Rhenium carbyne and η2-vinyl complexes from one-pot reactions of ReH5(PMe2Ph)3 with terminal alkynes

Article abstract of DOI:10.1021/om100122a

Treatment of the rhenium polyhydride complex ReH₅(PMe ₂Ph)₃ with HC≡CR (R = Ph, SiMe₃, (CH ₂)₄Me) in the presence of 2.2 equiv of HCl produces a mixture of the carbyne complexes Re(≡CCH₂R)Cl ₂(PMe₂Ph)₃ and the η²-vinyl complexes Re(η²-CH₂CR)Cl₂(PMe ₂Ph)₃. When HC≡CC(OH)Ph₂ was used, the reaction gave the carbyne complexes Re(≡CCH=CPh₂)Cl ₂(PMe₂Ph)₃ and Re(≡CCH ₂C(OH)Ph₂)Cl₂(PMe₂Ph)₃ along with the η²-vinyl complex Re(η²-CH ₂CC(OH)Ph₂)Cl₂(PMe₂Ph)_3.

Full text of DOI:10.1021/om100122a

Organometallics 2010, 29, 2693–2701 2693
DOI: 10.1021/om100122a
Rhenium Carbyne and η2-Vinyl Complexes from One-Pot Reactions of
ReH5(PMe2Ph)3 with Terminal Alkynes
Jiangxi Chen, Guomei He, Herman Ho-Yung Sung, Ian Duncan Williams, Zhenyang Lin,*
and Guochen Jia*
Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay,
Kowloon, Hong Kong
Received February 15, 2010
Treatment of the rhenium polyhydride complex ReH5(PMe2Ph)3 with HCtCR (R = Ph, SiMe3,
(CH2)4Me) in the presence of 2.2 equiv of HCl produces a mixture of the carbyne complexes
Re(tCCH2R)Cl2(PMe2Ph)3 and the η2-vinyl complexes Re(η2-CH2CR)Cl2(PMe2Ph)3. When HCt
CC(OH)Ph2 was used, the reaction gave the carbyne complexes Re(tCCHdCPh2)Cl2(PMe2Ph)3
and Re(tCCH2C(OH)Ph2)Cl2(PMe2Ph)3 along with the η2-vinyl complex Re(η2-CH2CC(OH)-
Ph2)Cl2(PMe2Ph)3.
Introduction
Rhenium forms a large number of mononuclear polyhy-
dride complexes with the number of hydride ligands ranging
from 3 to 9. Under thermal or photochemical conditions,
rhenium polyhydride complexes were found to react with
olefins and saturated hydrocarbons.10 Remarkably, the opera-
tionally unsaturated complexes ReH4((R2PCH2SiMe2)2N)
(R=i-Pr, Cy, t-Bu) react with olefins and alkanes to give car-
byne complexes.11 Here, “operationally unsaturated com-
plexes” refer to those complexes that have an electron count
of 16 but contain π-donor ligand(s) showing certain degrees of
π-donation or π-stabilization.12 However, the reactivity of
rhenium polyhydrides toward alkynes has rarely been investi-
gated and only a few interesting observations have appeared
in the literature. The pentahydride complexes ReH5(PhP-
((CH2)3PPh2)2) and ReH5(PhP((CH2)3PCy2)2) react with act-
ivated alkynes RO2CCtCCO2R (R = Me, Et) to afford
Re(η3-RO2CCdCHCO2R)(η2-(RO2 CCHdCHCO2R)(PhP-
((CH2)3PPh2)2) and ReH3(η2-RO2CCHdCHCO2R)(PhP-
((CH2)3PCy2)2), respectively.13 Reactions of ReH4(mq)-
(PPh3)2 (mq is the monoanion of 2-mercaptoquinoline)
with alkynes in the presence of EPF6 (E=H, Ph3C) produces
the hydrido alkylidyne species [ReH2(tCCH2R)(mq)-
(PPh3)2]þ.14 The operationally unsaturated tetrahydride
There has been much interest in the reactions of metal
hydride complexes with alkynes due to their relevance to
catalysis and organometallic synthesis. In the case of rhe-
nium, reactions of alkynes with several rhenium mono- and
dihydride complexes have been reported: for example, ReH-
(CO)5,1 ReH(CO)5-n(PMe3)n (n = 2-4),2 Cp2ReH,3 CpRe-
(CO)(NO)H,4 ReH(Rpz)(HRpz)(NO)(PPh3)2,5 Re(Br)(H)-
(NO)(PR3)2] (R = Cy, i-Pr),6 [Re(η2-H2)(CO)2P3]þ (P =
P(OEt)3, PPh(OEt)2, PPh2OEt),7 and [ReH2Cl(bpy)(PPh-
(OEt)2)3]BPh4.8 The reactions usually lead to insertion of
alkynes into a Re-H bond to give η1-vinyl complexes, with
the exception of [Re(η2-H2)(CO)2P3]þ, which reacts with
terminal alkynes to give vinylidene complexes, and ReH-
(Rpz)(HRpz)(NO)(PPh3)2, which reacts with arylacetylenes
to give acetylide complexes. Insertion of alkyne into a Re-H
bond also occurred in the protonation reactions of Cp*Re-
(CO)2(RCtCR) (R = Me, Ph) with HBF4 to give the η2-
vinyl complexes [Cp*Re(CO)2(η2-RCHdCR)]BF4.9
*To whom correspondence should be addressed. E-mail: chjiag@
ust.hk.
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r
2010 American Chemical Society
Published on Web 05/25/2010
pubs.acs.org/Organometallics

2694 Organometallics, Vol. 29, No. 12, 2010
Chen et al.
Scheme 1
complex (PNP-t-Bu)Re(H)4, where PNPtBu is (t-Bu2PCH2-
SiMe2)2N, reacts at 23 °C with HCtCR (R = t-Bu, SiMe3,
Ph) to give first H2 and (PNP-t-Bu)ReH3(CtCR), then H2
and (PNP-t-Bu)Re(CtCR)2.15
In this work, we have studied the reactions of ReH5-
(PMe2Ph)3 with terminal alkynes in the presence of HCl.
As will be described below, the reactions in general give a
mixture of carbyne and η2-vinyl complexes.
Results and Discussion
Reaction of Phenylacetylene. Complex ReH5(PMe2Ph)3
(1) was found to have very low reactivity toward phenylace-
tylene. Thus, no appreciable reactions were observed after a
mixture of 1 and excess (ca. 8 equiv) PhCtCH were stirred at
room temperature for 2 days or refluxed for 4.5 h in benzene.
The low reactivity of 1 toward PhCtCH is not surprising, as
rhenium polyhydride complexes are in general relatively
stable and unreactive. For example, the reaction of ReH5-
(PMe2Ph)3 with COD can only be achieved with photolysis,
and [ReH4(PMe2Ph)4]þ is even unreactive toward PhCtCPh
and CO.16
Figure 1. Molecular structure of ReCl2(tCCH2Ph)(PMe2Ph)3
(2).
complex ReCl2(tCCH2Ph)(PMe2Ph)3 (2) and the η2-vinyl
complex ReCl2(η2-CH2CPh)(PMe2Ph)3 (3) (Scheme 1).
