hydroxycarbyne complexes in a molar ratio of
0.25:1.
of E with HCl at the β-carbon followed by elimination of H2 would give
the γ-hydroxycarbyne complex G. Protonation of E with HCl at the ox-
ygen of the OH group followed by elimination of H2 and H2O would give
the vinylcarbyne complex H. Intermediate C2 could undergo an inser-
tion reaction by transferring the hydride to the terminal carbon of the
The vinylcarbyne complex 12 has been characterized by NMR and
elemental analysis. The structure of 12 has also been confirmed by X-ray
diffraction. The molecular structure of 12 is shown in Fig. 4. The
selected bond distances and angles are given in Table 1. Complex 12
contains three meridionally bound PMe2Ph ligands, two mutually cis
chloride ligands and a carbyne ligand trans to one of the chloride li-
gands. The Re≡C bond distance is 1.766(3) Å and Re-C(1)-C(2) angle is
176.6(3)◦. The structural data are similar to those of complex 2. The
alkyne to give the
η
2-vinyl complex F. Protonation of F with HCl fol-
lowed by loss of a molecule of H2 would give the
η
2-vinyl complex I.
Protonation of vinylidene complexes to give carbyne complexes [32]
and electrophilic abstraction of the OH group of hydroxyvinylidene
complexes to give vinylcarbyne complexes [33] are well documented
5

G. He et al.
Inorganica Chimica Acta 518 (2021) 120239
–
–
–
–
–
–
–
–
Scheme 4. Reactions of ReH5(PMe2Ph)3 (1) with propargyl alcohols HC CC(OH)Ph(C CSiMe3) and HC CC(OH)(C CSiMe3)2.
–
–
–
–
Fig. 3. ORTEP drawing of 11 with ellipsoids at 35%
probability level. Solvent and the hydrogen atoms on
PMe2Ph ligands and TMS groups are omitted for
clarity. Selected bond lengths [Å] and angles [◦]: Re
(1)-C(2) 1.890(5), Re(1)-C(1) 2.176(5), Re(1)-P(2)
2.4257(16), Re(1)-P(1) 2.4714(15), Re(1)-P(3)
2.4530(15), Re(1)-Cl(1) 2.5290(14), Re(1)-Cl(2)
2.4785(13), C(1)-C(2) 1.410(7), C(2)-C(3) 1.554(7);
C(2)-Re(1)-C(1) 39.81(19), C(2)-C(1)-Re(1) 59.1(3), C
(1)-C(2)-C(3) 128.3(5), C(1)-C(2)-Re(1) 81.1(3), C(3)-
C(2)-Re(1) 150.6(4).
6

G. He et al.
Inorganica Chimica Acta 518 (2021) 120239
–
–
Scheme 5. Reactions of ReH5(PMe2Ph)3 (1) with HC CC(OH)Me2.
–
Fig. 4. ORTEP drawing of 12 with ellipsoids at 35% probability level. The hydrogen atoms on PMe2Ph ligands and methyl groups are omitted for clarity.
reactions.
complexes and
η
2-vinyl complexes are strongly dependent on the steric
The proposed pathways for the formation of γ -hydroxycarbyne
properties of substituents of propargyl alcohols. The presence of steri-
cally demanding groups at the C-OH carbon disfavors the formation of
complex G and the
η
2-vinyl complex I are analogous to those previously
2-vinyl complexes. For example, the reaction of HC CC(OH)
–
η
–
–
proposed for the formation of carbyne complexes Re(≡CCH2Ar)
Cl2(PMe2Ph)3 (an analog of complex G) and
η
2-vinyl complexes Re(η2
-
2-vinyl complex, the reaction of
–
(C CSiMe3)2 produced only the η
–
–
CH2=CAr)Cl2(PMe2Ph)3 (an analog of complex I) from the reaction of 1
HC CC(OH)Ph2 produced a mixture of carbyne and
η
2-vinyl complexes
–
–
–
–
–
–
–
with terminal arylalkynes HC CAr in the presence of HCl, which have
while the reactions of HC CC(OH)Ar2 (Ar = o-C6H4Br or o,o’-C6H3Cl2)
–
–
been studied computationally [19]. The computational study on the
produced only carbyne complexes. The observed trend in the selectivity
for carbyne and η
2-vinyl complexes could be related to the relative
–
–
reactions with HC CAr reveals that the selectivity for the carbyne and
–
η
2-vinyl complexes is kinetically controlled and is related to the relative
stability of the intermediates C1 and C2, which can be influenced by the
stability of the
η
2-alkyne complex intermediates analogous to C1 and C2.
steric properties of the substituents. According to the mechanism shown
We observed experimentally that the relative amounts of carbyne
in Scheme 6,
η
2-vinyl complexes are derived from the insertion reactions
7

G. He et al.
Inorganica Chimica Acta 518 (2021) 120239
–
–
Scheme 6. A proposed general mechanism for the reactions of ReH5(PMe2Ph)3 (1) with HC CC(OH)R’2. PR3 = PMe2Ph.
