Versatile Reaction Patterns of Phosphanylhydrosilylalkyne with B(C6F5)3: A Remarkable Group Substitution Effect

Article abstract of DOI:10.1002/ejic.202000506

Phosphanylhydrosilylalkynes R₂HSiCCPAr₂ (R,Ar: Me,4-tBuC₆H₄ 1, Me,Mes 2, Mes,Ph 3; Mes = 2,4,6-Me₃C₆H₂) were prepared and the reactions with B(C₆F₅)₃

Full text of DOI:10.1002/ejic.202000506

European Journal of Inorganic Chemistry
Accepted Article
Title: Versatile Reaction Patterns of Phosphanylhydrosilylalkyne with
B(C6F5)3: Remarkable Group Substitution Effect
Authors: Yanting Huang, Wenjun Jiang, Xin Xi, Yan Li, Xiaoping Wang,
Ming-Chung Yang, Zheng-Feng Zhang, Ming-Der Su, and
Hongping Zhu
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To be cited as: Eur. J. Inorg. Chem. 10.1002/ejic.202000506
Link to VoR: https://doi.org/10.1002/ejic.202000506
01/2020

10.1002/ejic.202000506
European Journal of Inorganic Chemistry
FULL PAPER
Versatile Reaction Patterns of Phosphanylhydrosilylalkyne with
B(C6F5)3: Remarkable Group Substitution Effect
Yanting Huang,[a] Wenjun Jiang,[a] Xin Xi,[a] Yan Li,*[b] Xiaoping Wang,[a] Ming-Chung Yang,[c] Zheng-
Feng Zhang,[c] Ming-Der Su,*[c,d] and Hongping Zhu*[a]
[a]
[b]
Y. Huang, W. Jiang, X. Xi, X. Wang, Prof. H. Zhu
State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.
E-mail: hpzhu@xmu.edu.cn. https://chem.xmu.edu.cn/info/1186/1219.html.
Prof. Y. Li
Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou, 311121, China. E-
mail: yli@hznu.edu.cn. https://yjg.hznu.edu.cn/c/2019-05-29/2175518.shtml.
M.-C. Yang, Z.-F. Zhang, Prof. M.-D. Su
Department of Applied Chemistry, National Chiayi University, Chiayi, 60004, Taiwan
Prof. M.-D. Su
[c]
[d]
Department of Medicinal and Applied Chemistry, Kaohsiung Medical University, Kaohsiung, 80708, Taiwan. E-mail: midesu@mail.ncyu.edu.tw.
https://www.ncyu.edu.tw/chem_eng/content.aspx?site_content_sn=7686.
Supplementary Information (ESI) available: Table for crystal data and refinements, kinetic study, DFT calculation details, collected NMR spectra. CCDC:
CCDC 2004665 (2), 1903424 (4), 1903425 (5), 1903427 (7), 1903429 (8), 1903430 (9), 1903431 (10), and 1903433 (11).
Abstract: Phosphanylhydrosilylalkynes R2HSiCCPAr2 (R,Ar:
Me,4-tBuC6H4 1, Me,Mes 2, Mes,Ph 3; Mes = 2,4,6-Me3C6H2)
were prepared and the reactions with B(C6F5)3 were studied.
upon catalysis by the transition metal (M), where the SiH
group was able to convert into the MH and/or M-silyl that is
(or are) highly active facilitating reactions toward alkene,[3]
alkyne,[4] and ketone and aldehyde,[5] although the related
mechanisms were proposed to be diverse. In recent years,
the borane-promoted hydrosilylation of unsaturated
organics has attracted particular attention because of
advantage either as a mild method or without use of the
transition metal. Notably, Piers and co-workers have cleanly
Reaction of
1
and B(C6F5)3 produced E-alkene {(E)-
and
(C6F5)3BCHC[P(4-tBuC6H4)2]SiMe2}2 (4) and that of
2
B(C6F5)3 yielded Z-alkene (Z)-(C6F5)2BCHC(PMes2)SiMe2(C6F5)
(5). The former is proposed to go through a key [Me2HSi]+ for
function while the latter via the phosphacyclopropene
intermediate, both of which are a result by self-hydrosilylation.
Reaction of 3 and B(C6F5)3 generated at room temperature a
P→B coordination compound Mes2HSiCCP(Ph2)B(C6F5)3 (6)
and at 100 °C the 1,1-carboboration E-alkene (E)-
Mes2HSi(Ph2P)CC(C6F5)B(C6F5)2 (7). Kinetic study and DFT
calculations were accomplished for reaction of 2 and B(C6F5)3 to
5. The mechanisms of these reactions have been discussed.
The reactions of the P/Si+ LPs Me2Si(Ph2P)CCHB(C6F5)3}2 (3a)
and 4 were also investigated. Compound 4 disassociated H2O
into {(E)-(C6F5)3BCHC[PH-4-tBuC6H4)2]Si(Me2)}2(μ-O) (8) and
demonstrated
a Si−H···B(C6F5)3 activation mode that
conducts well hydrosilylation of the C=O or C=N bond
molecules in catalysis, by means of which an interaction of
the O or N donor at the Si nucleus allows the bond
rearrangement into the [HB(C6F5)3]‾ for further Hˉ transfer to
the multiple bond C atom finalizing the catalytic cycle.[6]
Then Oestreich and co-workers showed a combination of
cyclohexa-2,5-dien-1-ylsilanes as the surrogate, where
B(C6F5)3 was able to form [HB(C6F5)3]‾ and [R3Si(C6H6)]+ for
addition into the C≡C bond of PhCCPh.[7] Ingleson and
Curless reported on the B(C6F5)3-catalyzed hydrosilylation
of 4-RC6H4CCR' by Ph2SiH2 through forming the Ph2HSi‒
(μ-H)‒B(C6F5)3 intermediate in work.[8] These results
together with other related studies[9] showed that activation
of the Si−H bond for function appears more favourable than
that of the C=O, C=N, or probably C≡C bond of
substrates.[10]
(E)-(C6F5)3BCHC[PH(4-tBu-C6H4)2]Si(Me2)O(HNC5H5)
Compound 3a reacted with tBuNCO by [3+2] dipolar
cycloaddition to give C2OPSi-heterocycle
[(C6F5)3BHC]CSi(Me2)P(Ph2)OC(NtBu) (10). Furthermore,
(9).
a
4
reacted with tBuNCO and then H2O to afford (E)-
(F5C6)3BHCC[P(4-tBuC6H4)2C(O)NHtBu][Si(Me2)OH(NC5H5)]
(11) through a C2OPSi-heterocycle intermediate followed by the
H2O-disassociation under the C2OPSi-ring opening.
Aluminium hydrides (R'2HAl, R'2 is dianionic group(s)) are
commonly known to carry well the hydroalumination of
multiple bond organics without promotion because of the
strong Lewis acidity of the Al center.[11] To be compared,
the silylium ion of the type of [R2HSi]+ (R2 is dianionic
group(s)) is isoelectronic and isolobal to the R'2HAl in
essence. Such species are reported rarely and only several
compounds
[Ph2HSi]+[(C6F5)2HBCH2CH2PMes2]ˉ,[12]
[C6H4O2H3O2C6H4]ˉ,[13] and [tBu3-nHnSi]+[CHB11H5Br6]ˉ (n = 1
and 2)[14] were found and well characterized. An open
question is then arising whether such [R2HSi]+ is capable of
the hydrosilylation. Up to now no such reaction was
Introduction
Hydrosilylation has now become
a
convenient and
important way for production of functionalized silanes.[1]
Progress of such reaction, however, meets often with
difficulty due to relatively inert reactivity of the SiH
functionality contained in hydrosilanes as the reagent
species.[1] Promotion of the SiH reactivity for function is thus
of great research effort and the number of routes has been
reported. The hydrosilylation of 1-octene into n-
octyltrichlorosilane was early reported, which was thought
to be promoted by the peroxide radical when trichlorosilane
was used.[2] Efficiency of the hydrosilylation was later found
[PhH2Si]+[(C6F5)2HB-CH2CH2PMes2]ˉ,[12]
[(C5Me5)2HSi]+-
documented.
We
have
recently
prepared
the
phosphanylhydrosilylalkyne, a functionalized alkyne of the
1
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10.1002/ejic.202000506
European Journal of Inorganic Chemistry
FULL PAPER
new type containing the PAr2 and SiHR2 substituents.[15]
However, no reaction was direct to the adjacent SiH group
and C≡C bond even upon heat treatment. Nonetheless, it
was found that such alkyne readily reacted with B(C6F5)3 to
form two types of the alkenes as the respective P/Si+ and
and PAr2 in 1‒3 together with those in 1a and 2a for comparison.