Electrophiles such as Hþ and Ph3Cþ have been used
successfully by Walton et al. to activate ReH4(mq)(PPh3)2
(mq is the monoanion of 2-mercaptoquinoline) to react with
alkynes.14 Thus, we initially tried the reaction of PhCtCH
with 1 in the presence of HBF4, hoping that [ReH6(PMe2Ph)3]-
BF4 generated in situ by protonation of 1 with HBF4 will be
more reactive toward PhCtCH. As monitored by in situ NMR,
the reaction between 1 and PhCtCH in the presence of HBF4
did occur. Unfortunately, the reaction produced a mixture of
species which were difficult to separate and identify. A similar
The carbyne complex 2 has been characterized by NMR
and elemental analysis as well as X-ray diffraction. The
molecular structure of 2 is shown in Figure 1, and crystal-
lographic details and selected bond distances and angles are
given in Tables 1 and 2, respectively. As shown in Figure 1,
the complex contains three meridionally bound PMe2Ph
ligands, two mutually cis chloride ligands, and a carbyne
ligand trans to one of the chloride ligands. The RetC bond
distance is 1.767(3) A, and the Re-C(1)-C(2) angle is
177.6(3)°. The structural data are similar to those for repor-
ted carbyne complexes such as [ReCl(tCC6H2Me3-2,4,6)-
17
mixture was obtained when preformed [ReH6(PMe2Ph)3]BF4
was used.
19
(o-(PPh2)2C6H4)]ClO4 and ((tBu2PCH2SiMe2)2N)ReH-
We then carried out the reaction of 1 with PhCtCH in the
presence of HCl. When 1 equiv of HCl was used, the reaction
produced two new complexes in a ca. 1:1 molar ratio along
with unreacted starting materials 1. When 2.2 equiv of HCl
was used, 1 was consumed almost completely, and the same
two new complexes were obtained as the major products
along with small amounts of the known complexes mer-
ReCl3(PMe2Ph)3 and fac-ReCl3(PMe2Ph)318 and trace amounts
of other unknown species. The two new complexes can be
separated by recrystallization and were identified as the carbyne
(tCCH2CMe3).11 Consistent with the solid-state structure,
the 13C{1H} NMR spectrum shows the carbyne signal at
268.1 ppm and that of CH2 at 54.6 ppm. The 31P{1H} NMR
spectrum shows a triplet at -21.3 ppm and a doublet at
-16.5 ppm with a coupling constant of 12.4 Hz.
Rhenium carbyne complexes have attracted considerable
attention for their relevance to catalytic metathesis reac-
tions20 and photophysical properties.19 Previously reported
synthetic routes to obtain rhenium carbyne complexes include
(19) (a) Xue, W. M.; Wang, Y.; Mak, T. C. W.; Che, C. M. J. Chem.
Soc., Dalton Trans. 1996, 2827. (b) Xue, W. M.; Chan, M. C. W.; Mak,
T. C. W.; Che, C. M. Inorg. Chem. 1997, 36, 6437. (c) Xue, W. M.; Wang, Y.;
Chan, M. C. W.; Su, Z. M.; Cheung, K. K.; Che, C. M. Organometallics
1998, 17, 1946.
(20) (a) Vaughan, G. A.; Toreki, R.; Schrock, R. R.; Davis, W. M.
J. Am. Chem. Soc. 1993, 115, 2980. (b) Toreki, R.; Vaughan, G. A.; Schrock,
R. R.; Davis, W. M. J. Am. Chem. Soc. 1993, 115, 127.
(15) Ozerov, O. V.; Watson, L. A.; Pink, M.; Baik, M. H.; Caulton,
K. G. Organometallics 2004, 23, 4934.
(16) Lunder, D. M.; Green, M. A.; Streib, W. E.; Caulton, K. G.
Inorg. Chem. 1989, 28, 4527.
(17) Moehring, G. A.; Walton, R. A. J. Chem. Soc., Dalton Trans.
1987, 715.
(18) Douglas, P. G.; Shaw, B. L. Inorg. Synth. 1977, 17, 65.

Article
Organometallics, Vol. 29, No. 12, 2010 2695
Table 1. Crystallographic Details for Complexes 2, 3, 8, and 9
2
3 CH2Cl2
3
8 CHCl3
3
9
empirical formula
formula wt
temp, K
wavelength, A
cryst syst
space group
a, A
b, A
C
32H40Cl2P3Re
C33H42Cl4P3Re
859.58
100(2)
0.710 73
orthorhombic
Pnma
23.7835(15)
11.2713(7)
13.8111(9)
90
90
90
3702.4(4)
4
1.542
3.722
1712
C40H45Cl5P3Re
982.12
100(2)
0.710 73
monoclinic
P21/c
10.1416(4)
19.4068(8)
20.9570(8)
90
94.468(2)
90
4112.1(3)
4
1.586
3.425
1960
C39H46Cl2OP3Re
880.77
173(2)
1.541 78
triclinic
P1
8.1451(10)
12.1004(10)
21.0248(13)
102.461(7)
97.347(7)
104.028(7)
1927.2(3)
2
774.65
100(2)
0.710 73
monoclinic
P21/n
8.403(4)
23.344(12)
16.545(9)
90
96.283(9)
90
3226(3)
4
1.595
c, A
R, deg
β, deg
γ, deg
V, A3
Z
calcd d, Mg/m3
abs coeff, mm-1
F(000)
1.518
8.838
884
3.95-67.50
4.101
1544
1.51-26.00
θ range for data
collecn, deg
no. of rflns collected
no. of indep rflns
completeness to
θ = 25.00° (%)
abs cor
2.00-27.00
1.43-26.00
14 043
6159 (R(int) = 0.0417)
97.3
20 381
4115 (R(int) = 0.0600)
97.3
22 835
7955 (R(int) = 0.0264)
98.8
13 102
6576 (R(int) = 0.0604)
94.7
semiempirical
semiempirical
from equivalents
1.00 and 0.78
4115/34/206
semiempirical
from equivalents
1.00 and 0.80
7955/0/442
semiempirical
from equivalents
1.00 and 0.61
6576/0/415
from equivalents
1.815 and -0.635 e
6159/0/343
max and min transmissn
no. of
data/restraints/params
goodness of fit on F2
final R indices (I > 2σ(I))
1.024
1.025
1.009
1.036
R1 = 0.0260,
wR2 = 0.0515
1.00 and 0.62
R1 = 0.0492,
wR2 = 0.1178
1.835 and -1.622
R1 = 0.0223,
wR2 = 0.0478
0.972 and -0.357
R1 = 0.0589,
wR2 = 0.1479
2.815, -1.709
largest diff peak and
hole, e A-3
R-abstraction from C-bonded ligands, especially ligating
neopentylidene,21,22 O-abstraction of acyl complexes,19,23
protonation of coordinated isonitrile,24 protonation of vi-
nylidene complexes,25 and reaction of rhenium halide with
phosphorus ylide.26 While there have been many reports on
the formation of carbyne complexes from the reactions of
alkynes with appropriate ruthenium27 and osmium28 pre-
cursors, similar transformations with rhenium complexes are
very limited. As rare examples, rhenium carbyne complexes
were reported to be generated from the reactions of alkynes
with the edge-sharing bioctahedral dicarbonyl complex Re2-
(μ-Cl)(μ-CO)Cl3(CO)(μ-dppm)2 in the presence of TlX29 and
with ReH4(mq)(PPh3)2 (mq is the monoanion of 2-mercapto-
quinoline) in the presence of EPF6 (E=H, CPh3).14 The ope-
rationally unsaturated complexes ReH4((R2PCH2SiMe2)2N)
(R=i-Pr, Cy, t-Bu) also react with olefins and alkanes to give
carbyne complexes.11 Our work provides a new example of the
direct formation of carbyne complexes from the reactions of
alkynes with rhenium complexes.
(21) (a) LaPointe, A. M.; Schrock, R. R. Organometallics 1995, 14,
1875. (b) Toreki, R.; Schrock, R. R.; Davis, W. M. J. Am. Chem. Soc. 1992,
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1991, 10, 1844. (d) Weinstock, I. A.; Schrock, R. R.; Davis, W. M. J. Am.