–
of propargyl alcohols into the Re-H of intermediate C2, while carbyne
complexes are derived from insertion reactions of propargyl alcohols
into the Re-H of the intermediate C1. In the presence of sterically
demanding substituents, intermediate C2 is expected to be less favorable
β-carbon of the intermediate E. It is expected that protonation at the OH
group of intermediate E will become easier if the OH group is more
basic, leading to the production of a relatively larger amount of vinyl-
carbyne complexes. The basicity of OH group will be higher if the sub-
stituent is more electron donating. The relative electron donating ability
of Me, Ph, and o,o’-C6H3Cl2 is the order of Me > Ph > o,o’-C6H3Cl2. The
order is in line with the observed trend in the relative amount of
vinylcarbyne complexes produced in the reactions of the corresponding
propargyl alcohols with ReH5(PMe2Ph)3.
than intermediate C1 due to steric effect, making the formation of η2
-
vinyl complexes I to be less favorable than the formation of carbyne
complexes G and H).
We also noted that the relative amounts of vinylcarbyne and γ
-hydroxycarbyne complexes are dependent on the electronic properties
of the substituents. In general, the relative amount of vinylcarbyne
complexes increases as substituent of propargyl alcohols become more
3. Summary
–
–
electron donating. For example, the reactions of HC CC(OH)Ar2 (Ar =
–
o-C6H4Br, o,o’-C6H3Cl2) only produced the γ -hydroxycarbyne com-
Reactions of the rhenium polyhydride ReH5(PMe2Ph)3 with prop-
–
–
–
–
plexes, the reaction of HC CC(OH)Ph2 produced a mixture of γ
argyl alcohols HC CC(OH)RR’ in the presence of HCl can produce
–
–
-hydroxycarbyne and vinylcarbyne complexes, while the reaction of
vinylcarbyne Re(≡CCH = CRR’)Cl2(PMe2Ph)3, γ -hydroxycarbyne Re
HC CC(OH)Me2 produced only vinylcarbyne complex. The trend in the
{≡CCH2C(OH)RR’}Cl2(PMe2Ph)3 or
η
2-vinyl Re{
η
2-CH2=CC(OH)RR’}
–
–
–
relative amounts of the hydroxycarbyne and vinylcarbyne complexes
produced appears to be related to the basicity of the OH group, which
can be influenced by the electronic properties of the substituents. Ac-
cording to mechanism shown in Scheme 6, vinylcarbyne complexes are
derived from the protonation at the OH group of the intermediate E,
while γ -hydroxycarbyne complexes are derived from protonation at
Cl2(PMe2Ph)3 complexes or a mixture of these depending on the sub-
stituents on the C-OH carbon. The reaction with the bisalkyl substituted
–
–
propargyl alcohol HC CC(OH)Me2 produced only a vinylcarbyne
–
complex. The reaction with the bis-alkynyl substituted propargyl alcohol
η
2-vinyl complex. The re-
–
–
–
–
HC CC(OH)(C CSiMe3)2 produced only an
–
–
actions with the bis(o-functionalized aryl) substituted propargyl
8

G. He et al.
Inorganica Chimica Acta 518 (2021) 120239
–
–
alcohols HC CC(OH)Ar2 (Ar = o-C6H4Br, o,o’-C6H3Cl2) produced only
mixture was filtered through a filter paper and the residue was washed
by benzene (5 mL × 2) to give a brownish yellow solid, which was
identified as the known paramagnetic complex fac-ReCl3(PMe2Ph)3.
Yield, 256 mg, 45.7%. The solvent of the brownish-yellow filtrate was
removed under vacuum and the residue was washed with hexane (10
mL × 2) and then methanol (0.5 mL × 2) to give Re{≡C-CH2C(OH)(o,o’-
C6H3Cl2)2}Cl2(PMe2Ph)3 (7) as a greenish-yellow solid and dried under
vacuum. Yield, 274 mg, 33.9%. 31P{1H} NMR (161.98 MHz, CD2Cl2): δ
ꢀ 20.0 (d, JPP = 12.3 Hz), ꢀ 26.9 (t, JPP = 12.1 Hz). 1H NMR (400.13
MHz, CD2Cl2): δ 1.46 (d, JPH = 9.6 Hz, 6H, PMe2Ph), 1.72 (t, JPH = 4.2
Hz, 6H, PMe2Ph), 1.80 (t, JPH = 4.0 Hz, 6H, PMe2Ph), 3.18 (q, JPH = 3.6
Hz, 2H, Re≡C-CH2), 5.28 (s, 1H, OH), 6.57 (dd, JPH = 9.0 Hz, JHH = 7.6
Hz, 2H, PMe2Ph), 7.03–7.09 (m, 2H, PMe2Ph), 7.21 (t, JHH = 8.0 Hz,
C6H3Cl2), 7.15–7.22 (m, 1H, PMe2Ph), 7.30 (d, JHH = 8.0 Hz, C6H3Cl2),
7.31–7.37 (m, 6H, PMe2Ph), 7.37–7.43 (m, 4H, PMe2Ph). 13C{1H} NMR
(100.63 MHz, CD2Cl2): δ 267.5 (dt, JPC = 15.9 Hz, 14.0 Hz, Re≡C),
141.9 (d, JPC = 45.8 Hz, PMe2Ph), 140.3 (t, JPC = 19.9 Hz, PMe2Ph),
138.9 (s, C6H3Cl2), 134.3 (s, C6H3Cl2), 130.7 (s, C6H3Cl2), 129.8 (t, JPC
= 4.4 Hz, PMe2Ph), 128.8 (d, JPC = 8.2 Hz, PMe2Ph), 128.2 (s, C6H3Cl2),
127.8 (d, JPC = 2.0 Hz, PMe2Ph), 127.5 (t, JPC = 4.1 Hz, PMe2Ph), 127.3
(d, JPC = 8.8 Hz, PMe2Ph), 80.7 (d, JPC = 2.8 Hz, CH2COH), 61.0 (s,
CH2COH), 19.5 (d, JPC = 35.9 Hz, PMe2Ph), 16.2 (t, JPC = 17.0 Hz,
–
hydroxycarbyne complexes. The reactions with the monoaryl
–
–
–
–
–
substituted propargyl alcohol HC CC(OH)Ph(C CSiMe3) produced a
–
mixture of vinylcarbyne, γ-hydroxycarbyne and
η
2-vinyl complexes.