Compound 1 holds the SiHMe2 and P(4-tBuC6H4)2 substituents
1
and the H, 29Si and 31P NMR spectra record the resonances at
δSi ‒37.6, δH 4.24, and δP ‒35.6 ppm respectively, close to those
found in 1a and 2a. Compound 2 contains the SiHMe2 and
P/B Lewis pairs (LPs) both as a result by self-hydrosilylation. PMes2, and then the silicon (δSi ‒38.1 ppm) and proton (δH 4.12
Combined reaction kinetics and DFT calculations disclosed
the B(C6F5)3-promoted formation of the [R2HSi]+ in situ for
function.[15] This indicates, to our knowledge, a new way to
ppm) resonances are comparable, but the phosphorus
resonance (δP ‒54.7 ppm) appears at a higher field. In
comparison, compound 3 has the SiHMes2 and PPh2 and
improve the SiH reactivity for work. Of particular importance, exhibits the phosphorus resonance (δP ‒31.5 ppm) near to those
this reaction results in unique way to produce the P/Si+ and
P/B LPs, of which the former P/Si+ LP is rare and the way to
it is significantly distinguished from the routes by reacting
the as-made FLP with terminal alkyne,[16] the silane with
R3P/[Ph3C]+[B(C6F5)4]ˉ,[17] or Me3SiOTf with p-block Lewis
bases.[18] We herein report that changes of either the
hydrosilyl or phosphanyl groups, as expansion of such
functionalized alkyne, have a great influence on the
reaction pattern of the phosphanylhydrosilylalkynes newly
prepared when treated with B(C6F5)3. The reactions of the
derived P/Si+ LPs with water and/or isocyanate were also
investigated.
in 1a‒2a and 1, but the silicon (δSi ‒61.1 ppm) and proton (δH
5.62 ppm) resonances markedly shifted. Clearly, ligation of the
Mes group gives rise to a particular effect on the electronic
environment and then the NMR resonance around either the P
or Si nucleus when compared with that of the other groups.
Nonetheless, the alkynyl carbon resonances (δPC≡ 105.2‒107.2
and δSiC≡ 112.7‒113.5 ppm) in 1a‒2a and 1–3 are close,
irrespective of the change of the SiHR2 and PAr2 substituents.
The IR spectrometry exhibits the Si‒H (at ν 2141 cm-1 in 1, 2126
cm-1 in 2, and 2148 cm-1 in 3) and C≡C (at ν 2104 cm-1 in 1,
2086 cm-1 in 2, and 2091 cm-1 in 3) bond vibrations in character
respectively, which are comparable to those found in 1a and
2a.[15] Compound
2
is further characterized by X-ray
crystallography, which confirms composition and structure in line
with those analyzed by the aforesaid NMR and IR spectroscopy.
Of notice is exhibition of a pyramidal geometry at the P atom in 2,
as indicates existence of a lone electron pair around the P
center (Figure 1).
Results and Discussion
Starting
from
Me3SiCCH,
phosphanylhydrosilylalkyne
R2HSiCCPAr2 was prepared through a C≡C-centered, three-
folded substituent transformation (Scheme 1). An nBuLi
deprotonation followed by LiCl-elimination with Ar2PCl led
smoothly to Me3SiCCPAr2 that underwent a Me3Si/H exchange
in the presence of MeOH and K2CO3 to give HCCPAr2.
Compound HCCPAr2 reacted again by the nBuLi deprotonation
and then the LiCl-elimination using R2HSiCl to result in the target
compound. This way has been demonstrated to be
straightforward and effective for synthesis of compounds
Me2HSiCCPPh2 (1a) and Me2HSiCCP(4-MeC6H4)2 (2a).[15] By
changing the PAr2 group, compounds Me2HSiCCP(4-tBuC6H4)2
(1, an off-white solid, 85% yield) and Me2HSiCCPMes2 (Mes =
2,4,6-Me3C6H2, 2, an orange solid, 71% yield) were synthesized.
While alternating the R2HSi group, compound Mes2HSiCCPPh2
(3, a slight-grey solid, 75% yield) was produced.
Table 1. Summarized NMR data for groups of 1a−1b and 1–3.
1H NMR
SiH
13C NMR
29Si
NMR
31P
NMR
Comp.
SiC≡
≡CP
1a
2a
1
4.45
113.5
112.7
112.7
112.8
113.2
105.2
−37.4 −32.5
−37.5 −34.4
−37.6 −35.6
−38.1 −54.7
−61.1 −31.5
4.26
4.24
4.12
5.62
106.0
106.0
106.8
107.2
2
3
1a Me2HSiCCPPh2 and 2a Me2HSiCCP(4-MeC6H4)2.
Scheme 1. The C≡C-centered, three-folded substituent reaction to form
phosphanylhydrosilylalkynes 1‒3.
Figure 1. X-ray crystal structure of 2 with thermal ellipsoids at 50% probability
level. H atoms except for those of SiH are omitted for clarity. Selected bond
lengths (Å) and angles (°): C(1)–C(2) 1.198(4), C(1)–P(1) 1.771(3), C(2)–Si(1)
1.886(5) (av), Si(1)–H(1) 1.46(5) (av); P(1)–C(1)–C(2) 167.2(3), C(1)–C(2)–
Si(1) 164.0(3), C(1)–P(1)–C(5) 109.47(11), C(1)–P(1)–C(14) 98.75(10), C(5)–
P(1)–C(14) 104.21(10).
Compounds 1‒3 are characterized by NMR and IR
spectroscopy as well as by elemental analysis. Table 1
summarizes characteristic NMR data for groups of SiHR2, C≡C
2
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10.1002/ejic.202000506
European Journal of Inorganic Chemistry
FULL PAPER
Scheme 3. Postulated reaction mechanism for 1 and B(C6F5)3 to 4.
Reaction of 1 with equivalent B(C6F5)3 was monitored by the
1H and 31P NMR spectra in CDCl3 from –70 to 25 °C, which
revealed a process similar to that of 1a and B(C6F5)3 to generate
[(E)-(C6F5)3BCHC(PPh2)SiMe2]2
(C6F5)2BCHC(PPh2)SiMe2(C6F5) (5a) or of 2a and B(C6F5)3 to
{(E)-(C6F5)3BCHC[P(4-MeC6H4)2]SiMe2}2 (4a) and (Z)-
(3a)
and
(Z)-
(C6F5)2BCHC[P(4-Me-C6H4)2]SiMe2(C6F5) (6a).[15] This suggests
a probable common pattern conducted for these reactions,[15]
essentially due to close electronic property of the
phosphanylhydrosilylalkyne with respect to the PAr2 (Ar = Ph
(1a), 4-MeC6H4 (2a), 4-tBuC6H4 (1)) versus the SiHMe2
substituent as indicated by the NMR data. The large-scale
reaction in toluene at room temperature afforded compound
{(E)-(C6F5)3BCHC[P(4-tBuC6H4)2]SiMe2}2 (4, Scheme 2) that was
precipitated as an off-white solid in a yield of 35%. A suggested
formation of 4 is enhanced in Scheme 3. However, an attempt to
isolate another compound was not successful due to formation
of a messy mixture after separation of 4. Compound 4 is
characterized by NMR spectroscopy and X-ray crystallography,
which features a dimer structure (Figure 2), comparable to that
of 3a or 4a.[15] The P(1)–Si(1) bond length is 2.3241(6) Å and
compares well with those in 3a (2.323(1) Å) and 4a (2.314(1) Å).
In other related species of (C6F5)2HBCH2CH2(Mes)2P→SiH2Ph
Figure 2. X-ray crystal structure of 4 with thermal ellipsoids at 50% probability
level. H atoms except for those of =CH are omitted for clarity. Selected bond
lengths (Å) and angles (°): C(1)–C(2) 1.359(3), C(1)–B(1) 1.649(3), C(2)–
Si(1A) 1.8717(18), C(2)–P(1) 1.8156(18), P(1)–Si(1) 2.3241(6); C(1)–C(2)–
Si(1) 127.50(14), C(1)–C(2)–P(1) 114.25(13), C(2)–C(1)–B(1) 133.57(16),
C(2)–C(1)–H(1A) 113.2, P(1)–C(2)–Si(1) 118.22(10).
(2.309(1)
(OSOCF3)2 (2.3061(1) Å),[18] (Me3P→SiMe3)(OSOCF3) (2.294(1)
Å),[18] Å),[17]
(tBu3P→SiiPr3)[B(C6F5)4] (2.4843(5) and
Å),[12]
[Me3Si←P(Me2)CH2CH2(Me2)P→SiMe3]-
(tBu3P→SiPhMe2)[BH(C6F5)3] (2.3764(8) Å),[19] varied P–Si
lengths are found because of the group steric influence. In the
structure of monomeric part, newly formed C=C bond (1.359(3)
Å) is surrounded by four substituents H, B(C6F5)3, P(4-tBuC6H4)2,
and SiMe2 in an E-configuration. The B, Si, and P centers all are
four-coordinate, adopting the tetrahedral geometry. The B atom
holds the negative charge whereas the Si center the positive
charge. Compound 4 is an alkenyl-linked silylium borate.