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Chem. Soc. 1982, 104, 6806.
The structure of the η2-vinyl complex 3 has been con-
firmed by X-ray diffraction. The molecular structure of 3 is
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Roth, W. Z. Naturforsch., B 1995, 50, 1382.
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G. P. A.; Fogg, D. E. Adv. Synth. Catal. 2002, 344, 757. (b) Shaffer, E. A.;
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P.; Weberndorfer, B.; Ilg, K.; Wolf, J.; Werner, H. Angew. Chem., Int. Ed.
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Chem. 2001, 25, 1101. (h) Gonzalez-Herrero, P.; Weberndorfer, B.; Ilg, K.;
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4640. (l) Bustelo, E.; Jimenez-Tenorio, M.; Mereiter, K.; Puerta, M. C.;
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Valerga, P. Organometallics 2002, 21, 1903. (m) Bustelo, E.; Jimenez-
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2696 Organometallics, Vol. 29, No. 12, 2010
Chen et al.
˚
Table 2. Selected Bond Distances (A) and Angles (deg) for
Rhenium Carbyne Complexes ReCl2(tCR)(PMe2Ph)3 (2, 8, 9)
˚
Table 3. Selected Bond Distances (A) and Angles (deg) for
ReCl2(η2-CH2dCPh)(PMe2Ph)3 (3)
2
8
9
bond length
bond angle
Re(1)-C(1)
Re(1)-P(3)
Re(1)-P(1)
Re(1)-P(2)
Re(1)-Cl(2)
Re(1)-Cl(1)
C(1)-C(2)
C(2)-C(3)
1.767(3)
1.768(3)
2.3810(7)
2.4331(7)
2.4467(7)
2.4507(6)
2.5400(6)
1.428(4)
1.357(4)
1.740(8)
2.3770(19)
2.452(2)
2.439(2)
2.489(2)
2.550(2)
1.511(12)
1.542(11)
Re(1)-C(2)
1.935(7)
2.156(7)
C(2)-C(1)-Re(1)
61.6(4)
78.4(4)
40.0(3)
2.3905(13)
2.4190(15)
2.4377(15)
2.5022(13)
2.5427(12)
1.477(5)
Re(1)-C(1)
Re(1)-P(1)
Re(1)-P(2)#1
Re(1)-P(2)
Re(1)-Cl(1)
Re(1)-Cl(2)
C(1)-C(2)
C(2)-C(3)
C(3)-C(8)
C(3)-C(4)
C(4)-C(5)
C(5)-C(6)
C(6)-C(7)
C(7)-C(8)
C(1)-C(2)-Re(1)
C(2)-Re(1)-C(1)
C(2)-Re(1)-P(1)
C(1)-Re(1)-P(1)
C(2)-Re(1)-P(2)#1
C(1)-Re(1)-P(2)#1
C(2)-Re(1)-P(2)
C(1)-Re(1)-P(2)
C(2)-Re(1)-Cl(1)
C(1)-Re(1)-Cl(1)
C(2)-Re(1)-Cl(1)
C(2)-Re(1)-Cl(2)
C(1)-Re(1)-Cl(2)
2.4161(19)
2.4333(14)
2.4333(14)
2.4741(18)
2.4935(18)
1.415(10)
1.452(9)
1.388(10)
1.409(10)
1.404(10)
1.380(12)
1.373(13)
1.385(10)
115.9(2)
75.89(18)
90.10(4)
94.25(4)
90.10(4)
94.25(4)
167.9(2)
152.10(19)
88.54(3)
88.7(2)
1.510(5)
C(2)-C(1)-Re(1)
C(1)-Re(1)-P(3)
C(1)-Re(1)-P(1)
C(1)-Re(1)-P(2)
C(1)-Re(1)-Cl(2)
C(1)-Re(1)-Cl(1)
177.6(3)
173.2(2)
92.69(8)
89.46(8)
92.85(8)
104.38(8)
171.61(8)
171.5(6)
89.5(3)
93.1(2)
91.9(2)
102.5(3)
171.9(3)
93.24(12)
89.93(12)
93.26(12)
100.37(12)
175.36(11)
128.71(19)
longer than typical CdC double bonds. The structural feat-
ures associated with the Re(η2-CH2C) fragment are similar
to those of reported η2-vinyl rhenium complexes: for exam-
ple, [Cp*Re(CO)2(η2-PhCHCPh)]BF49a and trans-[ReCl(η2-
CH2C(CH2Ph))(dppe)2]BF4.30 Consistent with the solid-
state structure, the 13C{1H} NMR spectrum of 3 shows the
CPh signal at 245.6 ppm and that of CH2 at 11.7 ppm. The
31P{1H} NMR spectrum shows a triplet at -25.3 ppm and a
doublet at -27.7 ppm with a coupling constant of 16.9 Hz.
A few η2-vinyl complexes have been obtained previously
from other routes. Pombeiro et al. isolated trans-[ReCl(η2-
CH2C(CH2Ph))(dppe)2]BF4 from the protonation reaction
of the allene complex trans-ReCl(η2-PhCHdCdCH2)-
(dppe)2 with HBF4.30 Green et al. prepared CpReBr(η2-
CHPhCPh)(PPh3) by addition of H- to the alkyne complex
[CpReBr(η2-PhCtCPh)(PPh3)]PF6.31 Casey et al. obtained
[Cp*Re(CO)2(η2-RCHCR)]BF4 (R = Ph, Me) from the
protonation reactions of Cp*Re(CO)2(RCtCR) with
HBF4.9 η2-Vinyl complexes have also been reported for other
transition metals such as Mo,32 W,33 and Os.34,35
Figure 2. Molecular structure of ReCl2(η2-CH2dCPh)(PMe2Ph)3
(3).
shown in Figure 2, and crystallographic details and selected
bond distances and angles are given in Tables 1 and 3,
respectively. The coordination sphere of 3 is very similar to
that of complex 2, except that 2 has the carbyne ligand
CCH2Ph while 3 has the η2-CH2CPh ligand. In complex 3,
the Re-C(1) bond (2.156(7) A) is significantly longer than
the Re-C(2) bond (1.935(7) A). The C(1)-C(2) bond
(1.415(10) A) is shorter than typical C-C single bonds and
(29) (a) Kort, D. A.; Shih, K. Y.; Wu, W.; Fanwick, P. E.; Walton,
R. A. Organometallics 1995, 14, 448. (b) Shih, K. Y.; Fanwick, P. E.;
Walton, R. A. J. Chem. Soc., Chem. Commun. 1994, 861.
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P. N.; Russo, M. V.; Manojlovic-Muir, L.; Muir, K. W. J. Chem. Soc.,
(28) Examples of Os-carbyne complexes prepared from alkynes:
(a) Weber, B.; Steinert, P.; Windmuller, B.; Wolf, J.; Werner, H.
J. Chem. Soc., Chem. Commun. 1994, 2595. (b) Richter, B.; Werner, H.
Chem. Commun. 1981, 1059. (b) Green, M.; Norman, N. C.; Orpen, A. G.
J. Am. Chem. Soc. 1981, 103, 1267. (c) Allen, S. R.; Green, M.; Orpen, A. G.;
Williams, I. D. J. Chem. Soc., Chem. Commun. 1982, 826. (d) Allen, S. R.;
Baker, P. K.; Barnes, S. G.; Bottrill, M.; Green, M.; Orpen, A. G.; Williams,
I. D.; Welch, A. J. J. Chem. Soc., Dalton Trans. 1983, 927. (e) Davidson,
€
Organometallics 2009, 28, 5137. (c) Werner, H.; Jung, S.; Weberndorfer, B.;
Wolf, J. Eur. J. Inorg. Chem. 1999, 951. (d) Espuelas, J.; Esteruelas, M. A.;
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Lahoz, F. J.; Oro, L. A.; Ruiz, N. J. Am. Chem. Soc. 1993, 115, 4683.