Formation of
η
2-vinyl complexes is favored over that carbyne complexes
when the substituents are sterically less demanding. Formation of
vinylcarbyne complexes is favored over γ -hydroxycarbyne complexes
when the substituents are electron releasing.
4. Experimental section
All manipulations were carried out under a nitrogen atmosphere
using standard Schlenk techniques unless otherwise stated. Solvents
were distilled under nitrogen from sodium benzophenone (hexane,
ether), sodium (benzene), or calcium hydride (CH2Cl2). The starting
material ReH5(PMe2Ph)3 (1) was prepared following the procedure
described in the literature [34]. Propargyl alcohols were prepared from
ethynylmagnesium bromide and related ketones following a procedure
–
–
similar to that for the preparation of HC CC(OH)Ph2 [35]. All other
–
reagents were used as purchased from Aldrich Chemical Co. Micro-
analyses were performed by Mꢀ Hꢀ W Laboratories (Phoenix, AZ). 1H,
13C{1H}, and 31P{1H} spectra were collected on a Bruker ARX-400
spectrometer (400 MHz). 1H and 13C NMR shifts are relative to TMS,
and 31P chemical shifts relative to 85% H3PO4. For cases involving vir-
tual coupling, the reported coupling constants were obtained assuming
that the spectra are first order.
PMe2Ph), 12.2 (t, JPC
= 16.0 Hz, PMe2Ph). Anal. Calcd. for
C
39H42Cl6OP3Re: C, 45.99; H, 4.16. Found: C, 46.13; H, 4.32.
–
–
–
–
Reaction of 1 with HC CC(OH)Ph(C CSiMe3). To a solution of
–
–
ReH5(PMe2Ph)3 (27 mg, 0.044 mmol) and 3-phenyl-1-(trimethylsilyl)
penta-1,4-diyn-3-ol (11.0 mg, 0.048 mmol) in benzene‑d6 (0.4 mL) in
an NMR tube was slowly added hydrogen chloride (1.0 M in diethyl
ether, 90 µL, 0.09 mmol). The mixture was stood at room temperature
for 8 h to give a brown solution with a small amount of brown precip-
itate. NMR spectra of the reaction mixture were then collected, which
–
–
Reaction of 1 with HC CC(OH)(o-C6H4Br)2. To a solution of
–
–
–
ReH5(PMe2Ph)3 (780 mg, 1.29 mmol) and HC CC(OH)(o-C6H4Br)2
–
(600 mg, 1.64 mmol) in benzene (20 mL) was slowly added hydrogen
chloride (1.0 M in diethyl ether, 1.50 mL, 1.50 mmol). After the mixture
was stirred at room temperature for 13 h, another portion of hydrogen
chloride (1.0 M in diethyl ether, 1.30 mL, 1.30 mmol) was slowly added
again and the reaction mixture was stirred for further 5 h to give a
brownish-green solution with a small amount of brown oily precipitate
which contains mainly fac-ReCl3(PMe2Ph)3. The solvent of the reaction
mixture was removed under vacuum. Dichloromethane (5 mL) was
added to the residue and the mixture was stirred for 30 min. Then ether
(20 mL) was added into the green suspension. After stirring for 20 min,
the mixture was filtered through a filter paper and the residue was
washed by ether (20 mL) to give Re{≡C-CH2C(OH)(o-C6H4Br)2}
Cl2(PMe2Ph)3 (6) as a greenish yellow solid and dried under vacuum.