Under similar condition, compound 2 reacted with B(C6F5)3 to
give product (Z)-(C6F5)2BCHC(PMes2)SiMe2(C6F5) (5, Scheme 2)
that was isolated as colorless crystals in 55% yield. It was noted
that this reaction proceeded through apparent color changes
from orange to red, dark red, and then this dark red faded
gradually. This process is in sharp contrast to that of the former
reaction by keeping little color change in the course, implying
undergoing of a probably differed reaction mode. Compound 5 is
characterized by NMR spectroscopy and X-ray crystallography,
which displays a structure differing from 4 (3a or 5a) indeed but
resembling to 4a or 6a.[15] A phosphaboracyclobutene of 5 is
formed owing to a strong P–B bonding (2.118(3) Å, Figure 3),
and around the C=C bond (1.341(4) Å) are four groups H,
B(C6F5)2, PMes2, and SiMe2(C6F5) arranged in a Z-configuration.
The P(1)‒C(2)‒C(1) (96.0(2)°) and B(1)‒C(1)‒C(2) (110.0(3)°)
bond angles significantly deviate from the alkenyl 120° indicative
of a C2BP-ring strain character. We performed further the 1H and
31P NMR spectra-monitored reaction of 2 with B(C6F5)3 in CDCl3
from –70 to 25 °C. As shown in Figure 4, an HSi resonance at
δSiH 4.12 ppm assigned to 2 was gradually consummed and the
HC= one at δHC= 8.68 ppm to 5 formed instead. This discloses a
general reaction conversion process. During this course were
found mediation of several other resonances. The resonance at
δSiH 4.75 ppm might correspond to Me2HSiCCP(Mes2)→B(C6F5)3
(Int1), as comparable data are detected for similar
Mes2HSiCCP(Ph2)→B(C6F5)3 (δSiH 5.59 ppm, vide infra) and
Me2HSiCCP(Ph2)→B(C6F5)3 (δSiH 4.70 ppm).[15] The resonance
Scheme 2. Reactions of 1 and 2 each with B(C6F5)3 to form 4 and 5.
at δSiH 4.10 ppm as
a
doublet could be from
a
phosphacyclopropene Mes2PC2[B(C6F5)3](SiHMe2) (Int2) since
its PMes2 resonance was observed at δPMes2 −151.2 ppm (Figure
S1 in the SI) which is close to those in Mes2PC2[B(C6F5)3]Ar (Ar
= 4-MeC6H4, δPMes2 −137.8 ppm; Ar = Ph, δPMes2 −137.4 ppm)
reported by Erker and coworkers.[20] Accordingly, we reason that
the reaction of 2 and B(C6F5)3 to 5 occured by a starting P→B
coordination interaction to form Int1 that proceeded further via a
3
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10.1002/ejic.202000506
European Journal of Inorganic Chemistry
FULL PAPER
at δ 3.75−4.85 ppm are due to the SiHMe2 and at δ 8.25−9.25 ppm to the HC=.
1 Data for 2 at ‒70 ºC before addition of B(C6F5)3.
(C6F5)3B-PMes2 exchange resulting in Int2'. The Int2' reacted by
an H-group 1,3-transfer under the PC2-ring opening to give Int3'
(δHC= 9.10 and δPMes2= 23.8 ppm) that was followed by a C6F5-
migration (Scheme 4). It was mentioned that occurance of the
complicated color changes during the reaction might be due to
formation of the PC2-ring Int2. We have tried isolation of this
species by controlling the reaction at low temperature, but were
not successful. The particular formation of the Int2 ought to be
induced due to unique electronic property of the PMes2
substituented at the C≡C bond.
Scheme 4. Postulated reaction mechanism for 2 and B(C6F5)3 to 5.
Figure 3. X-ray crystal structure of 5 with thermal ellipsoids at 30% probability
level. H atoms except for that of =CH are omitted for clarity. Selected bond
lengths (Å) and angles (°): C(1)–C(2) 1.341(4), C(1)–B(1) 1.603(5), C(2)–Si(1)
1.867(3), C(2)–P(1) 1.817(3), P(1)–B(1) 2.118(3); Si(1)–C(2)–C(1) 124.1(2),
P(1)–C(2)–C(1) 96.0(2), B(1)–C(1)–C(2) 110.0(3), H(1A)–C(1)–C(2) 125,
P(1)–C(2)–Si(1) 137.34(18), C(2)–P(1)–B(1) 75.35(14), C(1)–B(1)–P(1)
77.69(17).
Figure 5. Computed free energy profile (kcal/mol) for reaction of 2 and
B(C6F5)3 to 5 at the M06-2X/def2-SVP level.
We furthermore accomplished DFT calculations at the M06-
2X/def2-SVP level to detect this complicated process. The study
details that the P→B coordination between 2 and B(C6F5)3 is
thermodynamically favoured by G of –4.1 kcal/mol leading to
Int1'. Subsequent (C6F5)3B-PMes2 exchange forming Int2' is
also smoothly going with further exothermic energy of 11.5
kcal/mol. This process compares significantly different from the
(C6F5)3B-SiHMe2 group exchange to generate the Int2-type
HSi
(Int2′)
HSi
(Int1′)
T (℃)
HC=
(Int3’)
HC= (5)
HSi
(2)
25 (10 h)
25 (5 h)
25
20
species (Scheme 3), where
a
chemical change of the
into the
Me2HSiCCP(Ph2)→B(C6F5)3
(C6F5)3BCCP(Ph2)→SiHMe2 was calculated to absorb an energy
by 13.0 kcal/mol for compensation in the reaction of 1a and
B(C6F5)3 to 3a and 5a we previously reported.[15] The conversion
to Int3′ requires to overcome a TS1′ barrier (at 15.5 kcal/mol),
and then an intermolecular C6F5-migration to form 5 still goes
through a TS2′ barrier (at 21.2 kcal/mol) under an energy
releasing of 56.5 kcal/mol (Figure 5). It is deserved to mention
that there suggests another possible TS1a state (Scheme S1 in
the SI). Due to a higher energy level (at 25.3 kcal/mol), the
TS1a was thought not to involve although it converts into 5
through the Int3a without any barrier. As a result, the reaction of
2 and B(C6F5)3 yielded only compound 5, as is in agreement with
the experiment.
5
−10
−25
−40
−55
−70
−701
δ (ppm)
Figure 4. 1H NMR spectra-recorded variable-temperature (from ‒70 to 25 ºC)
reaction of 2 and B(C6F5)3 in CDCl3 on Bruker Avance II 400. The resonances
The reaction using 3 with equivalent B(C6F5)3 was carried out
in toluene at room temperature as usual, which, however, led to
4
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10.1002/ejic.202000506
European Journal of Inorganic Chemistry
FULL PAPER
a prompt formation of compound Mes2HSiCCP(Ph2)B(C6F5)3 (6)
that was isolated as a colorless oil in an almost quantitative yield.
Upon heat treatment at 100 °C for 48 h such reaction further
produced
another
compound
(E)-
Mes2HSi(Ph2P)CC(C6F5)B(C6F5)2 (7) that was isolated as
colorless crystals in 80% yield. Compound 6 is an intermediate
for forming 7 (Scheme 5). The 11B and 31P NMR spectra of 6
exhibited resonances at δB ‒7.1 and δP 3.0 ppm, respectively.
These data compare well to those of HCCP(Ph2)→B(C6F5)3 (δB ‒
8.8 and δP 4.3 ppm) and HCCP[(4-MeC6H4)2]→B(C6F5)3 (δB ‒9.9
and δP 4.1 ppm) measured at ‒60 °C .[21] Moreover, the 31P
resonance
is
close
to
that
of
the
intermediate
Me2HSiCCP(Ph2)→B(C6F5)3 (δP 4.3 ppm) detected at ‒70 °C .[15]
These data suggest 6 a simple P→B coordination compound.
