Reactions of 1,3,2-diselenaphospholanes with lewis acids: Borane and (pentamethylcyclopentadienyl)rhodium and -iridium dichloride

Article abstract of DOI:10.1002/ejic.201402486

2-R-1,3,2-Diselenaphospholanes (R = iPr, Ph) with an annelated 1,2-dicarba-closo-dodecaborane(12) unit were treated with Lewis acids such as borane reagents (BH₃ in THF, and BH₃-SMe₂) as well as Cp^?-rhodium and -iridium dichloride (Cp? = pentamethylcyclopentadienyl). In all cases, the adduct formation in the beginning was followed by ring expansion through insertion of the borane or Cp^?MCl₂ into one of the P-Se bonds accompanied by transfer of a hydrido or chlorido ligand to phosphorus. Finally, the P-R unit was displaced from the ring to give the exchange products, in which the boron or the metal had become part of the five-membered rings. The reactions were monitored by NMR spectroscopy (¹H, ¹¹B, ¹³C, ³¹P, and ⁷⁷Se). The proposed reaction sequences were found to be in agreement with calculated [B3LYP/6-311+G(d,p), LANL2DZ (Rh, Ir) level of theory] relative energies of optimized gas-phase structures of the various products. The novel molecular structure of the preferred insertion product with M = Ir, R = iPr was determined by X-ray analysis. Borane reagents as well as Cp^?MCl₂ (Cp? = pentamethylcyclopentadienyl; M = Rh, Ir) react with 1,3,2-diselenaphospholanes by the formation of adducts, followed by ring insertion, and finally by exchange.

Full text of DOI:10.1002/ejic.201402486

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DOI:10.1002/ejic.201402486
Reactions of 1,3,2-Diselenaphospholanes with Lewis Acids:
Borane and (Pentamethylcyclopentadienyl)rhodium and
-iridium Dichloride
Bernd Wrackmeyer,*[a] Elena V. Klimkina,[a] and Wolfgang Milius[b]
Keywords: Main-group elements / Selenium / Phosphorus / Boron / Carboranes / Lewis acids
2-R-1,3,2-Diselenaphospholanes (R = iPr, Ph) with an annel-
ated 1,2-dicarba-closo-dodecaborane(12) unit were treated
with Lewis acids such as borane reagents (BH3 in THF, and
BH3–SMe2) as well as Cp*-rhodium and -iridium dichloride
(Cp* = pentamethylcyclopentadienyl). In all cases, the ad-
duct formation in the beginning was followed by ring expan-
sion through insertion of the borane or Cp*MCl2 into one of
the P–Se bonds accompanied by transfer of a hydrido or
chlorido ligand to phosphorus. Finally, the P–R unit was dis-
placed from the ring to give the exchange products, in which
the boron or the metal had become part of the five-mem-
bered rings. The reactions were monitored by NMR spec-
troscopy (1H, 11B, 13C, 31P, and 77Se). The proposed reaction
sequences were found to be in agreement with calculated
[B3LYP/6-311+G(d,p), LANL2DZ (Rh, Ir) level of theory] rela-
tive energies of optimized gas-phase structures of the various
products. The novel molecular structure of the preferred in-
sertion product with M = Ir, R = iPr was determined by X-ray
analysis.
77Se NMR spectra[9] as an attractive analytical tool, com-
bined with 31P NMR spectroscopy for monitoring reac-
tions.
Introduction
The basicity of three-coordinate phosphorus in phos-
pholanes appears to be markedly lower than in correspond-
ing six-membered rings or noncyclic derivatives, as has been
noted for complexation of 1,3,2-dioxaphospholanes with
H+, BH3, BF3,[1] and metals.[1,2] This was attributed to the
electronegativity of oxygen as well as to the ring strain in
the five-membered heterocycles.[3,4] There are no systematic
studies for other 1,3,2-dichalcogenophospholanes contain-
ing the chalcogens (E) S,[5] Se,[6] or Te. Our interest in such
compounds with an annelated 1,2-dicarba-closo-dodecabor-
ane(12) unit prompted us to explore the behavior of 1,3,2-
diselenaphospholanes 1[7] and 2[6,7] towards Lewis acids
such as BH3 (as adduct with THF or SMe2), Br2BH–SMe2,
and [Cp*MCl2]2 (M = Rh, Ir). Phospholanes 1 and 2 were
selected because 1 stays mainly as a monomer in solution
and 2 does not show any tendency at all for dimerization,
and both 1 and 2 possess analogous solution-state struc-
tures as far as the five-membered rings are concerned.[7,8]
Furthermore, selenium may compete with phosphorus for
the Lewis acid, in particular if the basicity of phosphorus
is reduced. An additional advantage is gained by measuring
Results and Discussion
Reactions of 1,3,2-Diselenaphospholanes with Boranes
Schemes 1 and 2 show the reactions of 1 and 2 with bor-
anes,[10] respectively. By using BH3/THF, 1 undergoes re-
versible adduct formation (3). Although the reaction ap-
pears to take place instantaneously, no more than approxi-
mately 60% of 1 was converted into 3, even with a large
excess amount of the borane reagent (see Figure 1). Because
of further reactions, the equilibrium constant could not be
determined. In principle, there could be two isomers for 3,
differing in the configuration at phosphorus, of which only
one was observed. No attempt has been made to assign the
solution-state structure, and the low stability of 3 (in the
mixture with 1) and further products prevented isolation of
crystalline materials. In the presence of an excess amount
of the borane reagent and upon removing volatile materials
in a vacuum, 3 rearranges within hours into 4 and 4Ј by
insertion of BH3 into one of the P–Se bonds, and 4/4Ј de-
compose in the reaction solution. The analogous reaction
[a] Anorganische Chemie II, Universität Bayreuth,
95440 Bayreuth, Germany
E-mail: b.wrack@uni-bayreuth.de
http://www.ac2.uni-bayreuth.de
[b] Anorganische Chemie I, Universität Bayreuth,
95440 Bayreuth, Germany
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.201402486.
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Scheme 1. Reactions of 1 with BH3 in THF, BH3–SMe2, and Br2BH–SMe2.