Yield, 1.101 g, 82.3%. 31P{1H} NMR (161.98 MHz, CD2Cl2): δ ꢀ 20.2 (d,
JPP = 12.5 Hz), ꢀ 24.0 (t, JPP = 12.5 Hz). 1H NMR (400.13 MHz, CD2Cl2):
δ 1.50 (d, JPH = 9.6 Hz, 6H, PMe2Ph), 1.68 (t, JPH = 4.2 Hz, 6H, PMe2Ph),
1.76 (t, JPH = 3.6 Hz, 6H, PMe2Ph), 2.30 (q, JPH = 3.6 Hz, 2H, Re≡C-
CH2), 3.95 (s, 1H, OH), 6.67 (dd, JPH = 9.0 Hz, JHH = 7.6 Hz, 2H,
PMe2Ph), 7.13–7.22 (m, 4H, 2H for PMe2Ph & 2H for C6H4Br),
7.26–7.38 (m, 7H, PMe2Ph), 7.38–7.49 (m, 4H, C6H4Br), 7.49–7.56 (m,
4H, PMe2Ph), 7.77–7.85 (m, 2H, C6H4Br). 13C{1H} NMR (100.63 MHz,
CD2Cl2): δ 267.2 (dt, JPC = 16.9 Hz, 13.1 Hz, Re≡C), 142.3 (s, C6H4Br),
141.7 (d, JPC = 47.1 Hz, PMe2Ph), 140.5 (t, JPC = 19.8 Hz, PMe2Ph),
134.0 (s, C6H4Br), 131.0 (s, C6H4Br), 130.1 (t, JPC = 4.4 Hz, PMe2Ph),
128.9 (d, JPC = 8.7 Hz, PMe2Ph), 128.8(s, C6H4Br), 128.4(br, PMe2Ph),
127.8 (d, JPC = 2.0 Hz, PMe2Ph), 127.6 (t, JPC = 4.1 Hz, PMe2Ph), 127.3
(d, JPC = 8.8 Hz, PMe2Ph), 126.7 (s, C6H4Br), 119.7 (s, C6H4Br), 77.2 (s,
CH2COH), 56.9 (s, CH2COH), 19.0 (d, JPC = 35.0 Hz, PMe2Ph), 15.8 (t,
JPC = 17.2 Hz, PMe2Ph), 12.1 (t, JPC = 16.0 Hz, PMe2Ph). Anal. Calcd. for
–
–
indicate that the mixture contains ReCl2{≡CCH=C(Ph)(C CSiMe3)}
–
–
–
(PMe2Ph)3 (8), ReCl2{≡CCH2C(OH)Ph(C CSiMe3)}(PMe2Ph)3 (9) and
–
ReCl2{η2-CH2CC(OH)Ph(C CSiMe3)}(PMe2Ph)3 (10) in a molar ratio of
–
–
–
0.25 : 1 : 1.44. Characterization data for 8: 31P{1H} NMR (161.98 MHz,
C6D6): δ ꢀ 18.6 (d, JPP = 11.6 Hz), ꢀ 28.3 (t, JPP = 12.2 Hz). 1H NMR
(400.13 MHz, C6D6): δ 4.86 (q, JPH = 2.9 Hz, 1H, Re≡CCH=C). Char-
acterization data for 9: 31P{1H} NMR (161.98 MHz, C6D6): δ ꢀ 20.3 (dd,
JPP = 225.2 Hz, 12.4 Hz), ꢀ 21.7 (dd, JPP = 225.4 Hz, 12.4 Hz), –22.7 (t,
JPP = 12.5 Hz). 1H NMR (400.13 MHz, C6D6): δ 4.56 (s, 1H, COH), 2.65
(m, 2H, Re≡CCH2). Characterization data for 10: 31P{1H} NMR (161.98
MHz, C6D6): δ ꢀ 27.1 (t, JPP = 17.1 Hz), ꢀ 29.0 (dd, JPP = 239.0 Hz, 16.9
Hz), ꢀ 31.4 (dd, JPP = 238.4 Hz, 16.8 Hz). 1H NMR (400.13 MHz, C6D6):
δ 9.32 (s, 1H, COH), 2.37 (m, 2H, Re(
η
2-CH2C)).
–
–
–
–
Reaction of 1 with HC CC(OH)(C CSiMe3)2. To a solution of
–
–
ReH5(PMe2Ph)3 (300 mg, 0.50 mmol) and 3-ethynyl-1,5-bis(trimethyl-
silyl)penta-1,4-diyn-3-ol (144 mg, 0.56 mmol) in benzene (12 mL) was
slowly added hydrogen chloride (1.0 M in diethyl ether, 0.50 mL, 0.50
mmol). After the mixture was stirred at room temperature for 1 h,
another portion of hydrogen chloride (1.0 M in diethyl ether, 0.55 mL,
0.55 mmol) was slowly added again and the reaction mixture was stirred
for further 12 h to give a brown solution with a small amount of
brownish yellow precipitate. The reaction mixture was filtered through
a filter paper to remove a small amount brownish yellow precipitate.
The volume of the filtrate was reduced to ca. 5 mL under vacuum. Then
the solution was carefully layered with hexane (30 mL) and stood for 1
2
–
–
η -CH2CC(OH)(C CSiMe3)2}Cl2(PMe2Ph)3 (11) as a
–
day to give Re{
purple crystal, which was collected by filtration and dried under vac-
uum. Yield, 392 mg, 86.0%. 31P{1H} NMR (161.98 MHz, CD2Cl2): δ
ꢀ 26.6 (t, JPP = 17.3 Hz), ꢀ 31.8 (d, JPP = 17.3 Hz). 1H NMR (400.13
MHz, CD2Cl2): δ 0.20 (s, SiMe3), 1.48 (d, JPH = 9.2 Hz, 6H, PMe2Ph),
1.66 (t, JPH = 4.0 Hz, 6H, PMe2Ph), 1.83 (t, JPH = 4.0 Hz, 6H, PMe2Ph),
C
39H44Br2Cl2OP3Re: C, 45.10; H, 4.27. Found: C, 44.91; H, 4.21.