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Article
Organometallics, Vol. 29, No. 12, 2010 2697
Scheme 2
Scheme 2 shows a plausible mechanism for the formation
HCl would give the cationic carbyne complex E, which then
loses a molecule of H2 and combines with the chloride counter-
anion to give carbyne complex 2. Intermediate C could also
undergo an insertion reaction to give the η1-vinyl complex F or
the η2-vinyl complex G. Protonation of G with HCl followed by
losing a molecule of H2 would give the η2-vinyl complex 3.
Reactions of Other Alkynes. Formation of rhenium carbyne
complexes has been reported for the reactions of alkynes with
ReH4(mq)(PPh3)2 in the presence of EPF6 (E = H, CPh3).14
Formation of η2-vinyl complexes have been reported for the
reactions of Cp*Re(CO)2(RCtCR) with HBF4.9 The reaction
of 1 with phenylacetylene described above represents a rare
example of the formation of both carbyne and η2-vinyl
complexes from the reaction of alkynes with rhenium hydride
complexes. In this regard, it is noted that Esteruelas et al.
recently showed34 that reactions of [OsH2(OAc)(H2O)(P-i-
Pr3)2]BF4 with HCtCC(OH)MeR (R = Me, Ph) can also
give both carbyne complexes [OsH(tCCH2C(OH)MeR)(OAc)-
(P-i-Pr3)2]BF4 and η2-vinyl complexes [OsH(η2-CH2CC(OH)-
MeR)(OAc)(P-i-Pr3)2]BF4. Interestingly, [OsH2(OAc)(H2O)-
(P-i-Pr3)2]BF4 reacts with HCtCR (R=Ph, C(OH)(Ph)2) to
give η2-vinyl complexes [OsH(η2-CH2CR)(OAc)(P-i-Pr3)2]BF4
and with HCtCR0 (R0 = H, CMe3, SiMe3) to give carbyne
complexes [OsH(tCCH2R0)(OAc)(PiPr3)2]BF4. A compu-
tational study suggests that the difference has a thermo-
dynamic origin.34 In order to see if a similar trend can be
observed for our rhenium system, we have studied the reac-
tions of 1 with other alkynes under similar reaction conditions.
Treatment of ReH5(PMe2Ph)3 with 1-heptyne in benzene
in the presence of 2.2 equiv of hydrogen chloride gave a
brown solution along with some brown precipitate. The
brown precipitate was found to be mainly fac-ReCl3(PMe2Ph)3.
of 2 and 3 from the reaction of 1 with phenylacetylene. Proto-
nation of 1 with HCl may initially give the cationic hexahydride
A, which may lose a molecule of H2 to give the neutral hydride
complex B. Hydride B can react with a molecule of alkyne to
give the η2-alkyne complex C, which may undergo isomeriza-
tion to give the vinylidene complex D. Protonation of D with
ꢀ
(33) See for example: (a) Davidson, J. L.; Shiralian, M.; Manojlovic-
Muir, L.; Muir, K. W. J. Chem. Soc., Chem. Commun. 1979, 30.
ꢀ
(b) Davidson, J. L.; Vasapollo, G.; Manojlovic-Muir, L.; Muir, K. W.
J. Chem. Soc., Chem. Commun. 1982, 1025. (c) Carlton, L.; Davidson,
J. L.; Miller, J. C.; Muir, K. W. J. Chem. Soc., Chem. Commun. 1984, 11.
ꢀ
(d) Davidson, J. L.; Shiralian, M.; Manojlovic-Muir, L.; Muir, K. W. J. Chem.
Soc., Dalton Trans. 1984, 2167. (e) Carlton, L.; Davidson, J. L.; Ewing, P.;
ꢀ
Manojlovic-Muir, L.; Muir, K. W. J. Chem. Soc., Chem. Commun. 1985,
1474. (f) Carlton, L.; Davidson, J. L. J. Chem. Soc., Dalton Trans. 1987,
895. (g) Gamble, A. S.; Birdwhistell, K. R.; Templeton, J. L. J. Am. Chem.
Soc. 1990, 112, 1818. (h) Silva, C. J.; Giner, J. L.; Djerassi, C. J. Am. Chem.
Soc. 1992, 114, 295. (i) Feng, S. G.; Templeton, J. L. Organometallics 1992,
11, 2168. (j) Kiplinger, J. L.; King, M. A.; Arif, A. M.; Richmond, T. G.
Organometallics 1993, 12, 3382. (k) Mayr, A.; Asaro, M. F.; Glines, T. J.;
Van Engen, D.; Tripp, G. M. J. Am. Chem. Soc. 1993, 115, 8187. (l) Lee,
T. Y.; Mayr, A. J. Am. Chem. Soc. 1994, 116, 10300. (m) Kiplinger, J. L.;
King, M. A.; Fechtenkotter, A.; Arif, A. M.; Richmond, T. G. Organome-
tallics 1996, 15, 5292. (n) Kiplinger, J. L.; Richmond, T. G.; Arif, A. M.;
Ducker-Benfer, C.; Van Eldik, R. Organometallics 1996, 15, 1545.
(o) Giannini, L.; Guillemot, G.; Solari, E.; Floriani, C.; Re, N.; Chiesi-Villa,
A.; Rizzoli, C. J. Am. Chem. Soc. 1999, 121, 2797. (p) Legzdins, P.; Lumb,
S. A.; Rettig, S. J. Organometallics 1999, 18, 3128. (q) Frohnapfel, D. S.;
White, P. S.; Templeton, J. L. Organometallics 2000, 19, 1497. (r) Guillemot,
G.; Solari, E.; Floriani, C.; Re, N.; Rizzoli, C. Organometallics 2000, 19,
5218.
(34) (a) Buil, M. L.; Eisenstein, O.; Esteruelas, M. A.; Garcıa-Yebra,
´
ꢀ
~
C.; Gutierrez-Puebla, E.; Olivan, M.; Onate, E.; Ruiz, N.; Tajada, M. A.
Organometallics 1999, 18, 4949. (b) Barrio, P.; Esteruelas, M. A.; Onate, E.
Organometallics 2003, 22, 2472. (c) Buil, M. L.; Esteruelas, M. A.; García-
Yebra, C.; Gutierrez-Puebla, E.; Olivan, M. Organometallics 2000, 19, 2184.
ꢀ
(d) Esteruelas, M. A.; García-Yebra, C.; Olivan, M.; Onate, E. Organome-
ꢀ
tallics 2000, 19, 3260. (e) Esteruelas, M. A.; García-Yebra, C.; Olivan, M.;
~
Onate, E.; Tajada, M. A. Organometallics 2000, 19, 5098.
(35) Chen, H.; Harman, W. D. J. Am. Chem. Soc. 1996, 118, 5672.

2698 Organometallics, Vol. 29, No. 12, 2010
Chen et al.