The other NMR (δSiH 5.59, δPC≡ 114.9 and δSiC≡ 119.9 ppm, δSi
‒
60.2 ppm) and IR (νC≡C 2124 and νSi−H 2190 cm‾1) data show
difference from those of the precursor 3 due by the P→B
bonding. Compound 7 was characterized to be an alkene with
the C=C bond (1.341(4) Å; δSiC= 150.3 and δBC= 182.9 ppm)
attached by four different groups C6F5 (δF ‒163.4, ‒157.2 and ‒
138.2 ppm), B(C6F5)2 (δB ‒3.9 and δF ‒163.7, ‒156.6 and ‒128.8
Figure 6. X-ray crystal structure of 7 with thermal ellipsoids at 30% probability
level. H atoms except for that of the SiH are omitted for clarity. Selected bond
lengths (Å) and angles (°): C(1)–C(2) 1.341(4), C(1)–P(1) 1.808(4), C(1)–Si(1)
1.893(4), C(2)–B(1) 1.649(5), P(1)–B(1) 2.033(4), Si(1)–H(1) 1.34(4); C(2)–
C(1)–Si(1) 137.3(3), C(2)–C(1)–P(1) 94.9(2), B(1)–C(2)–C(1) 108.1(3), P(1)–
C(1)–Si(1) 126.0(2).
ppm), PPh2 (δP 24.1 ppm), and SiHMes2 (δSiH 5.32 and δSiH
‒
50.7 ppm; νSi‒H 2174 cm-1) in an E-configuration (Figure 6).
Compound 7 can be viewed also as a phosphaboracyclobutene
due to a P–B bonding (2.033(4) Å), but the feature for
arrangement of four groups around the C2BP-ring is
distinguished from that in 5. To be reasoned, compound 7 is a
result obtained from typical 1,1-carboboration reaction[22,23] while
5 is deviated from the self-hydrosilylation (vide supra).
1,1-Carboboration
reaction
of
Me3SiCCPMes2
with
B(C6F5)2(CH2CH2PMes2) has been known to produce at room
temperature compound (E)-Me3Si(Mes2P)CC(CH2CH2PMes2)-
B(C6F5)2,
where
two
possibilities
via
the
(Mes2PCH2CH2)(C6F5)2B-PMes2 and (Mes2PCH2CH2)(C6F5)2B-
SiMe3 exchanges for further working exist.[23c] Also known is the
reaction of o-CCPPh2C6H4CCSiMe3 and B(C6F5)3 to form o-
C(PPh2)C(C6F5)B(C6F5)2C6H4CCSiMe3 at 60 °C , in which a prior
reactivity was found at the CCPPh2 directing to a (C6F5)3B-PPh2
change and then the 1,1-carboboration reaction.[24] Thus, we
speculate that a further conversion of 6 into 7 is going through a
(C6F5)3B-PPh2 exchange state for function rather than the
(C6F5)3B-SiHMes2 one (Scheme 5).
Scheme 5. Reaction of 3 and B(C6F5)3 to form 6 and 7.
Scheme 6. Reaction of 4 and H2O to 8 and that of 4 and H2O/pyridine to 9.
5
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10.1002/ejic.202000506
European Journal of Inorganic Chemistry
FULL PAPER
Figure 7. X-ray crystal structure of 8 with thermal ellipsoids at 30% probability
level. H atoms except for those of =CH and PH are omitted for clarity. Selected
bond lengths (Å) and angles (°): C(1)–C(2) 1.355(4), C(2)–B(1) 1.646(6),
C(1)–Si(1) 1.891(3), C(1)–P(1) 1.799(3), Si(1)–O(1) 1.648(2), P(1)–H(1)
1.33(3); C(2)–C(1)–Si(1) 131.4(2), C(2)–C(1)–P(1) 114.86(19), B(1)–C(2)–
C(1) 131.9(2), P(1)–C(1)–Si(1) 113.75(14), C(1)–Si(1)–O(1) 101.00(11), Si(1)–
O(1)–Si(2) 143.75(13).
Figure 8. X-ray crystal structure of 9 with thermal ellipsoids at 20% probability
level. H atoms except for those of the HC=, PH and NH are omitted for clarity.
Selected bond lengths (Å) and angles (°): C(1)–C(2) 1.349(3), C(1)–B(1)
1.642(4), C(2)–Si(1) 1.896(2), C(2)–P(1) 1.795(2), O(1)–Si(1) 1.645(2), P(1)–
H(1) 1.36(3); C(2)–C(1)–B(1) 134.6(2), C(1)–C(2)–P(1) 115.33(17), C(1)–
C(2)–Si(1) 132.21(19), Si(1)–C(2)–P(1) 112.43(12), C(2)–Si(1)–O(1)
103.19(11).
Compound 4 is a P/Si+ LP and its reactivity towards small
molecules of H2O and/or isocyanate is investigated. The reaction
of 4 and equivalent H2O was carried out in CDCl3 at room
temperature and generated compound [(E)-(C6F5)3BCHC[PH(4-
tBuC6H4)2]Si(Me2)]2(μ-O) (8, colorless crystals, 80% yield, Figure
7). When this reaction was conducted in the pyridine donor
solvent instead of CDCl3, compound (E)-(C6F5)3BCHC[PH(4-
tBuC6H4)2]Si(Me2)O(HNC5H5) (9, colorless crystals, 60% yield,
Figure 8) was yielded (Scheme 6). The reaction mechanism has
been previously discussed,[15] which involved a disassociation of
H2O by the P/Si+ LP, owning to the concerted silylium’s
electrophilic and P-donor’s nucleophilic interactions. Noted is the
disclosure of compound 9, which may reveal an intermediate
reaction because of the pyridine stabilization of the (E)-
We further carried out reactions using 4 and the
previously prepared 3a each with isocyanate tBuNCO.
Reaction of 3a and tBuNCO was conducted in pyridine at
room temperature and afforded smoothly compound
[(C6F5)3BHC]CSi(Me2)P(Ph2)OC(NtBu)
(
10
,
colorless
crystals, 46% yield). The reaction of
4 with tBuNCO was
performed as well in pyridine at room temperature. After
reaction, a standing of the solution top-layered with n-
hexane at –20 °C for crystallization, however, gave
compound
[Si(Me2)OH(NC5H5)]
(E)-(F5C6)3BCHC[P(4-tBuC6H4)2C(O)NHtBu]-
11), further H2O-dissociation
(
a
species. This is probably due to penetration of H2O in the
course of crystallization of the product. Nevertheless, we
repeated the reaction of
4 with tBuNCO and then
(C6F5)3BCHC[PH(4-tBuC6H4)2]Si(Me2)OH
species.
X-ray
stoichiometric H2O and obtained eventually compound 11
(colorless crystals, 45% yield) (Scheme 7). The reactions of
the FLP complexes with isocyanates have been reported
for a few, which showed two activation routes at the
respective C=O and N=C bonds of the isocyanate.[25] The
formation of 10 indicates a result by the P/Si+ LP reaction
crystallographic study indicated that final structural refinements
converged to an σ-bonded NH group more stable than the σ-
bonded OH group. Then, the data by O···H separation of 2.107
Å (av), H‒N bond length of 0.86 Å, and O···H‒N bond angle of
157.8° (av) confirmed cleanly a hydrogen bonding located within
the SiO···H‒NC5H5 part.
selectively at the C=O bond to give
a C2OPSi-five
membered heterocycle. The generation of compound 11
followed a way similar to 10, leading to similar C2OPSi-
cycle [(C6F5)3BHC]CSi(Me2)P[(4-tBuC6H4)2]OC(NtBu) (IntA),
and IntA further cleaved H2O under the C2OPSi-ring
opening (TSA). This shows a way uniquely to the P-bonded
acylamine molecules.
6
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10.1002/ejic.202000506
European Journal of Inorganic Chemistry
FULL PAPER
C2OPSi-cycle IntA with H2O (Figure 10). The pyridine molecule
behaves well again as a stabilizer for forming the hydrogen
bonding with the SiOH group.
Scheme 7. Reaction of 3a and tBuNCO to 10 and that of 4 and tBuNCO and
H2O to 11.
Figure 10. X-ray crystal structure of 11 with thermal ellipsoids at 50%
probability level. H atoms except for those of the HC=, NH, and OH are
omitted for clarity. Selected bond lengths (Å) and angles (°): C(1)–C(2)
1.351(2), C(1)–B(1) 1.638(2), C(2)–Si(1) 1.9027(16), C(2)–P(1) 1.7954(15),
Si(1)–O(2) 1.6290(12), P(1)–C(3) 1.8861(18), C(3)–O(1) 1.220(2), C(3)–N(1)
1.342(2), O(2)–H(2A) 0.81(3), N(2)···H(2A) 1.916(3); C(1)–C(2)–Si(1)
132.70(12), C(1)–C(2)–P(1) 116.20(11), B(1)–C(1)–C(2) 132.41(14), P(1)–
C(2)–Si(1) 110.91(8), C(2)–Si(1)–O(2) 100.66(7), C(2)–P(1)–C(3) 110.30(7),
P(1)–C(3)–O(1) 119.60(13), P(1)–C(3)–N(1) 112.91(12).