Scheme 2. Reactions of 2 with BH3–SMe2 and BH3 in THF.
with BH3–SMe2 also leads to an equilibrium between ad- products 6 and iPrPBr2 (Scheme 1). An adduct was not ob-
duct 3 and 1. However, in the presence of an excess amount served. In addition, this mixture finally contains dimer 8[7]
of BH3–SMe2, further slow (over weeks) reactions take and bis(diselane) 9.[13]
place via 4 and 4Ј towards exchange products (5, not de-
Gas-phase structures of the three isomers, adduct 3
tected), and 6[11] (from the reaction of 5 with SMe2), 7 (structure as shown; the alternative structure possesses al-
(from the reaction of iPrPH2 with BH3), and decomposition most exactly the same energy), the insertion products 4/4Ј,
(e.g., H3P–BH3). Monitoring these reactions using 31P, 11B, and the exchange product 5, were calculated and optimized
and 77Se NMR spectroscopy (Figure 1) as well H NMR at the B3LYP/6-311+G(d,p) level of theory[14] and their rel-
1
spectroscopy (Figure 2) supports the proposed mechanism ative energies were compared. These calculations predict
(see also Table 1). Interestingly, coupling constants that 4/4Ј (almost identical in energy) are more stable than
1J(31P,11B) for 3 and 4/4Ј are small and therefore the P–B 3 (by ≈11 kcalmol–1), and 5 is more stable than 4/4Ј (by
bonds are not clearly indicated in the 11B and 31P NMR ≈10.5 kcalmol–1).
1
spectra. However, the H{11B} NMR spectroscopy experi-
The phenyl derivative 2 shows a slightly different behav-
ments (Figure 2) unambiguously prove this bond for 3, ior to 1. Thus, reversible adduct formation (10) takes place,
since geminal 31P–B–1H spin–spin coupling is resolved [see followed by exchange (6,[11] 11[15]) in the case of an excess
also the 77Se NMR spectroscopic signal for 3 in Figure 1, amount of BH3–SMe2, or decomposition with an excess
which shows 3J(77Se,P,B,1H)]. In the case of 4/4Ј, the obser- amount of BH3 in THF (Scheme 2). An insertion product
1
vation of the vicinal H–B–P–1H spin–spin coupling (Fig- analogous to 4 was not observed. The proposed structure
ure 2) helps with the assignment, which confirms 11B, 31P, of 10 was drawn in analogy to the sulfide, for which an X-
and 77Se NMR spectroscopic results (Figure 1). Treatment ray structural analysis had been carried out.[6a] As for 3 (see
of 1 with Br2BH–SMe2 affords reversibly the exchange above), an alternative structure of 10 cannot be ruled out.
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Figure 1. 202.5 MHz 31P (upper trace), part of the 160.4 MHz 11B (framed), and 95.4 MHz 77Se (lower trace) NMR spectra of the
reaction solution (at room temperature), starting from 1 and an excess amount of BH3/THF, and removal of volatile materials under
vacuum. Compound 1 is still present together with adduct 3 [identified by the satellites due to 1J(77Se,31P) and the corresponding splitting
of the 77Se NMR spectroscopic signal]. The latter is further split by vicinal 77Se–PB–1H coupling to a quartet. The presence of 4 and 3
is indicated in the 11B NMR spectra by the triplet and the quartet [1H(11B,1H)] with typical chemical shifts δ11B, respectively. The slightly
1
different environments of 11B nuclei in 4 and 4Ј are not resolved. The insertion products 4/4Ј require two doublets in the H-coupled 31P
NMR spectrum, as observed, and four 77Se NMR spectroscopic signals, of which three are resolved, two of them as doublets with correct
1J(77Se,31P) values for the 77Se nuclei linked to 31P.
Figure 2. (A) Part of the 500.13 MHz 1H{11B} NMR spectrum of 3 showing the 1H(P–BH3) signal. (B) Part of the 500.13 MHz 1H NMR
spectrum of 4 showing the 1H(HP–B) signal; the extension shows that the small splittings are due to 3J(1H,CiPr,P,1H) (doublet) and
1
1
3J(1H,BBH ,P,1H) (triplet). (C) Part of the 500.13 MHz H NMR spectrum of 4Ј showing the H(HP–B) signal (all spectra measured at
2
23 °C in [D8]toluene).
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Table 1. 31P, 77Se, 11B, and 13C NMR spectroscopic data[a] of the ortho-carborane derivatives 3–6 and 10.
R
δ31P
δ77Se
δ11B (B–P)
δ13C [C(carb)]
Other δ13C
3
149.2
594.0
–35.3, q,
75.7 [157.0]
(6.8) {–8.2}
16.8 (4.5),
34.9 (2.7)
1J(77Se,31P) = 328.6 Hz
1J(77Se,31P) = 328.3 Hz
3J(77Se,1HBH) = 15.5 Hz
630.5
1J(11B,1H) = 100 Hz
3 (calcd.)
242.3
–29.6
96.4 (–5.8)
–
1J(31P,11B) = –13.9 Hz
16.5
1J(11B,1H) = +107 Hz
–28.2, t,
4
SeP: 341.1
61.0 (9.1) (3J),
57.0 (4.6) (2J)
18.0 (2.6),
34.2
1J(77Se,31P) = 285 Hz
1J(31P,1H) = 402 Hz
1J(31P,11B) ≈ 20 Hz
1J(77Se,31P) = 284.6 Hz
2J(77Se,1HPH) = 32 Hz,
SeB: 257.3
1J(11B,1H) = 113 Hz
h1/2 ≈ 125 Hz
SeP: 381.8,
SeB: 206.5
4 (calcd.)
4Ј
+20.7
–27.1
85.9 (+9.9) (3J),
73.2 (–5.6) (2J)
–
1J(31P,1H) = +282.8 Hz
1J(31P,11B) = +20.7 Hz
40.7
1J(11B,1H) = +115.0 Hz
1J(11B,1H) = +135.9 Hz
–28.2
SeP: 373.5
n.o.
n.o.
1J(77Se,31P) = 356 Hz
1J(31P,1H) = 380 Hz
1J(77Se,31P) = 356 Hz
2J(77Se,1HPH) = 33 Hz,
SeB: 257.3
4Ј (calcd.)
5 (calcd.)
+44.7
SeP: 335.4,
SeB: 242.5
–24.8
88.1 (+11.8) (3J),
78.7 (–4.2) (2J)
–
–
1J(31P,1H) = +325.3 Hz
1J(31P,11B) = +12.6 Hz
–47.8
1J(11B,1H) = +113.7 Hz
1J(11B,1H) = +134.5 Hz
–6.3
355.3
97.5 (–1.5)
1J(31P,1H) = +323.7 Hz
1J(31P,11B) = +47.2 Hz
–
1J(11B,1H) = +130.6 Hz
[11]
6
409.1 (br.)
n.o.
4.9 (HBSe), d,
1J(11B,1H) = 145 Hz
–29.0
75.4
21.8 (SMe2)
10
124.6
n.o.
n.o.
–
1J(77Se,31P) = 340 Hz
10 (calcd.) 193.1
749.3
–28.5
94.2 (–3.6)
1J(31P,11B) = –16.6 Hz
1J(11B,1H) = +108 Hz
n
n
[a] In [D8]toluene at 296 K. Coupling constants J(31P,13C) are given in parentheses (Ϯ0.5 Hz); J(77Se,13C) are given in square brackets
[Ϯ0.5 Hz]; Δ10/11B[13C(carb)][12] are given in braces {Ϯ0.5 ppb}; isotope-induced chemical shifts Δ are given in ppb, and the negative
1
1
sign denotes a shift of NMR spectroscopic signal of the heavy isotopomer to lower frequency; n.o.: not observed.