Scheme 3
A solid was obtained from the solution by removing the solvents
followed by washing with hexane. The 31P{1H} NMR spectrum
of the solid shows that it contains two major products in a molar
ratio of 1:1.4, a small amount of unreacted ReH5(PMe2Ph)3,
and other unidentified species. One of the major products
exhibits a doublet 31P{1H} NMR signal at -17.7 ppm and a
triplet 31P{1H} NMR signal at -20.4 ppm with a coupling con-
stant of 12.2 Hz in CD2Cl2. The other product shows 31P{1H}
NMR signals at -26.1 (t) and -27.9 (d) ppm with a coupling
constant of 15.7 Hz. The compound with 31P{1H} NMR signals
at -17.7 and -20.4 ppm can be isolated as a pale red solid by
repeated recrystallization and was identified to be the carbyne
complex ReCl2(tC(CH2)5Me)(PMe2Ph)3 (4). Its structure can
be readily assigned on the basis of its NMR data. In particular,
the 31P{1H} NMR data are very similar to those of the ana-
logous carbyne complex 2. The 13C{1H} NMR spectrum shows
the carbyne signal at 273.8 (dt, J(PC) = 16.7, 12.6 Hz) ppm.
The NMR data suggest that the complex with 31P signals
at -26.1 and -27.9 ppm is the η2-vinyl complex ReCl2(η2-
CH2C(CH2)4CH3)(PMe2Ph)3 (5). Consistent with this for-
mulation, its 31P{1H} NMR data are very similar to those of
Figure 3. Molecular structure of ReCl2(tCCHdCPh2)(PMe2Ph)3
(8).
We have also studied the reactions of 1 with the alkynol
HCtCC(OH)Ph2 in the presence of HCl. Treatment of 1
with 1.2 equiv of HCtCC(OH)Ph2 in the presence of 2.2
equiv of HCl for ca. 24 h produced a brownish green solu-
tion. An in situ NMR study shows that a small amount of
ReH5(PMe2Ph)3 remained and the reaction produced the
carbyne complexes ReCl2(tCCHdCPh2)(PMe2Ph)3 (8) and
ReCl2(tCCH2C(OH)Ph2)(PMe2Ph)3 (9) and the η2-vinyl
complex ReCl2(η2-CH2CC(OH)Ph2)(PMe2Ph)3 (10), in a
molar ratio of 0.59:1:0.94 (Scheme 3). Pure samples of car-
byne complexes ReCl2(tCCHdCPh2)(PMe2Ph)3 (8) and
ReCl2(tCCH2C(OH)Ph2)(PMe2Ph)3 (9) can be obtained
by column chromatography. However, we have failed to obt-
ain pure samples of η2-vinyl complex 10 by either column
chromatography or recrystallization.
1
the analogous η2-vinyl complex 3. The H NMR spectrum
shows a 1H signal at 1.70 ppm assignable to Re(CH2). In the
13C{1H} NMR spectrum, 13C signals assignable to Re(η2-
CH2C(CH2)4CH3) were observed at 8.0 and 265.8 ppm. Our
attempts to obtain a pure sample of η2-vinyl complex 5 failed,
however. The complex decomposed on a silica gel column. It is
also very difficult to separate it from 4 by recrystallization due
to their similar solubilities.
The major product for the reaction of Me3SiCtCH with 1
in the presence of 2.2 equiv of HCl was found to be the car-
byne complex ReCl2(tCCH2SiMe3)(PMe2Ph)3 (6), which
can be isolated as a pale-green solid in 44% yield (Scheme 1).
Its structure can be readily assigned on the basis of its NMR
data. In particular, the 31P{1H} NMR data are very similar
to those of the analogous carbyne complexes 2 and 4. The
13C{1H} NMR spectrum shows the carbyne signal at 270.1
ppm and that of CH2 at 44.5 ppm.
The structures of complexes 8 (Figure 3) and 9 (Figure 4)
have also been confirmed by X-ray diffraction. Consistent with
the solid-state structures, the 13C{1H} NMR spectrum of 8
shows the Re(tCCH) signals at 259.1 (RetC) and 135.2 (CH)
ppm; the 13C{1H} NMR spectrum of 9 shows the Re(tCCH2)
signals at 268.6 (RetC) and 61.4 (CH2) ppm. Complex 8shows
31P{1H} signals at -19.7 (d) and -28.0 (t) ppm, while complex
9 shows 31P{1H} signals at -21.7 (d) and -19.8 (t) ppm.
The identity of the complex 10 can be inferred from its 31P
and 1H NMR data. The complex showed 31P{1H} signals at
-30.2 (d) and -27.3 (t) ppm with a coupling constant of 16.8
An in situ NMR study shows that the reaction involving
HCtCSiMe3 also produced the η2-vinyl complex ReCl2(η2-
CH2CSiMe3)(PMe2Ph)3 (7) as a minor product in the initial
stage of the reaction. Although we have not been able to get a
pure sample of the complex by either recrystallization or column
chromatography, the identity of the complex can be inferred
1
from its 31P{1H} and H NMR data. The complex showed
31P{1H} signals at -29.1 (t) and -29.5 (d) ppm with a coupling
constant of 16.5 Hz in C6D6. In the H NMR spectrum (in
1
1
1
Hz. In the H NMR spectrum (in C6D6), the H signal of
C6D6), the 1H signal of Re(η2-CH2C) was observed at 2.6 ppm.
Re(η2-CH2C) was observed at 2.86 ppm. In the 13C{1H}

Article
Organometallics, Vol. 29, No. 12, 2010 2699
vacuum. Careful addition of methanol (1 mL ꢀ 2) to the residue
gave a yellow precipitate, which was collected by filtration and
dried under vacuum to give Re(tCCH2Ph)Cl2(PMe2Ph)3 (2).
Yield: 0.20 g, 31%. Characterization data for 2 are as follows. 31P-
{1H} NMR (121.5 MHz, CDCl3): δ -16.5 (d, J(PP)=12.4 Hz),
1
-21.3 (t, J(PP) = 12.4 Hz). H NMR (300.13 MHz, CDCl3):
δ 1.33 (d, J(PH)=9.3 Hz, 6 H, PMe2Ph), 1.73 (t, J(PH)=3.9 Hz,
12 H, PMe2Ph), 2.40 (q, J(PH) = 3.7 Hz, 2 H, RetCCH2), 6.66
(dd, J(PH)=9.2 Hz, J(HH)=7.3 Hz, 2 H, Ph), 7.00 (t, J(HH)=
7.3 Hz, 2 H, Ph), 7.05-7.40 (m, 16 H, other aromatic protons).
13C{1H} NMR (75.5 MHz, CDCl3): δ 268.1 (dt, J(PC) = 14.8,
14.6 Hz, RetC), 142.7 (d, J(PC)=46.7 Hz, Ph), 141.0 (t, J(PC)=
19.7 Hz, Ph), 133.3 (s, Ph), 130.0 (t, J(PC)=4.4 Hz, Ph), 129.0 (d,
J(PC)=8.6 Hz, Ph), 128.7 (s, Ph), 128.5 (s, Ph), 128.2 (d, J(PC)=
1.7 Hz, Ph), 127.9 (t, J(PC)=4.0 Hz, Ph), 127.5 (d, J(PC)=8.9
Hz, Ph), 126.6 (s, Ph), 54.6, (s, RetCCH2Ph), 20.0 (d, J(PC) =
34.9 Hz, PMe2Ph), 17.7 (t, J(PC) = 17.5 Hz, PMe2Ph), 12.2
(t, J(PC) =15.7Hz, PMe2Ph). Anal. Calcd for C32H40Cl2P3Re: C,
49.61; H, 5.20. Found: C, 49.16; H, 5.25. Characterization data for
3 are as follows. 31P{1H} NMR (121.5 MHz, CDCl3): δ -25.3
1
(t, J(PP) = 16.9 Hz), -27.7 (d, J(PP) = 16.9 Hz). H NMR
Figure 4. Molecular structure of ReCl2(tCCH2C(OH)Ph2)-
(PMe2Ph)3 (9).