Conclusion
In summary, by the C≡C-centered, three-folded substituent
transformation, phosphanylhydrosilylalkynes R2HSiCCPAr2 (R,Ar:
Me,4-tBuC6H4 1, Me,Mes 2, Mes,Ph 3) have been prepared. The
NMR spectral data indicate a distinguished property of the
phosphanylhydrosilylalkyne with substitution of either the
SiHMes2 (in 2) or PMes2 (in 3) group. Therefore, the reaction of
1 and B(C6F5)3 yielded E-alkene dimer 4 although isolation of
another compound was not successful. This reaction proceeded
through a B(C6F5)3-SiHMe2 exchange generating the [SiHMe2]+
for self-hydrosilylation. The reaction of 2 and B(C6F5)3 gave Z-
alkene C2BP-heterocycle 5, which went through a B(C6F5)3-
PMes2 exchange rendering a phosphacyclopropene for function,
Figure 9. X-ray crystal structure of 10 with thermal ellipsoids at 50%
probability level. H atoms except for that of the HC= are omitted for clarity.
Selected bond lengths (Å) and angles (°): C(1)–C(2) 1.351(3), C(1)–B(1)
1.620(3), C(2)–Si(1) 1.892(2), C(2)–P(1) 1.789(2), P(1)–C(3) 1.834(1), O(1)–
C(3) 1.356(2), O(1)‒Si(1) 1.7025(16), C(3)–N(1) 1.248(3); Si(1)–C(2)–P(1)
106.11(10), C(2)–P(1)–C(3) 101.20(9) ， P(1)–C(3)–O(1) 111.36(14), C(3)–
O(1)–Si(1) 121.16(13), O(1)–Si(1)–C(2) 98.57(8).
showing
a new self-hydrosilylation way. Furthermore, the
X-ray crystallographic study of 10 clearly discloses the
C2OPSi-heterocycle nature (Figure 9). The C‒O bond length
inside the cycle is 1.356(2) Å and the C‒N bond length outside
is 1.248(3) Å. Both these two bond lengths compare a little
longer than those in isocyanate.[26] It is noted that the C‒O bond
distance is a little shorter than that of the formal single bond,
moreover the C−N bond length compares shorter than that of
the double bond. Therefore, these data indicate a yet electronic
reaction of 3 and B(C6F5)3 afforded E-alkene C2BP-heterocycle 7
at elevated temperature. This is probably a result by a B(C6F5)3-
PPh2 exchange to form [PPh2]+ conducting 1,1-carboboration. All
of these results reveal diverse reaction patterns of the
phosphanylhydrosilylalkynes due to variation of either hydrosilyl
or phosphanyl substituent. Of particular attention is the Mes
group substitution at either the Si or P nucleus. Furthermore,
reactions using 4 and the previously prepared 3a both as the
P/Si+ LP toward H2O and/or tBuNCO were accomplished, which
afforded novel H2O-dissociation and/or tBuNCO-cycloaddition
compounds.
conjugation over the O‒C=N part after
a
[3+2] polar
cycloaddition. Compound 10 is still an intramolecular zwitterion
with the negative charge located at the B atom outside but the
positive charge at the P center inside the C2OPSi-ring. X-ray
structure of 11 confirms feature of the PC(O)NHtBu (P–C
1.8861(18), C–O 1.220(2), C–N 1.342(2) Å) and SiO‒H···NC5H5
(Si–O 1.6290(12), O–H 0.81(3), H···N 1.916(3) Å, O‒H···N
161.4°) moieties as a result by the further reaction of the
Experimental Section
7
This article is protected by copyright. All rights reserved.

10.1002/ejic.202000506
European Journal of Inorganic Chemistry
FULL PAPER
Materials and Methods All manipulations were carried out under dry
argon or nitrogen atmosphere by using Schlenk line and glovebox
techniques. Organic solvents toluene, n-hexane and diethyl ether
were dried by refluxing with sodium/potassium benzophenone
under N2 prior to use. NMR (1H, 11B, 13C, 19F, 29Si, and 31P) spectra
were recorded on Bruker Avance II 400 or 500 Spectrometer.
Melting point of compound was measured in a sealed glass tube
using the Büchi-540 instrument. Elemental analysis was performed
on a Thermo Quest Italia SPA EA 1110 instrument. Commercial
reagents were purchased from Energy Chemical and J&K Chemical
Co. and used as received. Compounds Mes2SiHCl,[27] Ar2PCCH (Ar
{(E)-(C6F5)3BCHC[P(4-tBuC6H4)2]SiMe2}2 (4) A solution of
g, 1 mmol) and B(C6F5)3 (0.51 g, 1 mmol) in toluene (20 mL) was
stirred at room temperature. After 1.5 h, compound started to
precipitate from the solution. After stirring for additional 10.5 h, n-
hexane (30 mL) was added till no more precipitates were generated.
1 (0.38
4
Compound
4 was collected by filtration and dried in vacuum. Yield:
1
0.31 g (35%). Mp: 277 °C. H NMR (400 MHz, CDCl3, 298 K, ppm):
δ = 0.0 (d, JPH = 8.0 Hz, 6 H, SiMe), 1.4 (s, 18 H, tBu), 7.33 (m, 4 H),
7.56 (m, 4 H) (C6H4), 9.32 (d, JPH = 48.7 Hz, 1 H, HC=). 11B{1H}
NMR (128 MHz, CDCl3, 298 K, pp m): δ = ‒14.8. 19F{1H} NMR (376
MHz, CDCl3, 298 K, ppm): δ = ‒164.3 (m, 6 F, m-F), ‒158.8 (m, 3 F,
p-F), ‒128.2 (m, 6 F, o-F). 31P{1H} NMR (162 MHz, CDCl3, 298 K,
ppm): δ = 2.2. The 13C and 29Si NMR data were not obtained due to
=
Ph, 2,4,6-Me3C6H2, 4-tBuC6H4),[21,28] B(C6F5)3,[29] and [(E)-
(C6F5)3BCHC(PPh2)SiMe2]2 (3a)
[15] were prepared by referencing to
literatures.
a not good solubility of
1785.12): C 56.52, H 3.73. Found: C 56.55, H 3.71. X-ray quality
single-crystals of were obtained from its CDCl3 solution after
4. Anal. calcd (%) for C84H66B2F30P2Si2 (Mr =
Me2HSiCCP(4-tBuC6H4)2 (1) At –78 °C, nBuLi (5.30 mL, 2.4 M n-
hexane solution, 12.5 mmol) was added dropwise to a stirring
solution of (4-tBuC6H4)2PCCH (4.05 g, 12.5 mmol) in Et2O (80 mL).
The mixture was left to warm to room temperature and kept stirring
for additional 6 h. And then this reaction mixture was cooled again
to ‒78 °C and to it a little excess of Me2SiHCl (1.4 mL, 12.6 mmol)
was added. The mixture was left to warm to room temperature and
kept stirring for additional 12 h. After the reaction, the LiCl
generated was filtered off and the filtrate was evaporated to dryness.
The residue was washed with cold n-hexane (‒20 °C , 2 mL) and
4
keeping undisturbedly at room temperature for 12 h.
(Z)-(C6F5)2BCHC(PMes2)SiMe2(C6F5) (5) At room temperature, a
solution of
2 (0.353 g, 1.0 mmol) in toluene (10 mL) was slowly
added to a solution of B(C6F5)3 (0.512 g, 1.0 mmol) in toluene (10
mL). During addition, a color change promptly to red and then dark-
red was observed. After addition, the mixture was stirred for two
days and finally an almost colorless solution was developed. The
toluene solvent was removed under reduced pressure and the
residue was extracted with n-hexane (10 mL). The extract was kept
then dried in vacuum to give
1 as an off-white solid. Yield: 4.06 g
(85%). Mp: 96 °C. 1H NMR (400 MHz, CDCl3, 298 K, ppm): δ = 0.32
at –20 °C. 72 h later, colorless crystals of
5 were formed. Yield:
3
3
(d, JHH = 3.8 Hz, 6 H, SiMe), 1.31 (s, 18 H, tBu), 4.24 (ds, JHH
=
0.48 g (55%). Mp: 168 °C (decomposed). 1H NMR (400 MHz, CDCl3,
298 K, ppm): δ = 0.51 (d, JPH = 1.9 Hz, 3 H) and 0.52 (d, JPH = 1.9
Hz, 3 H) (SiMe), 2.0 (s, 12 H, o-Me), 2.2 (s, 6 H, p-Me), 6.7 (m, 4 H,
C6H2), 8.68 (d, JPH = 110.0 Hz, 1 H, HC=). 13C{1H} NMR (100 MHz,
CDCl3, 298 K, ppm): δ = ‒0.03 (m, SiMe), 20.7 (p-Me), 23.2, 23.3
(o-Me), 125.2 (d, JPC = 27.9 Hz, SiC=), 130.5 (d, JPC = 8.1 Hz),
141.1 (d, JPC = 8.2 Hz), 141.2 (d, JPC = 2.4 Hz), 143.0 (d, JPC = 25.5
Hz) (C6H2), 108.3 (m), 117.3 (br), 135.8 (br), 138.3 (br), 139.0 (br),
141.5 (br), 143.6 (br), 146.1 (br), 147.8 (br), 148.5 (br), 150.4 (br)
(C6F5), 188.8 (br, BC=). 11B{1H} NMR (128 MHz, CDCl3, 298 K,
ppm): δ = ‒3.9. 19F{1H} NMR (376 MHz, CDCl3, 298 K, ppm): δ = ‒
163.9 (m, 4 F, m-F), ‒157.3 (m, 2 F, p-F), ‒125.2 (m, 4 F, o-F)
(BC6F5), ‒161.1 (m, 2 F, m-F), ‒151.0 (m, 1 F, p-F), ‒125.2 (m, 2 F,
o-F) (SiC6F5). 29Si{1H} NMR (79 MHz, CDCl3, 298 K, ppm): δ = ‒
13.3. 31P{1H} NMR (162 MHz, CDCl3, 298 K, ppm): δ = 24.3. Anal.
calcd (%) for C40H29BF15PSi (Mr = 864.50): C 55.57, H 3.38. Found:
C 55.59, H 3.34.