Reactions of 1,3,2-Diselenaphospholanes with
(Pentamethylcyclopentadienyl)rhodium and -iridium
Dichloride
Conceivable products that may result from the reaction
of 1 or 2 with [Cp*RhCl2]2 and [Cp*IrCl2]2 are shown in
Scheme 3. It is assumed that the reactions start with adduct
Scheme 3. Principal products from the reactions of 1 or 2 with [Cp*MCl2]2 (M = Rh, Ir). Products 14 (M = Ir, R = iPr) and 18 (M =
Rh, R = iPr) were isolated and studied by X-ray analysis.
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Table 2. 31P, 77Se, and 13C NMR spectroscopic data[a] of the ortho-carborane derivatives 13–18 (M = Ir, Rh; R = Ph, iPr).
R
Solvent
CD2Cl2
δ31
P
δ77Se
δ13C [C(carb)]
Other δ13
C
13 (M = Ir, R = Ph)
84.4
602.7
74.5 (7.3) {–8.8} 8.8 (1.5) CH3,
95.3 (3.4) C–Me,
1J(77Se,31P) = 370.0 Hz
1J(77Se,31P) = 372.0 Hz
129.0 (11.0) Cm,
131.7 (11.3) Cp,
132.6 (2.5) Co,
134.9 (20.1) Ci
Unassigned insertion
product with Ir (R = Ph)
CD2Cl2
CD2Cl2
109.8
SeP: 694.1
77.8 CSeIr,
88.5 (7.1) CSeP
9.3 (1.5) CH3,
98.2 (3.5) C–Me,
129.2 (12.8) Cm,
131.5 (13.9) Cp,
132.6 (3.1) Co,
134.9 (45.6) Ci
1J(77Se,31P) = 317.5 Hz
1J(77Se,31P) = 317.0 Hz,
SeIr: 299.1
2J(77Se,31P) = 21.5 Hz
Unassigned insertion
products with Ir (R = Ph)
82.4
n.o.
n.o.
CH3: 8.5 (1.9),
1J(77Se,31P) = 373.1 Hz,
104.9,
9.2 (1.8), 9.3 (1.7),
C–Me: 96.6 (3.6),
98.2 (3.8), 99.5 (3.4)
120.3
1J(77Se,31P) = 297.3 Hz
18 (M = Rh, R = Ph)
[D8]toluene 151.0
419.3 (pseudo t)
69.0 (4.4)
9.1 (2.8) CH3 from Cp*,
105.0 Ͻ4.6Ͼ (4.6) C–Me,
127.3 (11.3) Cm,
1J(103Rh,31P) = 213.5 Hz 1J(103Rh,77Se) = 47.5 Hz,
2J(77Se,31P) = 47.8 Hz
2J(77Se,31P) = 47.5 Hz
132.7 (2.4) Cp,
134.7 (10.3) Co,
138.5 (44.3) Ͻ3.5Ͼ Ci
Unassigned Rh
complexes (R = Ph)
[D8]toluene 122.9
n.o.
n.o.
n.o.
1J(103Rh,31P) = 163.6 Hz,
126.4
1J(103Rh,31P) = 154.1 Hz,
138.0
1J(103Rh,31P) = 201.9 Hz,
152.7
1J(103Rh,31P) = 198.8 Hz
14 (M = Rh, R = iPr)
18 (M = Rh, R = iPr)
[D8]toluene 174.4
649.9
n.o.
8.6 (2.1) CH3 from Cp*,
19.1 (2.0) CH3 from iPr,
42.5 CH,
1J(103Rh,31P) = 190.3 Hz 1J(77Se,31P) = 380 Hz,
1J(77Se,31P) = 380.6 Hz
634.8
1J(103Rh,77Se) = 55 Hz
101.3 Ͻ6.7Ͼ (3.5) C–Me
[D8]toluene 194.3
398.9 (pseudo t)
69.4 (4.4) [171.1] 9.4 (2.4) CH3 from Cp*,
20.3 (3.3) CH3 from iPr,
1J(103Rh,31P) = 207.6 Hz 1J(103Rh,77Se) = 43.5 Hz,
2J(77Se,31P) = 42.5 Hz
2J(77Se,31P) = 43.5 Hz
43.4 Ͻ8.8Ͼ (2.8) CH,
105.3 Ͻ4.3Ͼ (4.3) C–Me
Unassigned Rh
complexes (R = iPr)
[D8]toluene 189.8
n.o.
n.o.
n.o.
1J(103Rh,31P) = 192.8 Hz
14 (M = Ir, R = iPr)
CD2Cl2
114.1
SeP: 634.1
56.6 (8.9) {–9.6}, 9.4 (1.7) CH3 from Cp*,
1J(77Se,31P) = 375.9 Hz
1J(77Se,31P) = 375.0 Hz,
SeIr: 521.6
70.8 [144.0]
(5.1) {–9.6}
18.59 (3.1) CH3 from iPr,
18.62 (7.6) [17.6] CH3
from iPr,
2J(77Se,31P) Ͻ 5 Hz
35.7 (18.8) [15.6] CH,
99.2 (3.2) C–Me
Unassigned insertion
products with Ir (R = iPr)
CD2Cl2
152.0
SeP: 595.9
77.3,
84.5 (6.5)
9.6 (1.5) CH3 from Cp*,
19.5 (6.0) CH3 from iPr,
19.6 (7.5) CH3 from iPr,
42.9 (23.1) [9.6] CH,
98.0 (3.6) C–Me
1J(77Se,31P) = 329.2 Hz
1J(77Se,31P) = 329.0 Hz,
SeIr: 300.4
2J(77Se,31P) = 23.7 Hz
165.4
SeP: 547.1
n.o.
9.7 (1.7) CH3 from Cp*,
17.9 (9.4) CH3 from iPr,
19.2 (8.0) CH3 from iPr,
41.0 (20.5) CH,
1J(77Se,31P) = 303.3 Hz
1J(77Se,31P) = 308.6 Hz,
SeIr: 344.2
2J(77Se,31P) = 24.9 Hz
97.9 (3.9) C–Me
n
n
n
[a] Coupling constants J(31P,13C) are given in parentheses (Ϯ0.5 Hz); J(77Se,13C) are given in square brackets [Ϯ0.5 Hz]; J(103Rh,13C)
are given in angled brackets ϽϮ0.5 HzϾ; Δ10/11B[13C(carb)][12] are given in braces {Ϯ0.5 ppb}; isotope-induced chemical shifts Δ are
given in ppb, and the negative sign denotes a shift of NMR spectroscopic signal of the heavy isotopomer to lower frequency; n.o.: not
observed.