–
–
Reaction of 1 with HC CC(OH)(o,o’-C6H3Cl2)2. To a solution of
–
–
–
ReH5(PMe2Ph)3 (480 mg, 0.79 mmol) and HC CC(OH)(o,o’-C6H3Cl2)2
–
(329 mg, 0.95 mmol) in benzene (20 mL) was slowly added hydrogen
chloride (1.0 M in diethyl ether, 1.0 mL, 1.0 mmol). After the mixture
was stirred at room temperature for 13 h, another portion of hydrogen
chloride (1.0 M in diethyl ether, 0.70 mL, 0.70 mmol) was slowly added
again and the reaction mixture was stirred for further 5 h to give a
brownish-yellow solution with a brown oily precipitate. The reaction
2.35 (dt, JPH = 8.8 Hz, 3.6 Hz, 2H, Re{
η
2(=C-CH2)}), 6.47 (t, JPH = 8.0
Hz, JHH = 7.6 Hz, 2H, Ph), 7.09 (t, JHH = 7.6 Hz, 2H, Ph), 7.24 (t, JHH
=
7.4 Hz, 1H, Ph), 7.30–7.50 (m, 10H, Ph), 8.32 (s, 1H, OH). 13C{1H} NMR
(100.63 MHz, CD2Cl2): δ 248.1 (dt, JPC = 8.8 Hz, 12.6 Hz, Re{
η
2(=C-
9

G. He et al.
Inorganica Chimica Acta 518 (2021) 120239
CH2)}), 140.8 (d, JPC = 49.2 Hz, PMe2Ph), 136.7 (t, JPC = 20.1 Hz,
PMe2Ph), 130.4 (t, JPC = 4.0 Hz, PMe2Ph), 128.9 (d, JPC = 7.0 Hz,
PMe2Ph), 128.4(s, PMe2Ph), 128.1(d, JPC = 3.0 Hz, PMe2Ph), 127.4 (t,
CRediT authorship contribution statement
Guomei He: Conceptualization, Methodology, Investigation,
Writing - original draft. Jiangxi Chen: Conceptualization, Methodol-
ogy, Investigation, Writing - original draft. Herman Ho-Yung Sung:
Methodology, Investigation, Writing - original draft. Ian Duncan Wil-
liams: Supervision, Writing - review & editing. Guochen Jia: Supervi-
sion, Funding acquisition, Writing - review & editing.
–
–
JPC = 4.0 Hz, PMe2Ph), 127.3 (d, JPC = 8.0 Hz, PMe2Ph), 100.1 (s, C C),
–
–
–
89.0 (s, C C), 80.8 (s, COH), 18.4 (d, JPC = 37.6 Hz, PMe2Ph), 14.4 (t,
–
JPC = 16.2 Hz, PMe2Ph), 13.2 (t, JPC = 16.4 Hz, PMe2Ph), 12.5 (d, JPC
=
17.1 Hz, Re(
η
2-CH2C)), ꢀ 1.4 (s, SiMe3). Anal. Calcd. for C37H54Cl2O-
P3ReSi2: C, 48.25; H, 5.91. Found: C, 48.07; H, 5.85.
–
–
Reaction of
1
with HC CC(OH)Me2. To
a
solution of
–
ReH5(PMe2Ph)3 (500 mg, 0.83 mmol) in benzene (10 mL) was added 2-
methyl-butyn-2-ol (0.10 mL, 1.03 mmol) and then hydrogen chloride
(1.0 M in diethyl ether, 0.90 mL, 0.90 mmol). After the mixture was
stirred at room temperature for 3 h, another portion of hydrogen chlo-
ride (1.0 M in diethyl ether, 0.90 mL, 0.90 mmol) was slowly added
again and the reaction mixture was stirred for further 12 h to give a
reddish brown solution with a brownish yellow oily precipitate. The
reaction mixture was filtered through a filter paper and the residue was
washed by benzene (3 mL × 2) to give a brownish yellow solid, which
was identified as the known paramagnetic complex fac-ReCl3(PMe2Ph)3.
Yield, 112 mg (19.2%). The solvent of the reddish brown filtrate was
removed under vacuum and the residue was washed with methanol (1
mL × 2) to give Re(≡CCH = CMe2)Cl2(PMe2Ph)3 (12) as a red solid and
dried under vacuum. Yield, 314 mg (51.5%). 31P{1H} NMR (161.98
MHz, CD2Cl2): δ ꢀ 17.6 (d, JPP = 12.6 Hz), ꢀ 26.2 (t, JPP = 12.6 Hz). 1H
NMR (400.13 MHz, CD2Cl2): δ 1.37 (d, JPH = 9.2 Hz, 6H, PMe2Ph), 1.52
(s, 3H, CH3), 1.82 (t, JPH = 4.0 Hz, 6H, PMe2Ph), 1.90 (t, JPH = 4.0 Hz,
6H, PMe2Ph), 2.00 (s, 3H, CH3), 4.66 (br, 1H, Re≡C-CH=C), 6.84 (t, JPH
= 8.8 Hz, 2H, Ph), 7.02 (t, JHH = 7.6 Hz, 2H, Ph), 7.14 (t, JHH = 7.6 Hz,
1H, Ph), 7.30–7.38 (m, 6H, Ph), 7.40–7.505 (m, 4H, Ph). 13C{1H} NMR
(100.63 MHz, CD2Cl2): δ 261.7 (dt, JPC = 16.0 Hz, 14.0 Hz, Re≡C),
151.2 (q, JPC = 3.4 Hz, CH=C(CH3)2), 142.2 (d, JPC = 46.0 Hz, Ph),
140.9 (t, JPC = 19.7 Hz, Ph), 134.9 (q, JPC = 2.7 Hz, CH=C(CH3)2), 129.6
(t, JPC = 4.4 Hz, Ph), 128.8 (d, JPC = 8.4 Hz, Ph), 128.1 (s, Ph), 127.5 (d,
JPC = 1.6 Hz, Ph), 127.4 (t, JPC = 4.0 Hz, Ph), 126.8 (d, JPC = 8.8 Hz, Ph),
24.5 (s, CH3), 21.3 (s, CH3), 19.0 (d, JPC = 35.1 Hz, PMe2Ph), 17.2 (t, JPC
= 17.3 Hz, PMe2Ph), 11.0 (t, JPC = 15.2 Hz, PMe2Ph). Anal. Calcd. for
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
This work was supported by the Hong Kong Research Grants Council
(Project No.: 16321516, 16308719) and Natural Science Foundation of
China (Project No.: 21971218).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.ica.2020.120239.