3.8 Hz, JPH = 1.2 Hz, 1 H, SiH), 7.38 (m, 4 H), 7.55 (m, 4 H) (C6H4).
13C{1H} NMR (100 MHz, CDCl3, 298 K, ppm): δ = ‒2.9 (SiMe), 31.4
(CMe3), 34.7 (CMe3), 106.0 (d, JPC = 15.1 Hz, PC≡), 112.7 (d, JPC
=
3.0 Hz, SiC≡), 125.7 (d, JPC = 7.9 Hz), 132.4 (d, JPC = 5.2 Hz),
132.5 (d, JPC = 21.2 Hz), 152.1 (C6H4). 29Si{1H} NMR (79 MHz,
CDCl3, 298 K, ppm): δ = ‒37.6. 31P{1H} NMR (162 MHz, CDCl3, 298
K, ppm): δ = ‒35.6. IR (KBr plate, cm-1): ν = 2104 (C≡C), 2141 (Si‒
H). Anal. calcd (%) for C24H33PSi (Mr = 380.59): C 75.74, H 8.74.
Found: C 75.65, H 8.66.
Me2HSiCCPMes2 (2) At –78 °C, nBuLi (2.30 mL, 2.4 M n-hexane
solution, 5.40 mmol) was added dropwise to a stirring solution of
Mes2PCCH (1.75 g, 5.40 mmol) in Et2O (60 mL). The mixture was
left to warm to room temperature and kept stirring for additional 6 h.
And then the reaction mixture was cooled again to ‒78 °C and to it
a little excess of Me2SiHCl (0.6 mL, 5.70 mmol) was added. The
mixture was left to warm to room temperature and kept stirring for
additional 12 h. After the reaction, the LiCl generated was filtered
off and the filtrate was evaporated to dryness. The residue was
Mes2HSiCCP(Ph2)B(C6F5)3 (6) At room temperature, to the NMR
tube was added
and CDCl3 (0.4 mL). A slight-yellow solution was developed, and
compound was formed as indicated upon analysis by the
combined H, 13C, 11B, 19F, 29Si and 31P spectra. After removal of
CDCl3, compound was obtained as colorless oil. Yield: 100% on
3 (0.048 g, 0.1 mmol), B(C6F5)3 (0.051 g, 0.1 mmol)
extracted with n-hexane and the extract was dried in vacuum to
1
give
2
as an orange solid. Yield: 1.33 g (71%). Mp: 56 °C. H NMR
6
1
3
(400 MHz, CDCl3, 298 K, ppm): δ = 0.22 (d, JHH = 3.8 Hz, 6 H,
SiMe), 2.25 (s, 6 H, p-Me), 2.38 (s, 12 H, o-Me), 4.12 (ds, 3JHH = 3.8
Hz, JPH = 1.5 Hz, 1 H, SiH), 6.80 (m, 4 H, C6H2). 13C{1H} NMR (100
MHz, CDCl3, 298 K, ppm): δ = ‒3.3 (SiMe), 21.0 (p-Me), 23.1 and
23.2 (o-Me), 106.8 (d, JPC =16.8 Hz, PC≡), 112.8 (SiC≡), 129.2 (d,
JPC = 11.4 Hz), 130.0 (d, JPC = 3.6 Hz), 138.4, 142.2 (d, JPC = 15.6
Hz) (C6H2). 29Si{1H} NMR (79 MHz, CDCl3, 298 K, ppm): δ = ‒38.1.
31P{1H} NMR (162 MHz, CDCl3, 298 K, ppm): δ = ‒54.7. IR (KBr
plate, cm-1): ν = 2086 (C≡C), 2126 (Si‒H). Anal. calcd (%) for
C22H29PSi (Mr = 352.52): C 74.96, H 8.29. Found: C 74.80, H 8.33.
6
1
the basis of the NMR spectral analysis. H NMR (400 MHz, CDCl3,
298 K, ppm): δ = 2.34 (br, 18 H, p-Me and o-Me), 5.59 (s, 1 H, SiH),
6.88 (m, 4 H, C6H2), 7.34‒7.39 (m, 6 H), 7.51‒7.56 (m, 4 H) (Ph).
13C{1H} NMR (100 MHz, CDCl3, 298 K, ppm): δ = 21.1 (p-Me), 23.3
(o-Me), 114.9 (PC≡), 119.9 (SiC≡), 125.0, 128.7 (d, JPC = 10.5 Hz),
129.1, 131.7, 133.0 (d, JPC = 10.8 Hz), 139.0, 147.3 (Ph and C6H2),
135.8 (br), 138.2 (br), 139.0 (br), 141.5 (br), 147.3 (br), 149.7 (br)
(C6F5). 11B{1H} NMR (128 MHz, CDCl3, 298 K, ppm): δ = ‒7.1.
19F{1H} NMR (376 MHz, CDCl3, 298 K, ppm): δ = ‒163.9 (m, 6 F, m-
F), ‒155.0 (m, 6 F, p-F), ‒126.9 (m, 4 F, o-F). 29Si{1H} NMR (79
MHz, CDCl3, 298 K, ppm): δ = ‒60.2. 31P{1H} NMR (162 MHz,
CDCl3, 298 K, ppm): δ = 3.0. IR (KBr plate, cm-1): ν = 2124 (C≡C),
2190 (Si‒H). Anal. calcd (%) for C50H33BF15PSi (Mr = 988.66): C
60.74, H 3.36. Found: C 60.82, H 3.75.
Mes2HSiCCPPh2 (3) At –78 °C, nBuLi (2.2 mL, 2.4 M n-hexane
solution, 5.20 mmol) was added dropwise to a stirring solution of
Ph2PCCH (1.09 g, 5.20 mmol) in Et2O (50 mL). The mixture was left
to warm to room temperature and kept stirring for additional 6 h.
And then the reaction mixture was cooled again to ‒78 °C and to it
a solution of Mes2SiHCl (1.57 g, 5.20 mmol) in Et2O (15 mL) was
added. The mixture was left to warm to room temperature and kept
stirring for additional 12 h. After the reaction, the LiCl generated
was filtered off and the filtrate was evaporated to dryness. The
residue was extracted with n-hexane and the extract was dried in
Mes2HSi(Ph2P)CC(C6F5)B(C6F5)2 (7) A solution of
3 (0.48 g, 1
mmol) and B(C6F5)3 (0.51 g, 1 mmol) in toluene (10 mL) was heated
at 100 °C for two days. After cooling to room temperature, the
solution was concentrated to ca. 4 mL and to it n-hexane (4 mL)
was added. This solution mixture was kept at ‒20 °C. 72 h later,
vacuum to give
3 as a slight-grey solid. Yield: 1.86 g (75%). Mp:
88 °C. 1H NMR (400 MHz, CDCl3, 298 K, ppm): δ = 2.27 (s, 6 H, p-
Me), 2.42 (s, 12 H, o-Me), 5.62 (s, 1 H, SiH), 6.83 (m, 4 H, C6H2),
7.31 (m, 6 H), 7.55 (m, 4 H) (Ph). 13C{1H} NMR (100 MHz, CDCl3,
298 K, ppm): δ = 21.2 (p-Me), 23.7 (o-Me), 107.2 (d, JPC =15.2 Hz,
PC≡), 113.2 (d, JPC = 3.2 Hz, SiC≡), 127.4, 129.1, 139.8, 144.8
colorless crystals of 7 were generated. Yield: 0.79 g (80%). Mp:
187 °C. 1H NMR (400 MHz, CDCl3, 298 K, ppm): δ = 2.12 (s, 12 H,
o-Me), 2.23 (s, 6 H, p-Me), 5.32 (d, JPH = 1.8 Hz, 1 H, SiH), 6.67 (s,
4 H, C6H2), 7.27‒7.31 (m, 4 H), 7.34‒7.39 (m, 4 H), 7.47‒7.52 (m, 2
H) (Ph). 13C{1H} NMR (100 MHz, CDCl3, 298 K, ppm): δ = 21.1 (p-
(C6H2), 128.7 (d, JPC = 7.5 Hz), 132.7, 132.9, 135.7 (d, JPC = 6.2 Hz) Me), 23.7 (o-Me), 126.0 (d, JPC = 42.0 Hz), 126.6 (d, JPC = 2.6 Hz),
(Ph). 29Si{1H} NMR (79 MHz, CDCl3, 298 K, ppm): δ = –61.1. 31P{1H} 128.7 (d, JPC = 10.5 Hz), 128.9, 132.1 (d, JPC = 2.7 Hz), 133.0 (d,
NMR (162 MHz, CDCl3, 298 K, ppm): δ = –31.5. IR (KBr plate, cm-1): JPC = 9.2 Hz), 140.3, 145.0 (Ph and C6H2), 150.3 (d, JPC = 22.3 Hz)
ν = 2091 (C≡C), 2148 (Si‒H). Anal. calcd (%) for C32H33PSi (Mr =
476.66): C 80.63, H 6.98. Found: C 80.57, H 6.92.