1
1
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Figure 3. NMR spectra of the reaction solution starting from 2 and [Cp*IrCl2]2. (A) 202.5 MHz 31P{1H} NMR spectrum (in CD2Cl2,
at 25 °C), the mixture of 13 (M = Ir, R = Ph) and one or several isomers 14–17 (after 3 h at room temp. in CD2Cl2). (B) The same
spectrum as in (A) after 18 h at room temperature (in CD2Cl2). (C) The same spectrum as in (B) in [D8]toluene. (D) 95.4 MHz 77Se
NMR spectrum of the same solution as in (A). (E) 95.4 MHz 77Se NMR spectrum of the same solution as in (B).
formation (Scheme 3, A), by which the metal is coordinated The structures of other Rh complexes initially present in
to phosphorus (12 or 13). Then, insertion of the metal into the reaction solution could not be assigned. Figure 4 shows
one of the P–Se bonds has to be considered (Scheme 3, B), the 31P and 77Se NMR spectra, in which the coupling con-
1
thereby transferring a chlorido ligand from the metal to stants 2J(77Se,Rh,31P) and J(103Rh,31P) are indicative. This
phosphorus. This may lead in principal to at least four dif-
ferent isomers (14, 15, 16, 17) if the conformation shown
for the six-membered rings prevails. For steric reasons, 16
and 17, in which Cp* and iPr or Ph groups are in cis posi-
tions, appear to be less favored than 14 and 15. The inser-
tion might be a prerequisite for exchange (Scheme 3, C),
which affords complexes 18 or 19. Although it proved im-
possible to identify a complete set of examples representing
the three stagesϪadduct, insertion, and exchangeϪfor Rh
and Ir complexes with R = iPr or Ph, we have collected
valuable NMR spectroscopic and crystallographic evidence
in support of the proposed reaction sequence.
NMR spectroscopy, in particular 31P and 77Se, offered
the best chances to monitor the ongoing reactions of 1 and
2 with [Cp*MCl2]2. Thus, in the case of the reaction of
[Cp*IrCl2]2 with 2, the first major product is 13 (M = Ir,
R = Ph), for which the 31P NMR spectroscopic signal is
1
accompanied by 77Se satellites owing to J(77Se,31P) with
relative intensities for two identical 77Se nuclei, and the 77Se
NMR spectrum shows the corresponding doublet (Table 2,
Figure 3, A, D). At least one of the other 31P NMR spec-
troscopic signals seems to belong to an insertion product
(Scheme 3, B: 14–17; only one Se is linked to phosphorus;
Figure 3, B), as indicated by two 77Se NMR spectroscopic
signals split into doublets because of one-bond and two-
bond 77Se,31P spin–spin couplings (Figure 3, E).
Figure 4. NMR spectra of the reaction solution starting from 2 and
[Cp*RhCl2]2. (A) 202.5 MHz 31P{1H} NMR spectrum (in [D8]-
toluene, at 25 °C), the mixture of 18 (M = Rh, R = Ph) and one
or several isomers 12–17 (after 10 min at room temperature in [D8]-
toluene). (B) The same spectrum as in (A) after 30 min at room
temperature. (C) 95.4 MHz 77Se NMR spectrum of the same solu-
By contrast, [Cp*RhCl2]2 reacts much faster with 2, to
give mainly the exchange product 18 (M = Rh, R = Ph). tion as in (B).
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type of complex with a structure analogous to 18, namely, spectroscopic signals [two doublets with large and small
[(B10H10C2Se2)M(Cp*)–PMe3] (M = Rh,[16,17] Ir[17,18]) has coupling constants 1J(77Se,31P) and 2J(77Se,31P)], suggest
been characterized previously, prepared from different that an insertion product had been formed, presumably 14
routes.
(M = Rh, R = iPr), the precursor of 18. Apparently, 14
Similarly, the reaction of 1 with [Cp*RhCl2]2 affords im- rearranges into 18 (isolated and structurally characterized
mediately 18 (M = Rh, R = iPr) as the major product (Fig- by X-ray analysis; see below), which after 24 hours is the
ure 5). However, in the beginning a second product can be sole product together with a small amount of an unidenti-
readily detected, for which 31P and particularly 77Se NMR fied Rh complex.
Figure 5. NMR spectra of the reaction solution starting from 1 and [Cp*RhCl2]2. (A) 202.5 MHz 31P{1H} NMR spectrum (in [D8]-
toluene, at 25 °C), the mixture of 14 (M = Rh, R = iPr) and 18 (M = Rh, R = iPr) (after 30 min at room temperature in [D8]toluene);
in the case of 14 (M = Rh, R = iPr), the relative intensities of the 77Se satellites correspond to one Se linked to phosphorus. (B) The
same spectrum as in (A) after 2 h at room temperature. (C) The same spectrum as in (A, B) after 24 h at room temperature. (D) 95.4 MHz
77Se NMR spectrum of the same solution as in (A) (after 1 h at room temperature in [D8]toluene).
Figure 6. NMR spectra of the reaction solution starting from 1 and [Cp*IrCl2]2. (A) 202.5 MHz 31P{1H} NMR spectrum and 95.4 MHz
77Se NMR spectrum (in CD2Cl2, at 25 °C) of the mixture of 14 (M = Ir, R = iPr) and two isomers (after 3 h at room temperature in
CD2Cl2). (B) 202.5 MHz 31P{1H} NMR spectrum and 95.4 MHz 77Se NMR spectrum of the same mixture in [D8]toluene after 24 h at
room temperature. A certain amount of 14 has crystallized from the solution, and one of the isomers has almost vanished.
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Although insertion products such as 14 appear as likely and 5), leading to isolated samples of 18 (M = Rh, R =
intermediates in going from the adduct to exchange, their iPr).
proposed structures on the basis of NMR spectroscopic
Although chemical shifts (δ77Se) appeared to be most
data need further confirmation. This was provided by the sensitive to structural changes, in particular for insertion
reaction of [Cp*IrCl2]2 with 1. Monitoring of the reaction products, the differences between calculated[20,21] and exper-
by 31P and 77Se NMR spectroscopy measurements (Fig- imental data were rather large and not encouraging for
ure 6) shows the formation of one of the insertion products structural assignment. This is most likely due to limitations
as the major species, subsequently identified as 14 (M = Ir, of the theoretical model used for the metal atoms. Thus,
R = iPr). Of the two minor products, only one could be calculations of δ77Se for the 16-electron complexes
detected after 24 h, and both appear to also be insertion [(B10H10C2Se2)M(Cp*)] (M = Rh, Ir) and their PMe3 ad-
products, on the basis of the combined information from ducts with known structures [using LAN2DZ[19] for Rh and
31P and 77Se NMR spectra. Fortunately, one isomer crys- Ir and the B3LYP/6-311+G(d,p) basis set[14] for all other
tallized from the mixture, and X-ray analysis proved its elements] gave δ77Se values that were wrong by 100–
structure as that of 14 (M = Ir, R = iPr; see below).