(300.13 MHz, CDCl3): δ 1.51 (d, J(PH)=8.9 Hz, 6 H, PMe2Ph),
1.56 (t, J(PH) = 4.1 Hz, 6 H, PMe2Ph), 1.75 (t, J(PH) =4.0 Hz,
6 H, PMe2Ph), 1.85 (d, J(PH) = 7.1 Hz, 2 H, Re(η2-CH2CPh),
6.43 (dd, J(PH) = 8.3 Hz, J(HH) =7.3 Hz, 2 H, Ph), 6.70-7.20
(m, 15 H, aromatic protons), 7.30 (t, J(HH) = 7.3 Hz, 1 H, Ph),
8.99 (d, J(HH) = 7.3 Hz, 2 H, Ph). 13C{1H} NMR (75.5 MHz,
CD2Cl2): δ 245.6 (dt, J(PC)=9.2 Hz, 11.9 Hz, Re(η2-CH2CPh)),
149.2 (s, Ph), 142.6(d, J(PC)=43.3Hz, Ph), 137.5(t, J(PC)=18.9
Hz, Ph), 131.6 (s, Ph), 130.2 (t, J(PC)=4.2 Hz, Ph), 130.0(s, Ph),
129.8 (d, J(PC) = 6.8 Hz, Ph), 128.5(d, J(PC) = 20.0 Hz, Ph),
128.3(d, J(PC) =2.2 Hz, Ph), 127.9 (t, J(PC)=3.9 Hz, Ph), 127.7
(d, J(PC) = 8.7 Hz, Ph), 127.3 (s, Ph),19.8 (d, J(PC) = 36.0 Hz,
PMe2Ph), 15.0 (t, J(PC) = 17.2 Hz, PMe2Ph), 12.2 (t, J(PC) =
15.1 Hz, PMe2Ph), 11.7 (d, J(PC) = 16.4 Hz, Re(η2-CH2CPh)).
Anal. Calcd. for C32H40Cl2P3Re: C, 49.61; H, 5.20. Found: C,
49.77; H, 4.99.
NMR spectrum, the Re(η2-CH2C) signals were observed at
15.5 and 258.1 ppm.
In summary, reactions of the rhenium polyhydride complex
ReH5(PMe2Ph)3 with HCtCR(R=Ph, SiMe3, (CH2)4Me) in
the presence of 2.2 equiv of HCl produce a mixture of the
carbyne complexes Re(tCCH2R)Cl2(PMe2Ph)3 and the η2-
vinyl complexes Re(η2-CH2CR)Cl2(PMe2Ph)3. When HCt
CC(OH)Ph2 was used, the reaction gave the carbyne com-
plexes Re(tCCHdCPh2)Cl2(PMe2Ph)3 and Re(tCCH2C-
(OH)Ph2)Cl2(PMe2Ph)3 along with the η2-vinyl complex Re-
(η2-CH2CC(OH)Ph2)Cl2(PMe2Ph)3. The reactions of ReH5-
(PMe2Ph)3 with various terminal alkynes studied here in
general produced both carbyne and η2-vinyl complexes. Thus,
the trend34 observed for the reactions of the osmium hydride
[OsH2(OAc)(H2O)(PiPr3)2]BF4 was not observed in our study.
Re(tC(CH2)5CH3)Cl2(PMe2Ph)3 (4). To a solution of ReH5-
(PMe2Ph)3 (0.50 g, 0.83 mmol) in benzene (10 mL) was added 1-
heptyne (0.90 mL, 6.7 mmol) and then hydrogen chloride (1.0 M
in diethyl ether, 1.80 mL, 1.80 mmol). The reaction mixture was
stirred at room temperature for 5 h to give a brown solution with
some green oily precipitate which contains mainly fac-ReCl3-
(PMe2Ph)3. The reaction mixture was filtered through a filter
paper to remove the oily solid. The solvent of the brown filtrate
was removed under vacuum, and the residue was dissolved in
methanol (1.5 mL). Addition of hexane (10 mL) to the above
solution gave a dark brown oil (presumably the decomposition
products of 5) in the lower layer and a light brown solution in the
upper layer. The upper layer (hexane solution) was carefully
separated through a syringe, the solvent was removed under vac-
uum, and the residue was washed with diethyl ether (1 mL ꢀ 2)
and methanol (0.5 mL ꢀ 2) to give a pale red precipitate, which
was collected by filtration and dried under vacuum. Yield: 0.165 g,
21.7%. 31P{1H} NMR (121.5 MHz, CDCl3): δ -16.6 (d, J(PP)=
Experimental Section
All manipulations were carried out under a nitrogen atmo-
sphere using standard Schlenk techniques unless otherwise
stated. Solvents were distilled under nitrogen from sodium ben-
zophenone (hexane, ether, THF), sodium (benzene), or calcium
hydride (CH2Cl2). The starting material ReH5(PMe2Ph)3 was
prepared by following the procedure described in the
literature.18 All other reagents were used as purchased from
Aldrich Chemical Co. or Strem Chemical Co.
Microanalyses were performed by M-H-W Laboratories
1
(Phoenix, AZ). H, 13C{1H}, and 31P{1H} NMR spectra were
collected on a Varian Mercury spectrometer (300 MHz) or a
1
Bruker ARX-300 spectrometer (300 MHz). H and 13C NMR
shifts are relative to TMS, and 31P NMR chemical shifts are
relative to 85% H3PO4.
12.2 Hz), -18.4 (t, J(PP) = 12.2 Hz). H NMR (300.13 MHz,
1
CDCl3): δ 0.78 (t, J(PH)=7.0 Hz, 3 H, (CH2)5CH3), 1.0-1.3 (m,
10 H, (CH2)5CH3), 1.31 (d, J(PH)=9.1 Hz, 6 H, PMe2Ph), 1.68 (t,
J(PH) = 3.9 Hz, 6 H, PMe2Ph), 1.90 (t, J(PH) =4.0 Hz, 6 H,
PMe2Ph), 6.89 (dd, J(PH) = 9.2 Hz, J(HH) = 7.3 Hz, 2 H, Ph),
7.02 (t, J(HH) = 7.3 Hz, 2 H, Ph), 7.05-7.50 (m, 11 H, Ph).
13C{1H} NMR (75.5 MHz, CDCl3): δ 273.8 (dt, J(PC)=16.7 Hz,
12.6 Hz, RetC), 143.6 (d, J(PC)=46.3 Hz, Ph), 141.0 (t, J(PC)=
19.7 Hz, Ph), 129.9 (t, J(PC) = 4.5 Hz, Ph), 129.1 (d, J(PC) =
8.7 Hz, Ph), 128.6 (s, Ph), 128.3 (d, J(PC)=1.9 Hz, Ph), 127.8 (t,
J(PC) = 4.1 Hz, Ph), 127.7 (d, J(PC) = 8.9 Hz, Ph), 49.9, 31.4,
29.3, 24.9, 22.6 (all s, (CH2)5CH3), 20.6 (d, J(PC) = 34.4 Hz,
PMe2Ph), 17.7 (t, J(PC) = 17.2 Hz, PMe2Ph), 14.2 (s, (CH2)5-
CH3), 12.7 (t, J(PC) = 15.8 Hz, PMe2Ph). Anal. Calcd for
C31H46Cl2P3Re: C, 48.44; H, 6.03. Found: C, 48.66; H, 6.23.
Re(tCCH2Ph)Cl2(PMe2Ph)3 (2) and Re(η2-CH2CPh)Cl2-
(PMe2Ph)3 (3). To a solution of ReH5(PMe2Ph)3 (0.50 g,
0.83 mmol) in benzene (10 mL) was added phenylacetylene
(0.500 mL, 4.55 mmol) and then hydrogen chloride (1.0 M in
diethyl ether, 1.80 mL, 1.80 mmol). The reaction mixture was
stirred at room temperature for 10 h to give a green solution.