(SiC=), 135.8 (br), 138.3 (br), 138.8 (br), 141.3 (br), 143.6 (br),
146.3 (br), 148.7 (br) (C6F5), 182.9 (BC=). 11B{1H} NMR (128 MHz,
8
This article is protected by copyright. All rights reserved.

10.1002/ejic.202000506
European Journal of Inorganic Chemistry
FULL PAPER
CDCl3, 298 K, ppm): δ = ‒3.9. 19F{1H} NMR (376 MHz, CDCl3, 298
K, ppm): δ = ‒163.7 (m, 4 F, m-F), ‒156.6 (m, 2 F, p-F), ‒128.8 (m,
4 F, o-F) (BC6F5), ‒163.4 (m, 2 F, m-F), ‒157.2 (m, 1 F, p-F), ‒
138.2 (m, 2 F, o-F) (CC6F5). 29Si{1H} NMR (79 MHz, CDCl3, 298 K,
ppm): δ = ‒50.7. 31P{1H} NMR (162 MHz, CDCl3, 298 K, ppm): δ =
24.1. IR (KBr plate, cm-1): ν = 2174 (Si‒H). Anal. calcd (%) for
C50H33BF15PSi (Mr = 988.66): C 60.74, H 3.36. Found: C 60.64, H
3.28.
1.9 (SiMe), 28.5 (CMe3), 31.0 (CMe3), 31.8 (CMe3), 35.5 (CMe3), 116.4
(d, JPC = 83.1 Hz, SiC=), 123.9, 136.3, 149.7 (NC5H5), 127.0 (d, JPC
=12.3 Hz), 133.8 (d, JPC =8.8 Hz), 158.7 (C6H4), 120.8 (m), 135.6 (m),
138.1 (m), 138.0 (m), 140.4 (m), 147.2 (m), 149.6 (br) (C6F5), 162.5 (d,
JPC = 95.6 Hz, C=O), 210.7 (br, BC=). 11B{1H} NMR (128 MHz, CDCl3,
298 K, ppm): δ = ‒21.7. 19F{1H} NMR (376 MHz, CDCl3, 298 K, ppm): δ =
‒165.0 (m, 6 F, m-F), ‒160.3 (m, 3 F, p-F), ‒130.5 (m, 6 F, o-F). 29Si{1H}
NMR (79 MHz, CDCl3, 298 K, ppm): δ = 8.0. 31P{1H} NMR (162 MHz,
CDCl3, 298 K, ppm): δ = 17.3. IR (KBr plate, cm-1): ν = 3702 (O‒H), 2912
(N‒H). Anal. calcd (%) for C52H49BF15N2O2PSi (Mr = 1088.80): C 57.36,
H 4.54, N 2.57. Found: C 57.31, H 4.50, N 2.54.
{(E)-(C6F5)3BCHC[PH(4-tBuC6H4)2]Si(Me2)}2(μ-O) (8) At room
temperature, H2O (0.001 g, 0.05 mmol) was added to a solution of
(0.089 g, 0.05 mmol) in CDCl3 (0.4 mL). The mixture was kept at
room temperature. 48 h later, colorless crystals of were generated.
Yield: 0.082 g (90%). Mp: 160 °C. 1H NMR (400 MHz, CDCl3, 298 K,
ppm): δ = ‒0.35 (s, 6 H, SiMe), 1.35 (s, 18 H, tBu), 7.45 (d, JPH
4
8
X-Ray Crystallographic Analysis Crystallographic data for compounds
2, 40.5·0.5 toluene·n-hexane, 5, 7·toluene, 8·2 CDCl3, 9·C 6D6, 10·0.5 n-
hexane and 11·0.5 n-hexane were collected on a Rigaku Oxford
Diffraction system. During measurements a graphite-monochromatic Cu-
Ka radiation (λ= 1.54178 Å) was applied for 40.5·0.5 toluene·n-hexane,
8·2 CDCl3, 9·C 6D6, 10·0.5 n-hexane and 11·0.5 n-hexane and the Mo-Ka
radiation (λ = 0.71073 Å) was used for 1, 5 and 7·toluene. Absorption
corrections were all employed using the spherical harmonics program
(multi-scan type). All the structures were solved by direct methods
(SHELXS-96)[30] and refined against F2 using SHELXL-2014.[31] In
general, the non-hydrogen atoms were located by difference Fourier
synthesis and refined anisotropically, and hydrogen atoms were included
using a riding mode with Uiso tied to the Uiso of the parent atoms unless
otherwise specified. In 2, the SiHMe2 group was disordered and treated
=
463.4 Hz, 1 H, PH), 7.39 (m, 4 H), 7.65 (m, 4 H) (C6H4), 8.71 (d, JPH
= 57.5 Hz, 1 H, HC=). 13C{1H} NMR (100 MHz, CDCl3, 298 K, ppm):
δ = 2.0 (SiMe), 31.0 (CMe3), 35.7 (CMe3), 113.5 (d, JPC = 86.6 Hz,
SiC=), 125.5, 127.7 (d, JPC = 13.0 Hz), 128.4, 129.2, 133.8 (d, JPC
=10.4 Hz), 160.0 (C6H4), 115.8 (br), 116.1(br), 135.7 (br), 138.0 (br),
140.3 (br), 138.1 (br), 140.4 (br), 146.9 (br), 149.4 (br) (C6F5), 208.1
(br, BC=). 11B{1H} NMR (128 MHz, CDCl3, 298 K, ppm): δ = ‒15.4
(br). 19F{1H} NMR (376 MHz, CDCl3, 298 K, ppm): δ = ‒165.0 (m, 6
F, m-F), ‒160.0 (m, 3 F, p-F), ‒130.2 (m, 6 F, o-F). 29Si{1H} NMR
(79 MHz, CDCl3, 298 K, ppm): δ = 5.1. 31P{1H} NMR (162 MHz,
CDCl3, 298 K, ppm): δ = 6.7. IR (KBr plate, cm-1): ν = 1989 (P‒H).
Anal. calcd (%) for C84H68B2F30OP2Si2 (Mr = 1803.13): C 55.95, H
3.80. Found: C 56.03, H 3.82.
by
PART
method,
in
which
Si(1)H(1)C(3)C(4)
and
Si(1A)H(1A)C(3A)C(4A) were located and refined in the respective
occupancies of 0.78283 and 0.21717. The H(1) and H(1A) atoms were
(E)-(C6F5)3BCHC[PH(tBuC6H4)2]Si(Me2)O(HNC5H5) (9) At room
temperature, to a solution of
4 (0.35 g, 0.19 mmol) in pyridine (6 mL) located by difference Fourier synthesis and refined isotropically. In
was added H2O (0.007 g, 0.39 mmol). The mixture was stirred to
give a solution. The solvent was removed in vacuum and the
residue was dissolved in toluene/n-hexane (2 mL/2 mL) mixture.