150 ppm (see Table S1 in the Supporting Information).
X-ray Analyses of the Metal Complexes
DFT Calculations of Metal Complexes
Attempts at the calculation [B3LYP/6-311+G(d,p),[14] Ir
(LANL2DZ[19])] of optimized gas-phase geometries for 14–
17 (M = Ir, R = iPr) resulted in minima of energy for 14–
16, whereas no minimum was found for 17. The calculations
indicate that 14 is lower in energy than 15 (by
1.5 kcalmol–1) and 16 (by 5.9 kcalmol–1). Indeed, 14 (M =
Ir, R = iPr) turned out to be the major product in the reac-
tion solution. Crystals could be grown, suitable for X-ray
analysis (see below).
Calculated (at the same level) optimized structures were
found as minima for 13 and 18 (M = Rh, Ir, R = iPr) (not
for 12 and 19!). In the cases of isomers 13, 14, and 18 (M
= Rh, R = iPr) the comparison of the respective energies
suggests that the exchange product 18 is of lowest energy,
followed by the insertion product 14 (plus 7.0 kcalmol–1)
and the initial adduct 13 (plus a further 9.9 kcalmol–1).
This is in agreement with experimental results (see Figures 4
The molecular structures of 18 (M = Rh, R = iPr) and
14 (M = Ir, R = iPr) are shown in Figures 7 and 8, respec-
tively (see also Table 3). Intermolecular interactions appear
to be negligible. Several attempts failed to obtain more suit-
able crystals for a more reliable data set of 18 (M = Rh, R
= iPr; see the Supporting Information). However, the main
structural features could be determined beyond doubt (see
the Supporting Information; Tables S2–S5), and the anal-
ogy to the known structure of [(B10H10C2Se2)Rh(Cp*)–
PMe3][16] became clearly apparent. The five-membered
CCSeSeRh ring in 18 is nonplanar with the Rh shifted by
80.7 pm out of the SeCCSe plane. This property and other
structural parameters compare well with the known data.[16]
Figure 8. ORTEP plot (50% probability; hydrogen atoms are omit-
ted for clarity) of the molecular structure of 14 (M = Ir, R = iPr)
(for selected bond lengths and angles, see Table 3).
There are no structural data of metal complexes available
to be compared with 14 (M = Ir, R = iPr). Most of the
bond lengths and angles are found in the usual range (see
Table 3). The bond angle C(1)–Se(1)–Ir [110.2(3)°] is less
acute, as one might expect [e.g., C(2)–Se(2)–P: 103.9(3)°].
Both iridium and phosphorus are in the centers of severely
distorted tetrahedrons. The conformation of the six-mem-
bered ring is reminiscent of the corresponding disilane de-
Figure 7. Molecular structure of 18 (M = Rh, R = iPr). Selected
bond lengths [pm] and angles [°]: C(1)–C(2) 167.9, C(1)–Se(1)
199.5, C(2)–Se(2) 190.2, Se(1)–Rh 248.0, Se(2)–Rh 246.2, Rh–P
221.5; Se(1)–Rh–Se(2) 90.8, Se(1)–Rh–P 92.0, Se(2)–Rh–P 87.8,
Rh–Se(1)–C(1) 102.5, Rh–Se(2)–C(2) 101.7, Se(1)–C(1)–C(2) 118.7,
Se(2)–C(2)–C(1) 123.5, Se(1)–Rh–Cp*(Z) 122.5, Se(2)–Rh–Cp*(Z)
124.2, P–Rh–Cp*(Z) 128.6, plane Se(1)–C(1)–C(2)–Se(2)/plane
Se(1)–Rh–Se(2) 152.4°.
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FULL PAPER
an atmosphere of argon. The starting 1,3,2-diselenaphospholanes
1 and 2 were prepared according to a published procedure.[7] Other
starting materials were purchased from Aldrich {BH3 (1.0 m in
THF), BH3–SMe2, HBBr2–SMe2 (1.0 m in CH2Cl2), [Cp*IrCl2]2,
[Cp*RhCl2]2}. Most syntheses were carried out on a small scale
sufficient for NMR spectroscopy studies. Because of the small scale
of the reactions, the sensitivity to hydrolysis, and the multiple reac-
tion pathways, it proved difficult to obtain materials suitable for
elemental analysis. Furthermore, small carbon and high boron con-
tent caused problems in reproducibility. NMR spectroscopy mea-
Table 3. Selected experimental and calculated bond lengths [pm]
and angles [°] of ortho-carborane derivative 14 (M = Ir, R = iPr).
14 (M = Ir, 14 (M = Ir,
R = iPr)
R = iPr) (calcd.)
C(1)–Se(1)
C(2)–Se(2)
C(1)–C(2)
193.9(9)
193.5(9)
167.8(13)
196.3
195.9
169.6
Se(1)–Ir
248.41(10) 254.2
Se(2)–P
Ir–P
P–Cl(1)
P–C(3)
226.1(2)
226.0(2)
206.7(3)
185.3(9)
239.6(2)
110.2(3)
103.9(3)
118.5(6)
120.3(5)
92.96(6)
81.51(6)
88.79(8)
124.5
231.0
231.3
213.0
190.0
246.1
110.4
104.3
119.4
120.2
91.8
82.7
90.1
–
1
surements: Bruker DRX 500: H, 11B, 13C, 31P, and 77Se; chemical
shifts are given relative to Me4Si [δ1H (CHDCl2) = 5.33 ppm,
(C6D5CD2H) = 2.08 ppm (Ϯ0.01); δ13C (CD2Cl2) = 53.8 ppm,
(C6D5CD3) = 20.4 ppm (Ϯ0.1)]; external BF3/OEt2 [δ11B = 0 ppm
(Ϯ0.3) for Ξ(11B) = 32.083971 MHz], neat Me2Se [δ77Se = 0 ppm
(Ϯ0.1) for Ξ(77Se) = 19.071523 MHz], external aqueous H3PO4
(85%) [δ31P = 0 ppm for Ξ(31P) = 40.480747 MHz]. Assignments
of 1H and 11B NMR spectroscopy signals are based on 1H{11B}
selective heteronuclear decoupling experiments. Mass spectra (EI,
70 eV): Finnigan MAT 8500 with direct inlet (data for 12C, 1H, 11B,
31P, 80Se, 103Rh, 193Ir). Melting points (uncorrected) were deter-
mined using a Büchi 510 melting-point apparatus.