References
[1] C. Coletti, Luca Gonsalvi, G. Antonella, L. Marvelli, M. Peruzzini, G. Reginato,
N. Re, Organometallics 31 (2012) 57–69.
[2] N. Mantovani, M. Brugnati, L. Gonsalvi, E. Grigiotti, F. Laschi, L. Marvelli,
M. Peruzzini, G. Reginato, R. Rossi, P. Zanello, Organometallics 24 (2005)
405–418.
[3] N. Mantovani, L. Marvelli, R. Rossi, C. Bianchini, I. de los Rios, A. Romerosa,
M. Peruzzini, J. Chem. Soc. Dalton Trans. 16 (2001) 2353–2361.
[4] C. Bianchini, N. Mantovani, L. Marvelli, M. Peruzzini, R. Rossi, A. Romerosa,
J. Organomet. Chem. 617–618 (2001) 233–241.
[5] C. Bianchini, N. Mantovani, A. Marchi, L. Marvelli, D. Masi, M. Peruzzini, R. Rossi,
A. Romerosa, Organometallics 18 (1999) 4501–4508.
C
29H40Cl2P3Re: C, 47.16; H, 5.46. Found: C, 47.18; H, 5.52.
[6] C. Coletti, L. Gonsalvi, A. Guerriero, L. Marvelli, M. Peruzzini, G. Reginato, N. Re,
Organometallics 29 (2010) 5982–5993.
Crystal structure analysis. The crystals of 6, 7, and 12 were grown
from a dichloromethane solution layered with hexane at room temper-
ature. The crystal of 11 was grown from a benzene solution layered with
hexane using acetone as the transition layer at room temperature. The
diffraction intensity data of 6 were collected with an Oxford Diffraction
[7] V. Bertolasi, N. Mantovani, L. Marvelli, R. Rossi, C. Bianchini, I. de los Rios,
M. Peruzzini, D.N. Akbayeva, Inorg. Chim. Acta 344 (2003) 207–213.
[8] M. Peruzzini, D. Akbayeva, C. Bianchini, I. de los Rios, A. Ienco, N. Mantovani,
L. Marvelli, R. Rossi, Inorg. Chim. Acta 339 (2002) 202–208.
[9] N. Mantovani, L. Marvelli, R. Rossi, V. Bertolasi, C. Bianchini, I. de Rios,
M. Peruzzini, Organometallics 21 (2002) 2382–2394.
Gemini™ S Ultra X-ray Diffractometer with monochromatized Cu-K
α
[10] N. Mantovani, P. Bergamini, A. Marchi, L. Marvelli, R. Rossi, V. Bertolasi,
V. Ferretti, I. De Rios, M. Peruzzini, Organometallics 25 (2006) 416–426.
[11] M. Peruzzini, P. Barbaro, V. Bertolasi, C. Bianchini, I. de los Rios, N. Mantovani,
L. Marvelli, R. Rossi, Dalton Trans. (2003) 4121–4131.
radiation (λ = 1.54178 Å) at 173 K. Lattice determination, data collec-
tion and reduction were carried out using CrysAlisPro 171.33.46. Ab-
sorption correction was performed using built-in SADABS program the
CrysAlisPro program suite. The diffraction intensity data of 7, 11, and
12 were collected with a Bruker Smart APEX CCD diffractometer with
[12] R.J. Baker, P.G. Edwards, J. Gracia-Mora, F. Ingold, K.M. Abdul Malik, J. Chem.
Soc. Dalton Trans. (2002) 3985–3992.
[13] G. Albertin, S. Antoniutti, E. Bordignon, D. Bresolin, J. Organomet. Chem. 609
(2000) 10–20.
graphite-monochromated Mo-Kαradiation (λ = 0.71073 Å) at 100 K.
Lattice determination and data collection were carried out using SMART
v.5.625 software. Data reduction and absorption correction by empirical
methods were performed using SAINT v 6.26 and SADABS v 2.03,
respectively. Structure solution and refinement for all compounds were
performed using the Olex2 software [36] package (which embedded
SHELXTL [37]). All the structures were solved by direct methods,
expanded by difference Fourier syntheses and refined by full matrix
least-squares on F2. All non-hydrogen atoms were refined anisotropi-
cally with a riding model for the hydrogen atoms except noted sepa-
rately. Crystallographic data have been deposited with the Cambridge
Crystallographic Data Centre as supplementary publication nos. CCDC
2,023,976 (complex 6), CCDC 2,023,977 (complex 7), CCDC 2,023,978
(complex 11) and CCDC 2,023,979 (complex 12). These data can be
obtained free of charge via: http://www.ccdc.cam.ac.uk/conts/retrie
ving.html, or from the Cambridge Crystallographic Data Centre, 12
Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-
mail: deposit@ccdc.cam.ac.uk.
[14] (a) S. Legoupy, C. Crevisy, J.-C. Guillemin, R. Gree, J. Organomet. Chem. 567
(1998) 75–81. (b) S. Legoupy, C. Crevisy, J.-C. Guillemin, R.J. Gree, Tetrahedron
Lett. 37 (1996) 1225–1228.