The solvent was removed under vacuum, and the residue was
redissolvedinCH2Cl2 (2mL). Additionofdiethyl ether(10mL) to
the residue gave a green precipitate and a brown solution, which
were separated by filtration. The green precipitate was extracted
with benzene (5 mL), and the extract was dried under vacuum
to give Re(η2-CH2CPh)Cl2(PMe2Ph)3 (3) as a green solid. Yield:
0.17 g (27%). The solvent of the brown filtrate was removed under

2700 Organometallics, Vol. 29, No. 12, 2010
Chen et al.
Observation of 5. To a solution of ReH5(PMe2Ph)3 (0.859 g,
1.42 mmol) in benzene (25 mL) was added 1-heptyne (0.178 g,
1.86 mmol) and then hydrogen chloride (1.0 M in diethyl ether,
3.1 mL, 3.10 mmol). The reaction mixture was stirred at room
temperature for 20 h to give a brown solution with some brown
oily precipitate. The reaction mixture was filtered through a
filter paper to remove the oily solid (mainly fac-ReCl3(PMe2Ph)3).
The solvent of the brown filtrate was removed under vacuum, and
the residue was washed with hexane (10 mL ꢀ 3) to give a brown
oily solid, which was dried under vacuum overnight. NMR
spectra of the resulting solid indicate that it contains 4 and 5
in a molar ratio of 1:1.4, a small amount of unreacted ReH5-
(PMe2Ph)3, and other unidentified species. Attempts to obtain a
pure sample of compound 5 by either recrystallization or chro-
matography failed. Characterization data for 5 are as follows.
31P{1H} NMR (161.98 MHz, CD2Cl2): δ -26.2 (t, J(PP) =
15.7 Hz), -27.7 (d, J(PP) = 15.7 Hz). 1H NMR (400.13 MHz,
CD2Cl2): δ 1.70 (br, 2 H, Re(η2-CH2C)), 2.33 (m, 2 H, Re(η2-
CH2CCH2), 1.39 (d, J(PH) = 9.2 Hz, 6 H, PMe2Ph), 1.60 (t,
J(PH) = 3.9 Hz, 6 H, PMe2Ph), 1.62 (t, J(PH) = 4.0 Hz, 6 H,
PMe2Ph). 13C{1H} NMR (100.63 MHz, CD2Cl2): δ 265.8 (dt,
J(PC)=9.2 Hz, 12.0 Hz, Re(η2-CH2C)), 8.0 (d, J(PC)=9.7 Hz,
Re(η2-CH2C)), 48.0, 31.9, 28.7, 22.0 (all s, (CH2)4), 18.5 (d,
J(PC)=35.3 Hz, PMe2Ph), 13.9 (t, J(PC)=17.0 Hz, PMe2Ph),
13.8 (s, (CH2)4CH3), 12.5 (t, J(PC) =15.0 Hz, PMe2Ph).
room temperature for 8 h, another portion of hydrogen chloride
(1.0 M in diethyl ether, 2.2 mL, 2.2 mmol) was slowly added again
and the reaction mixture was stirred for a further 16 h to give a
brownish green solution with a small amount of brown oily pre-
cipitate which contains mainly fac-ReCl3(PMe2Ph)3. The reac-
tion mixture was filtered through a filter paper to remove the oily
solid. The brown filtrate was concentrated to ca. 5 mL and was
loaded onto a silica gel column. The column was flashed with
hexane/acetone (25:1) to remove yellow impurities and then elu-
ted with hexane/acetone (15:1) to give a green solution. The
solvent of the green solution was removed under vacuum to give
a green solid (8), which was washed with 2 mLꢀ3 hexane/acetone
(2:1) and dried under vacuum. Yield: 0.495 g, 28.9%. Character-
ization data for 8 are as follows. 31P{1H} NMR (121.5 MHz,
CDCl3): δ -18.1 (d, J(PP)=13.0 Hz), -26.0 (t, J(PP)=13.0 Hz).
1H NMR (300.13 MHz, CDCl3): δ 1.44 (d, J(PH)=9.6 Hz, 6 H,
PMe2Ph), 1.54 (t, J(PH)=4.2 Hz, 6 H, PMe2Ph), 1.84 (t, J(PH)=
3.9 Hz, 6 H, PMe2Ph), 4.46 (br, 1 H, HCdC), 6.12 (dd, J(PH)=
9.1 Hz, J(HH)=7.1 Hz, 2 H, Ph), 6.80-7.45 (m, 21 H, Ph), 7.64
(d, J(HH) = 7.1 Hz, 2 H, Ph). 13C{1H} NMR (75.5 MHz,
CDCl3): δ 259.1 (dt, J(PC) = 14.9 Hz, 14.7 Hz, RetC), 148.6
(q, J(PC)=2.9 Hz, dCPh2), 141.5 (t, J(PC) =19.6 Hz, Ph), 141.1
(s, Ph), 139.9 (d, J(PC) =47.1 Hz, Ph), 138.1 (s, Ph), 135.2 (q,
J(PC)=3.0 Hz, CHdCPh2), 129.9 (s, Ph), 129.7 (t, J(PC) =8.8
Hz, Ph), 128.7 (d, J(PC) = 8.4 Hz, Ph), 127.2-128.4 (m, Ph),
127.1 (s, Ph), 126.8 (d, J(PC) = 8.8 Hz, Ph), 19.4 (d, J(PC) =
35.1 Hz, PMe2Ph), 17.8 (t, J(PC) = 17.6 Hz, PMe2Ph), 11.4 (t,
J(PC) =15.1 Hz, PMe2Ph). Anal. Calcd for C39H44Cl2P3Re: C,
54.29; H, 5.14. Found: C, 54.45; H, 5.26.
The column was further eluted with hexane/acetone (10:1) to
give a brown solution and then the solvent was removed under
vacuum. The residue was extracted with 5 mLꢀ3 hexane/acetone
(2:1), from which the compound (9) could be obtained as a pale
brown solid after the solvent was removed completely under
vacuum. Yield: 0.318 g, 17.9%. Characterization data for 9 are
as follows. 31P{1H} NMR (121.5 MHz, CD2Cl2): δ -18.6 (t,
J(PP)=12.4 Hz), -20.8 (d, J(PP)=12.5 Hz). 1H NMR (300.13
MHz, CD2Cl2): δ 1.42 (d, J(PH)=9.2 Hz, 6 H, PMe2Ph), 1.51 (t,
J(PH) = 3.9 Hz, 6 H, PMe2Ph), 1.71 (t, J(PH) = 4.2 Hz, 6 H,
PMe2Ph), 2.60 (q, J(PH)=3.4 Hz, 2 H, RetCCH2), 5.08 (s, 1 H,
OH), 6.97 (dd, J(PH) = 10.0 Hz, J(HH) = 7.3 Hz, 2 H, Ph),
7.10-7.60 (m, 23 H, Ph). 13C{1H} NMR (75.5 MHz, CD2Cl2):
δ 268.6 (dt, J(PC) = 18.1 Hz, 11.8 Hz, RetC), 148.1 (s, Ph),
143.7 (d, J(PC)=48.1 Hz, Ph), 139.7 (t, J(PC)=20.8 Hz, Ph),
131.1 (s, Ph), 130.8 (t, J(PC) = 4.3 Hz, Ph), 129.4 (d, J(PC) =
8.7 Hz, Ph), 129.0 (s, Ph), 128.9 (br, Ph), 128.6 (s, Ph), 128.3 (d,
J(PC)=9.1 Hz, Ph), 128.1 (t, J(PC)=4.1 Hz, Ph), 127.2 (s, Ph),
125.6 (s, Ph), 77.2 (s, CH2COH), 61.4 (s, CH2COH), 20.6
(d, J(PC) = 34.7 Hz, PMe2Ph), 15.9 (t, J(PC) = 16.3 Hz,
PMe2Ph), 14.0 (t, J(PC) = 16.7 Hz, PMe2Ph). Anal. Calcd for
C39H46Cl2OP3Re: C, 53.18; H, 5.26. Found: C, 53.43; H, 5.47.