Ir–Cl(2)
Ir–Se(1)–C(1)
P–Se(2)–C(2)
Se(1)–C(1)–C(2)
Se(2)–C(2)–C(1)
Se(1)–Ir–P
Se(1)–Ir–Cl(2)
P–Ir–Cl(2)
Se(1)–Ir–Cp*(Z)
Cl(2)–Ir–Cp*(Z)
P–Ir–Cp*(Z)
Se(2)–P–Ir
Se(2)–P–C(3)
Se(2)–P–Cl(1)
Ir–P–C(3)
119.3
134.1
–
–
120.56(10) 121.4
95.4(3) 99.0
102.23(11) 102.4
117.7(3) 117.5
115.81(12) 111.7
101.5(3)
0.8
2.2
All quantum-chemical calculations were carried out using the
Gaussian 09 program package.[23] Optimized geometries at the
B3LYP/6-311+G(d,p) level of theory,[14] and LANL2DZ[19] for Rh
and Ir, were found to be minima by the absence of imaginary fre-
quencies. NMR spectroscopy parameters were calculated[24,25] at
the same level of theory. Calculated chemical shifts δ13C, δ31P, δ11B,
and δ77Se were converted by δ13C(calcd.) = σ(13C, TMS) – σ(13C),
with σ(13C, TMS) = +181 ppm [δ13C (TMS) = 0 ppm], δ31P(calcd.)
= σ[31P, P(OMe)3] – σ(31P) + 138, with σ[31P, P(OMe)3] =
159.8 ppm {δ31P = 138 ppm and δ31P[aqueous H3PO4 (85%) =
0 ppm]}, δ11B (calcd.) = σ(11B, B2H6) – σ(11B) + 18, with σ(11B,
B2H6) = +84.1 ppm [δ11B (B2H6) = 18 ppm and δ11B (BF3/OEt2) =
0 ppm], and δ77Se(calcd.) = σ(77Se, SeMe2) – σ(77Se), with σ(77Se,
SeMe2) = +1621.7 ppm [δ77Se(SeMe2) = 0 ppm].
Ir–P–Cl(1)
C(3)–P–Cl(1)
Plane Se(1)–C(1)–C(2)–Se(2), Δ [pm]
102.0
–
–
[a]
¯
[a]
¯
Plane Se(1)–Ir–P–Se(2), Δ [pm]
Plane Se(1)–C(1)–C(2)–Se(2) /
plane Se(1)–Ir–P–Se(2) [°]
121.5
–
[a] Mean deviation from plane.
rivative B10H10C2Se2(SiMe2)2,[22] in which the four atoms
SeCCSe also form a plane.
Reaction of 1 with BH3/THF: A solution of 1 (0.25 mmol) in [D8]-
toluene (0.6 mL) was cooled to –30 °C and a solution of BH3/THF
in THF (0.25 mL of a 1.0 m solution in THF, 0.25 mmol) was
added through a microsyringe. The progress of the reaction was
Conclusion
The 1,3,2-diselenaphospholanes studied here react with
greatly different Lewis acids such as borane or transition- monitored by 31P, 1H, and 11B NMR spectroscopy. After 15 min
at room temperature, the formation of a light green solution was
observed, and the mixture contained 1 (25%) and 3 (75%). Volatile
materials were removed under vacuum to give a mixture containing
1 (20%), 3 (75%), and 4 (5%). After 20 h in [D8]toluene at room
temperature, the mixture contained 1 (35%), 3 (25%), 4 (32%),
and 4Ј(8%) (see Figures 1 and 2) together with HnB(OBu)3–n (see
Figure 2B). Products 3, 4, and 4Ј decompose in [D8]toluene at room
temperature with an excess amount of a solution of BH3/THF in
THF. Data for 3: 1H{11B} NMR (500.13 MHz, [D8]toluene, 25 °C):
δ = 0.85 [dd, 3J(31P,1H) = 22.0, 3J(1H,1H) = 7.0 Hz, 6 H, CH3],
metal fragments in a surprisingly similar way: The initial
formation of adducts involving the lone pair of electrons at
phosphorus is followed by insertion of the Lewis acid into
one of the P–Se bonds. Finally, the phosphorus is displaced
from the ring, and the exchange products turn out to be
favored. The consecutive steps of these reactions can be
monitored by multinuclear magnetic resonance spec-
troscopy (1H, 11B, 31P, 77Se NMR). The quantum-chemical
analysis of the optimized gas-phase structures for adduct-,
insertion-, and exchange products supports the proposed 1.62 [d, 2J(31P,1H) = 6.7 Hz, 3J(77Se,1H) = 15.6 Hz, 3 H, BH3], 2.34
[dsept, J(31P,1H) = 14.2 Hz, J(1H,1H) = 7.0 Hz, 1 H, PCH], 2.44
(br. s, 1 H, HB), 2.53 (m, 3 H, HB), 2.73 (m, 5 H, HB), 3.02 (br.
s, 1 H, HB) ppm. 11B{1H} NMR (160.5 MHz, [D8]toluene, 25 °C):
δ = –35.3 (1 B, BH3), –10.2 (2 B), –8.5 (2 B), –6.1 (2 B), –4.8 (2
B), –4.1 (1 B), –1.0 (1 B) ppm. 11B NMR (160.5 MHz, [D8]toluene,
25 °C): δ = –35.3 [q, 1J(11B,1H) = 100 Hz, 1B, BH3], –10.2 [d,
1J(11B,1H) = 178 Hz, 2B], –8.5 [d, 1J(11B,1H) = 175 Hz, 2B], –6.1
[d, 1J(11B,1H) = 165 Hz, 2B], –4.8 [d, 1J(11B,1H) = 160 Hz, 2 B],
–4.1 (1 B), –1.0 [d, 1J(11B,1H) = 181 Hz, 1B] ppm. Data for 4:
2
3
reaction pathway. In the case of insertion product 14 (M =
Ir, R = iPr), a novel type of structure was determined.
Experimental Section
General: All syntheses and the handling of the samples were carried
out by observing necessary precautions to exclude traces of air and
moisture. Carefully dried solvents and oven-dried glassware were
used throughout. CD2Cl2 was distilled from CaH2 in an atmo-
sphere of argon. All other solvents were distilled from Na metal in
1H{11B}
NMR
(500.13 MHz,
[D8]-
toluene, 25 °C): δ = 0.56 [dd, 3J(31P,1H) = 18.9 Hz, 3J(1H,1H) =
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7.1 Hz, 6 H, CH3], 2.45 (m, 2 H, BH2), 2.59 (m, 1 H, PCH), 4.20 ene, 25 °C): δ = –48.3 [tm, 1J(31P,1H) = 375 Hz] ppm. 31P{1H}
[ddt, 1J(31P,1H) = 402 Hz, 3J(1H,1HCH) = 8.0 Hz, 3J(1H,1HBH) = NMR (202.5 MHz, [D8]toluene, 25 °C): δ = –48.3 [m, 1J(31P,11B) =
1
5.8 Hz, 1 H, PH] ppm. Data for 4Ј: H NMR (500.13 MHz, [D8]- 36 Hz] ppm.
toluene, 25 °C): δ = 4.20 [dm, 1J(31P,1H) = 380.4 Hz, 1 H, PH] ppm.