[15] A.J.L. Pombeiro, S.S.P.R. Almeida, M.F.C.G. Silva, J.C. Jeffrey, R.L. Richards,
J. Chem. Soc. Dalton Trans. (1989) 2381–2387.
[16] K.F. Lee, W. Bai, H.H.Y. Sung, I.D. Williams, Z. Lin, G. Jia, Chem. Eur. J. 24 (2018)
9760–9764.
[17] K.W. Chan, W. Bai, K.F. Lee, K.-H. Lee, H.H.Y. Sung, I.D. Williams, Z. Lin, G. Jia,
Organometallics 35 (2016) 3520–3529.
[18] See, for example, (a) M.A. Alvarez, M.E. Garcia, D. Garcia-Vivo, E. Huergo, M.A.
Ruiz, Organometallics, 37 (2018) 3425–3436. (b) M.A. Alvarez, M.E. Garcia, D.
Garcia-Vivo, E. Huergo, M.A. Ruiz, Inorg. Chem. 57 (2018) 912–915. (c) Y. Jiang,
O. Blacque, T. Fox, C. Frech, H.M. Berke, Organometallics 28 (2009) 4670–4680.
(d) G. Albertin, S. Antoniutti, J. Castro, S. Garcia-Fontan, G. Schipilliti, Eur. J.
Inorg. Chem. (2007) 1713–1722. (e) G. Albertin, S. Antoniutti, A. Bacchi, G.
Pelizzi, M. Tollon, J. Organomet. Chem. 690 (2005) 4573–4582. (f) O.V. Ozerov, L.
A. Watson, M. Pink, M.H. Baik, K.G. Caulton, Organometallics 23 (2004)
4934–4943. (g) J.A. Cabeza, F. Grepioni, A. Llamazares, V. Riera, R. Trivedi, Eur. J.
Inorg. Chem. (2000) 1693–1697. (h) M. Leeaphon, P.E. Fanwick, R.A. Walton, J.
Am. Chem. Soc. 114 (1992) 1890–1892. (i) M. Leeaphon, A.L. Ondracek, R.J.
Thomas, P.E. Fanwick, R.A. Walton, J. Am. Chem. Soc. 117 (1995) 9715–9724. (j)
Y. Kim, J. Gallucci, A. Wojcicki, Organometallics 11 (1992) 1963–1967. (k) D.
10

G. He et al.
Inorganica Chimica Acta 518 (2021) 120239
Nietlispach, D. Veghini, H. Berke, Helv. Chim. Acta 77 (1994) 2197–2208. (l) G.
(1995) 1382–1395;
Albertin, S. Antoniutti, E. Bordignon, D. Bresolin, J. Organomet. Chem. 609 (2000)
10–20.
(l) A.M. LaPointe, R.R. Schrock, Organometallics 14 (1995) 1875–1884;
(m) D.S. Williams, R.R. Schrock, Organometallics 13 (1994) 2101–2104;
(n) R. Toreki, R.R. Schrock, W.M. Davis, J. Am. Chem. Soc. 114 (1992)
3367–3380;
[19] C. Bianchini, A. Marchi, L. Marvelli, M. Peruzzini, A. Romerosa, R. Rossi,
Organometallics 15 (1996) 3804–3816. (b) C. Bianchini, A. Marchi, N. Mantovani,
L. Marvelli, D. Masi, M. Peruzzini, R. Rossi, Eur. J. Inorg. Chem. (1998) 211–219.
[20] G. He, T. Fan, J. Chen, H.H.Y. Sung, I.D. Williams, Z. Lin, G. Jia, New J. Chem. 37
(2013) 1823–1832.
(o) I.A. Weinstock, R.R. Schrock, W.M. Davis, J. Am. Chem. Soc. 113 (1991)
135–144;
(p) W.A. Herrmann, J.K. Felixberger, R. Anwander, E. Herdtweck, P. Kiprof,
J. Riede, Organometallics 9 (1990) 1434–1443.
´
[21] (a) M.L. Buil, O. Eisenstein, M.A. Esteruelas, C. García-Yebra, E. Gutierrez-Puebla,
´
˜
M. Olivan, E. Onate, N. Ruiz, M.A. Tajada, Organometallics 18 (1999) 4949–4959;
[23] J. Chen, G. He, H.H.Y. Sung, I.D. Williams, Z. Lin, G. Jia, Organometallics 29
(2010) 2693–2701.
´
´
(b) M.L. Buil, M.A. Esteruelas, C. García-Yebra, E. Gutierrez-Puebla, M. Olivan,
Organometallics 19 (2000) 2184–2193;
[24] J. Chen, C. Shi, H.H.Y. Sung, I.D. Williams, Z. Lin, G. Jia, Chem. Eur. 18 (2012)
14128–14139.
´
˜
(c) M.A. Esteruelas, C. García-Yebra, M. Olivan, E. Onate, Organometallics 19
(2000) 3260–3262;
[25] J. Chen, H.H.Y.W. Sung, D. Ian, Z. Lin, G. Jia, Angew. Chem. Int. Ed. 50 (2011)
10675–10678.
´
˜
(d) M.A. Esteruelas, C. García-Yebra, M. Olivan, E. Onate, M.A. Tajada,
Organometallics 19 (2000) 5098–5106;
[26] J. Chen, C. Shi, H.H.Y. Sung, I.D. Williams, Z. Lin, G. Jia, Organometallics 31
(2012) 1817–1824.