The solution was kept at –20 °C for 24 h, generating colorless
40.5·0.5 toluene·n-hexane, a half moiety of 4 was disclosed and the whole
molecule was obtained via the symmetric operation. The 0.5 toluene
molecule was seriously disordered, which was treated by PART method
and refined to give two parts. The hydrogen atoms in these two parts
were not able to be added. In 7·toluene, the SiH hydrogen atom was
located by difference Fourier synthesis and refined isotropically. The
toluene molecule was disordered, which was treated by PART method
and refined into two parts C(61)C(62)C(63)C(64)C(65)C(66)C(67) and
C(61A)C(62A)-C(63A)C(64A)C(65A)C(66A)C(67A) with the respective
occupancies of 0.45743 and 0.54257. In 8·2 CDCl3, both two CDCl3
molecules were disordered and treated by PART method. One molecule
crystals of
9
. Yield: 0.23 g (60%). Mp: 167 °C (decomposed). 1H
NMR (400 MHz, CDCl3, 298 K, ppm): δ = ‒0.21 (s, 6 H, SiMe), 1.35
(s, 18 H, tBu), 3.66 (br, 1 H, NH), 7.29 (m, 2 H), 7.69 (m, 1 H), 8.47
(m, 2 H) (NC5H5), 7.48 (m, 4 H), 7.62 (m, 4 H) (C6H4), 7.87 (d, JPH
=
58.9 Hz, 1 H, PH), 8.63 (d, JPH = 58.9 Hz, 1 H, HC=). 13C{1H} NMR
(100 MHz, CDCl3, 298 K, ppm): δ = 0.9 (SiMe), 30.9 (CMe3), 35.5
(CMe3), 117.7 (d, JPC = 85.7 Hz, SiC=), 127.2 (d, JPC = 12.8 Hz),
128.4, 129.2, 133.6 (d, JPC =10.1 Hz), 158.8 (C6H4), 124.5, 137.0,
148.8 (NC5H5), 119.4 (m), 135.6 (m), 138.2 (m), 140.1 (m), 147.2
(br), 149.5 (br) (C6F5), 204.7 (br, BC=). 11B{1H} NMR (128 MHz,
CDCl3, 298 K, ppm): δ = ‒15.3 (br). 19F{1H} NMR (376 MHz, CDCl3,
298 K, ppm): δ = ‒165.5 (m, 6 F, m-F), ‒160.7 (m, 3 F, p-F), ‒130.4
(m, 6 F, o-F). 29Si{1H} NMR (79 MHz, CDCl3, 298 K, ppm): δ = 5.8.
31P{1H} NMR (162 MHz, CCl3, 298 K, ppm): δ = 11.4. IR (KBr plate,
was
C(85A)Cl(1A)Cl(2A)Cl(3A) with the respective occupancies of 0.67610
and 0.32390 and another into C(86)Cl(4)Cl(5)Cl(6) and
refined
into
two
parts
C(85)Cl(1)Cl(2)Cl(3)
and
C(86A)Cl(4A)Cl(5A)Cl(6A) with the respective occupancies of 0.74841
and 0.25159. The three methyl groups of one tBu were also disordered
and treated by PART method refining into C(54)C(55)C(56) and
C(54A)C(55A)C(56A) with the respective occupancies of 0.52062 and
0.47938. In addition, each H atom of the two PH moieties was located by
difference Fourier synthesis and refined isotropically. In 9·C 6D6, two
halves of the C6D6 molecules were disclosed, of which one half molecule
was seriously disordered. The carbon atoms in this molecule were
refined isotropically and to which the hydrogen atoms were not able to be
added. The pyridine molecule was disordered and treated by PART
cm-1):
ν = 2963 (N‒H), 1935 (P‒H). Anal. calcd (%) for
C47H40BF15NOPSi (Mr = 989.67): C 57.04, H 4.07, N 1.42. Found: C
57.01, H 4.05, N 1.43.
[(C6F5)3BHC]CSi(Me2)P(Ph2)OC(NtBu) (10) At room temperature,
tBuNCO (0.052 g, 0.52 mmol) was added to a solution of 3a (0.41 g,
0.26 mmol) in pyridine (6 mL). The mixture was stirred for 4 h. All
volatiles were removed in vacuum and the residue was dissolved in
toluene/n-hexane (2 mL/2 mL) mixture. The solution was kept at –
20 °C for 24 h, generating colorless crystals of 10. Yield: 0.21 g
method
refining
into
N(1)C(43)C(44)-C(45)C(46)C(47)
and
N(1A)C(43A)C(44A)C(45A)C(46A)-C(47A)
with the respective
occupancies of 0.59649 and 0.40351. One tBu group was disordered and
treated by PART method refining into C(11)C(12)C(13)C(14) and
C(11A)C(12A)C(13A)C(14A) with the respective occupancies of 0.57195
and 0.42805. Three methyl groups of the other tBu were disordered and
treated by PART method refining into C(22)C(23)C(24) and
C(22A)C(23A)C(24A) with the respective occupancies of 0.17963 and
0.82037. The PH hydrogen atom was located by difference Fourier
synthesis and refined isotropically. The H atom existed within hydrogen
bonding of the SiO···H‒NC5H5 part was refined to bond to the N atom
rather than the O atom. In 10·0.5 n-hexane, the half n-hexane molecule
was disordered and treated by PART method refining into
C(41)C(42)C(43) and C(41A)C(42A)C(43A) with the respective
occupancies of 0.48647 and 0.51353. In 11·0.5 n-hexane, the half n-
hexane molecule was disordered and treated by PART method refining
into C(53)C(54)C(55) and C(53A)C(54A)C(55A) with the respective
occupancies of 0.60299 and 0.39701. The H atom existed within
hydrogen bonding of the SiO‒H···NC5H5 part was refined to bond to the
O atom rather than the N atom. A summary of cell parameters, data
collection, and structure solution and refinements is given in Table S1.
1
(46%). H NMR (400 MHz, CDCl3, 298 K, ppm): δ = ‒0.08 (s, 6 H,
SiMe), 1.32 (s, 18 H, tBu), 7.64 (m, 8 H) (C6H4), 8.80 (d, JPH = 42.8
Hz , 1 H, HC=). 11B{1H} NMR (128 MHz, CDCl3, 298 K, ppm): δ = ‒
14.6. 19F{1H} NMR (376 MHz, CDCl3, 298 K, ppm): δ = ‒164.7.0 (m,
6 F, m-F), ‒159.9 (m, 3 F, p-F), ‒130.5 (m, 6 F, o-F). 31P{1H} NMR
(162 MHz, CDCl3, 298 K, ppm): δ = 5.0. The 13C and 29Si NMR
spectra were not measured. Anal. calcd (%) for C39H26BF15NOPSi
(Mr = 879.48): C 53.26, H 2.98, N 1.59. Found: C 53.27, H 3.02, N
1.61.
(E)-(F5C6)3BCHC[P(4-tBuC6H4)2C(O)NHtBu][Si(Me2)OH(NC5H5)] (11) At
room temperature, tBuNCO (0.02 g, 0.20 mmol) was added to a solution
of 4 (0.179 g, 0.10 mmol) in pyridine (6 mL). The mixture was stirred at
room temperature for 4 h. Then to the solution H2O (0.0036 g, 0.20
mmol) was added. The mixture was stirred for 4 h. The volatiles were
removed in vacuum and the residue was dissolved in toluene/n-hexane
(2 mL/2 mL). The solution was kept at –20 °C for 48 h, generating
1
colorless crystals of 11. Yield: 0.098 g (45%). Mp: 120 °C. H NMR (400
MHz, CDCl3, 298 K, ppm): δ = ‒0.17 (s, 6 H, SiMe), 1.33 (s, 18 H, tBu),
1.54 (s, 9 H, tBu), 2.58 (s, 1 H, NH), 6.87 (br, 1 H, SiOH), 7.28 (m, 1 H),
7.68 (m, 2 H), 8.51 (m, 2 H) (NC5H5), 7.60 (m, 8 H) (C6H4), 8.74 (d, JPH
=
55.1 Hz , 1 H, HC=). 13C{1H} NMR (100 MHz, CDCl3, 298 K, ppm): δ =
Acknowledgements
9
This article is protected by copyright. All rights reserved.

10.1002/ejic.202000506
European Journal of Inorganic Chemistry
FULL PAPER
G. Erker, Z. Naturforsch. 2012, 67b, 987-994; c) M. H. Holthausen, J. M.
Bayne, I. Mallov, R. Dobrovetsky, D. W. Stephan, J. Am. Chem. Soc.
2015, 137, 7298-7301; d) Y. Ma, S.-J. Lou, G. Luo, Y. Luo, G. Zhan, M.
Nishiura, Y. Luo, Z. Hou, Angew. Chem. Int. Ed. 2018, 57, 15222-
15226.
H. Z. acknowledges the National Natural Science Foundation of
China (21673191 and 21972112) and Guangdong Laboratory of
chemistry and fine chemicals (1922016) for financial support. Y.
L. thanks the National Natural Science Foundation of China (No.
21801055). M.-C. Y. and M.-D. S. are grateful to the National
Center for High-Performance Computing of Taiwan for generous
amounts of computing time, and the Ministry of Science and
Technology of Taiwan for the financial support.
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European Journal of Inorganic Chemistry
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Table of Contents
A Key Topic: Functionalized Alkyne
Text: Reactions of phosphanylhydrosilylalkynes with B(C6F5)3 produce compounds of several types, which are results from differed
reaction patterns induced due to the substituents effected on the C≡C bond.
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