Reaction of 2 with BH3/THF: A solution of 2 (0.11 mmol) in [D8]-
toluene (0.6 mL) was cooled to –30 °C and a solution of BH3/THF
in THF (0.11 mL of a 1.0 m solution in THF, 0.11 mmol) was
added through a microsyringe. The progress of the reaction was
monitored by 31P, 1H, and 11B NMR spectroscopy. After 15 min at
room temperature, the mixture contained 1 (75%) and 10 (25%).
Product 10 decomposes in [D8]toluene at room temperature with
an excess amount of a solution of BH3/THF in THF.
Reaction of 1 with BH3–SMe2: A solution of 1 (0.14 mmol) in [D8]-
toluene (0.6 mL) was cooled to –30 °C and BH3–SMe2 (0.013 mL,
0.14 mmol) was added through a microsyringe. The progress of the
reaction was monitored by 31P, 1H, and 11B NMR spectroscopy.
After 1 d at room temperature, the mixture contained 1 (80%) and
3 (20%). The second portion of BH3–SMe2 (0.05 mL) was added
to the reaction mixture. After 1 d at room temperature, the mixture
contained 1 (65%) and 3 (35%). Volatile materials were removed
under vacuum to give a mixture containing 1 (15%) and 3 (85%).
BH3–SMe2 (0.05 mL) was added to the reaction mixture in [D8]-
toluene. After 15 min at room temperature, the mixture contained
1 (70%) and 3 (30%); after 1 month at room temperature, the mix-
ture contained 6,[11] 7, H3P–BH3, and several unidentified materi-
Reaction of 2 with [Cp*IrCl2]2: A solution of 2 (0.108 mmol) in
CD2Cl2 (0.6 mL) was cooled to 0 °C and added to degassed
[Cp*IrCl2]2 (43 mg, 0.054 mmol). The progress of the reaction was
monitored by 31P and 77Se NMR spectroscopy. After 3 h at room
temperature, the color of the solution changed from dark red to
green, and the mixture contained 13 (M = Ir, R = Ph) as the major
product (ca. 75%) and several unidentified insertion Ir complexes
(see Figure 3, A, D). After 18 h at room temperature, the mixture
contained 13 (M = Ir, R = Ph) (30%) and one of the insertion
products as the major product (δ31P = 109.8 ppm) (55%) (see Fig-
ure 3, B, E). Data for 13 (M = Ir, R = Ph): 1H{11B} NMR
1
als. Data for H2(iPr)P–BH3 (7): H NMR (500.13 MHz, [D8]tolu-
ene, 25 °C): δ = 0.85 [dd, 3J(31P,1H) = 16.9 Hz, 3J(1H,1H) = 7.0 Hz,
6 H, CH3], 3.81 [ddq, 1J(31P,1H) = 355.3 Hz, 3J(1H,1HCH) = 7.7 Hz,
3J(1H,1HBH) = 5.5 Hz, 2 H, PH2] ppm. 11B NMR (160.5 MHz, [D8]-
1
1
toluene, 25 °C): δ = –42.5 [dq, J(11B,1H) = 100 Hz, J(31P,11B) =
36 Hz] ppm. 31P NMR (202.5 MHz, [D8]toluene, 25 °C): δ = –28.1
4
(500.13 MHz, CD2Cl2, 25 °C): δ = 1.42 [d, J(31P,1H) = 3.3 Hz, 15
[tm, J(31P,1H) = 355 Hz] ppm. 31P{1H} NMR (202.5 MHz, [D8]-
1
H, CH3], 2.06 [br. s, 1 H, HB for δ(11B) = –10.6 ppm], 2.13 [br. s,
1 H, HB for δ(11B) = –7.5 ppm], 2.18 [br. s, 2 H, HB for δ(11B) =
–5.2 ppm], 2.40 (m, 5 H, HB), 3.14 [br. s, 1 H, HB for δ(11B) =
–0.8 ppm], 7.51 (m, 1 H, Ph), 7.56 (m, 2 H, Ph), 8.01 (m, 2 H, Ph)
ppm. 11B{1H} NMR (160.5 MHz, CD2Cl2, 25 °C): δ = –10.6 (3 B),
–8.6 (2 B), –7.5 (1 B), –5.1 (3 B), –0.8 (1 B) ppm.
1
toluene, 25 °C): δ = –28.1 [m, J(31P,11B) = 35 Hz] ppm. 13C{1H}
NMR (125.8 MHz, [D8]toluene, 25 °C): δ = 19.7 [CH3, J(31P,13C)
2
= 1.7 Hz], 28.4 [CH, 1J(31P,13C) = 12.6 Hz] ppm. Data for H3P–
BH3: 11B NMR (160.5 MHz, [D8]toluene, 25 °C): δ = –38.5 [dq,
1J(11B,1H) = 95.6 Hz, 1J(31P,11B) = 45.8 Hz, BH3] ppm. 31P{1H}
NMR (202.5 MHz, [D8]toluene, 25 °C): δ = –39.1 ppm.
Reaction of 2 with [Cp*RhCl2]2: A solution of 2 (0.108 mmol) in
[D8]toluene (0.6 mL) was cooled to 0 °C and added to degassed
solid [Cp*RhCl2]2 (33.3 mg, 0.054 mmol). The progress of the reac-
tion was monitored by 31P and 77Se NMR spectroscopy. After
10 min at room temperature, the mixture contained 18 (M = Rh,
R = Ph) as the major product (ca. 70%) and several unidentified
intermediate Rh complexes (see Figure 4, A). After 30 min at room
temperature, the solution contained 18 (M = Rh, R = Ph) (Ͼ95%)
(see Figure 4, B, C). 1H{11B} NMR (500.13 MHz, [D8]-
Reaction of 1 with Br2BH–SMe2: A solution of 1 (0.15 mmol) in
[D8]toluene (0.6 mL) was cooled to –30 °C and Br2BH–SMe2
(0.15 mL of a 1.0 m solution in CH2Cl2, 0.15 mmol) was added
through a microsyringe. The progress of the reaction was moni-
tored by 31P, 1H, and 11B NMR spectroscopy. After 1 d at room
temperature, the mixture contained 1 (96%) and iPrPBr2 (4%)
(from 31P NMR spectra). The second portion of Br2BH–SMe2
(0.2 mL of a 1.0 m solution in CH2Cl2) was added to the reaction
mixture. After 1 d at room temperature, the mixture contained 1
(94%) and iPrPBr2 (6%). Volatile materials were removed under
vacuum to give a mixture containing 1 (98%) and iPrPBr2 (1–2%).