˜
(e) P. Barrio, M.A. Esteruelas, E. Onate, Organometallics 22 (2003) 2472–2485;
(f) M.L. Buil, M.A. Esteruelas, K. Garces, E. Onate, Organometallics 28 (2009)
5691–5696;
[27] A.J.L. Pombeiro, D.L. Hughes, R.L. Richards, J. Silvestre, R. Hoffmann, J. Chem.
Soc., Chem. Commun. (1986) 1125–1127.
(g) Q. Zhao, L. Gong, C. Xu, J. Zhu, X. He, H. Xia, Angew. Chem. Int. Ed. 50 (2011)
1354–1358;
[28] C. Carfagna, N. Carr, R.J. Deeth, S.J. Dossett, M. Green, M.F. Mahon, C.J. Vaughan,
Chem. Dalton Trans. Soc. (1996) 415–430.
(h) Q. Zhao, X. Cao, T.B. Wen, H. Xia, Chem. Asian J. 8 (2013) 269–275.
[22] (a) For examples of work on rhenium carbyne complexes, see: O.V. Ozerov, L.
A. Watson, M. Pink, K.G. Caulton J. Am. Chem. Soc. 129 (2007) 6003–6016;
(b) X. Li, M. Schopf, J. Stephan, J. Kipke, K. Harms, J. Sundermeyer,
Organometallics 25 (2006) 528–530;
[29] (a) C.P. Casey, J.T. Brady, T.M. Boller, F. Weinhold, R.K. Hayashi, J. Am. Chem.
Soc. 120 (1998) 12500–12511;
(b) C.P. Casey, J.T. Brady, Organometallics 17 (1998) 4620–4629.
[30] It has been reported in Reference 20 that the conversion of the alkyne complex Re{
η
2-(HC≡CPh)}ClH2(PMe3)3 via the η η 1-vinyl complex Re(HC=CHPh)ClH
(c) O.V. Ozerov, L.A. Watson, M. Pink, K.G. Caulton, J. Am. Chem. Soc. 126
(2004) 6363–6378;
(PMe3)3 to the vinylidene complex Re(=C=CHPh)ClH2(PMe3)3 has a relatively
low barrier than that involve direct 1,2-hydrogen shift.
(d) X. Li, M. Schopf, J. Stephan, J. Kippe, K. Harms, J. Sundermeyer, J. Am. Chem.
Soc. 126 (2004) 8660–8661;
[31] For additional examples of formation of vinylidene complexes via h1-vinyl
complkexes, see, (a) J.H. Lee, M. Pink, Y.D. Smurnyy, K.G. Caulton, J. Organomet.
Chem. 693 (2008) 1426–1438; (b) M. Olivan, E. Clot, O. Eisenstein, K.G. Caulton,
Organometallics, 17 (1998) 3091–3100.
(e) O.V. Ozerov, M. Pink, L.A. Watson, K.G. Caulton, J. Am. Chem. Soc. 126
(2004) 2105–2113;
(f) O.V. Ozerov, J.C. Huffman, L.A. Watson, K.G. Caulton, Organometallics 22
(2003) 2539–2541;
[32] See, for example, M. Jimenez-Tenorio, M.C. Puerta, P. Valerga, M.A. Ortuno, G.
Ujaque, A. Lledos, Organometallics 33 (2014) 2549–2560.
(g) W.M. Xue, Y. Wang, M.C.W. Chan, Z.M. Su, K.K. Cheung, C.M. Che,
Organometallics 17 (1998) 1946–1955;
[33] See, for example, (a) B. Richter, H. Werner, Organometallic 28 (2009) 5137–5141.
(b) T. Bolano, R. Castarlenas, M.A. Esteruelas, F.J. Modrego, E. Onate, J. Am.
Chem. Soc. 127 (2005) 11184–11195. (c) T.B. Wen, Y.K. Cheung, J. Yao, W.T.
Wong, Z.Y. Zhou, G. Jia, Organometallics 19 (2000) 3803–3809.
[34] P.G. Douglas, B.L. Shaw, Inorg. Synth. 17 (1977) 64–66.
(h) W.M. Xue, M.C.W. Chan, T.C.W. Mak, C.M. Che, Inorg. Chem. 36 (1997)
6437–6439;
(i) M.F.N.N. Carvalho, S.S.P.R. Almeida, A.J.L. Pombeiro, R.A. Henderson,
Organometallics 16 (1997) 5441–5448;
[35] C.D. Gabbutt, B.M. Heron, A.C. Instone, D.A. Thomas, S.M. Partington, M.
B. Hursthouse, T. Gelbrich, Eur. J. Org. Chem. (2003) 1220–1230.
[36] O.V. Dolomanov, L.J. Bourhis, R.J. Gildea, J.A.K. Howard, H.J. Puschmann, Appl.
Cryst. 42 (2009) 339–341.
(j) W.M. Xue, Y. Wang, T.C.W. Mak, C.M.J. Che, Chem. Dalton Trans. Soc. (1996)
2827–2834;
(k) E.O. Fischer, C. Apostolidis, E. Dornberger, A.C. Filippou, B. Kanellakopulos,
B. Lungwitz, J. Muller, B. Powietzka, J. Rebizant, W. Roth, Z. Naturforsch. B 50
[37] G.M. Sheldrick, Acta Cryst. A64 (2008) 112–122.
11