Observation of 10. To a solution of ReH5(PMe2Ph)3 (27 mg,
0.044 mmol) and 1,1-diphenyl-2-propyn-1-ol (10.1 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
allowed to stand at room temperature for 20 h, to give a brownish
green solution with a small amount of brown precipitate. NMR
spectra of the reaction mixture were then collected, which indicate
that it contains 8-10 in a molar ratio of 0.59:1:0.94, and a small
amount of ReH5(PMe2Ph)3. Characterization data for 10 are as
follows. 31P{1H} NMR (161.98 MHz, C6D6): δ -30.2 (t, J(PP) =
16.8 Hz), -27.3 (d, J(PP) = 16.8 Hz). 1H NMR (400.13 MHz,
C6D6): δ 2.86 (dt, J(PH)=9.0 Hz, 2.5 Hz, 2 H, Re(η2-CH2C)).
13C{1H} NMR (75.5 MHz, C6D6): δ 258.1 (dt, J(PC)=9.2 Hz,
11.0 Hz, Re(η2-CH2C)), 15.5 (d, J(PC) = 16.7 Hz, Re(η2-
CH2C)).
Re(tCCH2SiMe3)Cl2(PMe2Ph)3 (6). To a solution of ReH5-
(PMe2Ph)3 (0.50 g, 0.83 mmol) in benzene (10 mL) was added
(trimethylsilyl)acetylene (0.95 mL, 6.87 mmol) and then hydro-
gen chloride (1.80 mL, 1.80 mmol, 1.0 M in diethyl ether). The
reaction mixture was stirred at room temperature for 4 h to give
a green solution. The solvent was removed under vacuum, and
the residue was washed with methanol (0.5 mLꢀ2) and diethyl
ether (2 mL ꢀ 2) to give a pale green precipitate, which was
collected by filtration and dried under vacuum. Yield: 0.279 g,
43.6%. 31P{1H} NMR (121.5 MHz, CDCl3): δ -17.7 (d, J(PP)=
1
12.2 Hz), -20.8 (t, J(PP) = 12.0 Hz). H NMR (300.13 MHz,
C6D6): δ 0.07 (s, 9 H, Si(CH3)3), 0.88 (q, J(PH) =3.8 Hz, 2 H,
tCCH2), 1.31 (d, J(PH)=9.0Hz, 6 H, PMe2Ph), 1.70 (t, J(PH)=
4.0 Hz, 6 H, PMe2Ph), 1.88 (t, J(PH)=4.1 Hz, 6 H, PMe2Ph), 6.87
(dd, J(PH)=9.0 Hz, J(HH)=7.2 Hz, 2 H, Ph), 6.99 (t, J(HH)=
7.2 Hz, 2 H, Ph), 7.00-7.50 (m, 11 H, Ph). 13C{1H} NMR
(75.5 MHz, CD2Cl2): δ 270.1 (dt, J(PC) = 16.4 Hz, 12.3 Hz,
RetC), 143.7 (d, J(PC) = 45.6 Hz, Ph), 140.7 (t, J(PC) = 19.7
Hz, Ph), 130.5 (t, J(PC)=4.4 Hz, Ph), 129.5 (d, J(PC)=8.5 Hz,
Ph), 128.8 (s, Ph), 128.4 (d, J(PC)=1.9 Hz, Ph), 128.0 (t, J(PC)
=4.1 Hz, Ph), 127.8 (d, J(PC)=8.8 Hz, Ph), 44.5(s, CH2SiMe3),
20.0 (d, J(PC) = 34.4 Hz, PMe2Ph), 17.8 (t, J(PC) = 16.8 Hz,
PMe2Ph), 13.5 (t, J(PC)=16.0 Hz, PMe2Ph). FAB-MS (NBA,
m/z): 736.1 ([M - Cl]þ), 632.4 ([M - PMe2Ph]þ), 597.4 ([M -
Cl, PMe2Ph]þ). Anal. Calcd for C29H44Cl2P3SiRe: C, 45.19; H,
5.75. Found: C, 45.22; H, 5.60.
Observation of 7. To a solution of ReH5(PMe2Ph)3 (11.2 mg,
0.018 mmol) in benzene-d6 (0.4 mL) in an NMR tube was added
(trimethylsilyl)acetylene (3 μL, 0.021 mmol) and then hydrogen
chloride (0.050 mL, 0.05 mmol, 1.0 M in diethyl ether). The re-
action mixture was stood at room temperature for 4 h to give a
green solution with some brown precipitate. NMR spectra of the
reaction mixture were then collected; these indicated that it
contains 6 and 7 in a molar ratio of 1:0.32 and unreacted ReH5-
(PMe2Ph)3. Characterization data for 7 are as follows. 31P{1H}
NMR (161.98 MHz, C6D6): δ -29.1 (t, J(PP)=16.6 Hz), -29.5
(d, J(PP)=16.6 Hz). 1H NMR (400.13 MHz, C6D6): δ 2.60 (dt,
J(PH)=6.6 Hz, 3.0 Hz, 2 H, Re(η2-CH2C)), 1.42 (d, J(PH)=8.4
Hz, 6 H, PMe2Ph), 1.63 (t, J(PH)=4.0 Hz, 6 H, PMe2Ph), 1.87
(t, J(PH)= 4.1 Hz, 6 H, PMe2Ph).
Re(tCCHdCPh2)Cl2(PMe2Ph)3 (8) and Re(tCCH2C(OH)-
Ph2)Cl2(PMe2Ph)3 (9). Toa solution ofReH5(PMe2Ph)3 (1.200 g,
2.00 mmol) and 1,1-diphenyl-2-propyn-1-ol (0.500 g, 2.40 mmol)
in benzene (35 mL) was slowly added hydrogen chloride (1.0 M in
diethyl ether, 2.2 mL, 2.2 mmol). After the mixture was stirred at
Crystal Structure Analyses. Crystals of 2 and 8 were grown
from C6D6/hexane and CDCl3/hexane, respectively. Crystals of
3 and 9 were grown from CH2Cl2/hexane. The diffraction
intensity data of 2, 3, and 8 were collected with a Bruker Smart

Article
Organometallics, Vol. 29, No. 12, 2010 2701
APEX CCD diffractometer with graphite-monochromated Mo
KR radiation (λ = 0.71073 A). 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, res-
pectively. The diffraction intensity data of 9 were collected with
an Oxford Diffraction Gemini S Ultra with monochromated Cu
KR radiation (λ=1.541 78 A) at 173 K. Lattice determination,
data collection, and reduction were carried out using CrysAlis-
Pro 171.33.46. Absorption correction was performed using
SADABS built in to the CrysAlisPro program suite. Structure
solution and refinement were performed using the SHELXTL
v.6.10 software package. 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 anisotropically with a riding model for the hydrogen
atoms. Further details on crystal data, data collection, and refine-
ments are summarized in Table 1.
Acknowledgment. This work was supported by the
Hong Kong Research Grant Council (Project No. HKUST
601007).
Supporting Information Available: CIF files giving X-ray
crystallographic data for 2, 3, 8, and 9 and figures giving NMR
spectra. This material is available free of charge via the Internet at
http://pubs.acs.org.