BH3–SMe2 (0.2 mL of a 1.0 m solution in CH2Cl2) was added to
the reaction mixture in [D8]toluene. After 1 month at room tem-
perature, the mixture contained 1 (ca. 80%), iPrPBr2, 6,[11] the di-
mer 8,[7] and bis(diselane) 9.[13] Data for iPrPBr2: 1H NMR
(500.13 MHz, [D8]toluene, 25 °C): δ = 0.85 [dd, 3J(31P,1H) =
15.4 Hz, 3J(1H,1H) = 6.9 Hz, 6 H, CH3], 2.60 (m, 1 H, PCH) ppm.
31P NMR (202.5 MHz, [D8]toluene, 25 °C): δ = 203.1 [dsept,
4
toluene, 25 °C): δ = 1.41 [d, J(31P,1H) = 6.6 Hz, 15 H, CH3], 2.45
[br. s, 1 H, HB for δ(11B) = –5.9 ppm], 2.57 [br. s, 2 H, HB for
δ(11B) = –7.3 ppm], 2.63 [br. s, 2 H, HB for δ(11B) = –9.5 ppm],
2.74 [br. s, 1 H, HB for δ(11B) = –4.0 ppm], 2.80 [br. s, 1 H, HB for
δ(11B) = –7.3 ppm], 3.00 [br. s, 3 H, HB for δ(11B) = –4.0, –5.9,
–7.3 ppm], 7.08 (m, 3 H, Ph), 7.99 [m, 2 H, Ho from Ph, 3J(31P,1H)
= 11.7 Hz] ppm. 11B{1H} NMR (160.5 MHz, [D8]toluene, 25 °C):
δ = –9.5 (2 B), –7.3 (4 B), –6.0 (2 B), –4.1 (2 B) ppm. 11B NMR
1
(160.5 MHz, [D8]toluene, 25 °C): δ = –9.5 [d, J(11B,1H) = 166 Hz,
2B], –7.3 [d, 1J(11B,1H) = 145 Hz, 4B], –6.0 [d, 1J(11B,1H) = 150 Hz,
2
3J(31P,1H) = 15.4 Hz, J(31P,1H) = 20.4 Hz, 1 P] ppm.
1
2B], –6.0 [d, J(11B,1H) = 159 Hz, 2B] ppm.
Reaction of 2 with BH3–SMe2: A solution of 2 (0.11 mmol) in [D8]- Reaction of 1 with [Cp*RhCl2]2: A solution of 1 (0.146 mmol) in
toluene (0.6 mL) was cooled to –30 °C and BH3–SMe2 (0.05 mL,
0.55 mmol) was added through a microsyringe. The progress of the
reaction was monitored by 31P, 1H, and 11B NMR spectroscopy.
After 4 d at room temperature, the mixture contained 2 (95%) and
10 (5%). The second portion of BH3–SMe2 (0.1 mL) was added to
[D8]toluene (0.6 mL) was cooled to –30 °C and added to degassed
solid [Cp*RhCl2]2 (45 mg, 0.073 mmol). The formation of a dark
red solution was observed. The progress of the reaction was moni-
tored by 31P and 77Se NMR spectroscopy. After 30 min at room
temperature, the mixture contained 14 (M = Rh, R = iPr) (40%)
and 18 (M = Rh, R = iPr) (55%) as the major products (see Fig-
the reaction mixture. After 2 d at room temperature, the mixture
contained 6[11] and H2(Ph)P–BH3
together with BH3–SMe2. ure 5, A). After 2 h at room temperature, the mixture contained 18
[15]
1
Data for H2(Ph)P–BH3 (11): H NMR (500.13 MHz, [D8]toluene, (M = Rh, R = iPr) (85%) as the major product and only 7% of
1
25 °C): δ = 4.85 [dq, J(31P,1H) = 372.5 Hz, 3J(1H,1HBH) = 7.9 Hz,
the insertion complex 14 (M = Rh, R = iPr) (see Figure 5, B). After
24 h at room temperature, the solution contained 18 (M = Rh, R
2 H, PH2], 7.04 (m, 3 H, Ph), 7.28 (m, 2 H, Ph) ppm. 11B NMR
(160.5 MHz, [D8]toluene, 25 °C): δ = –41.8 [dq, 1J(11B,1H) = = iPr) (Ͼ95%) together with other unidentified Rh complex (see
103 Hz, 1J(31P,11B) = 33 Hz] ppm. 31P NMR (202.5 MHz, [D8]tolu-
Figure 5, C). Single red crystals of 18 (M = Rh, R = iPr) were
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grown from a solution in [D8]toluene after 1 week at room tempera-
ture; m.p. 195–205 °C (decomposition). The principle structure
(Figure 7) was confirmed by X-ray analysis, although the presence
of disorder as well as twinning prevented an exact determination
of a meaningful data set (see the Supporting Information). Data
for 14 (M = Rh, R = iPr): 1H NMR (500.13 MHz, [D8]toluene,
25 °C): δ = 1.03 [d, 3J(31P,1H) = 6.7 Hz, 3 H, CH3], 1.06 [dd,
3J(31P,1H) = 7.7 Hz, 3J(1H,1H) = 6.7 Hz, 3 H, CH3], 1.31 [d,
4J(31P,1H) = 4.6 Hz, 15 H, CH3], 3.36 [m, 1 H, PCH] ppm. Data
Table 4. Crystallographic data of the ortho-carborane derivative 14
(M = Ir, R = iPr).
14 (M = Ir, R = iPr)
Formula
Crystal
C15H32B10Cl2IrPSe2
orange block
0.12ϫ0.11ϫ0.11
133(2)
monoclinic
P21/n
Dimensions [mm3]
Temperature [K]
Crystal system
Space group
Lattice parameters
a [pm]
1
for 18 (M = Rh, R = iPr): H{11B} NMR (500.13 MHz, [D8]tolu-
ene, 25 °C): δ = 1.33 [dd, 3J(31P,1H) = 14.1 Hz, 3J(1H,1H) = 7.3 Hz,
913.96(18)
4
6 H, CH3], 1.36 [d, J(31P,1H) = 5.0 Hz, 15 H, CH3], 2.52 [br. s, 1
b [pm]
1329.8(3)
H, HB for δ(11B) = –5.6 ppm], 2.63 [br. s, 2 H, HB for δ(11B) =
–7.3, –9.0 ppm], 2.85 [br. s, 1 H, HB for δ(11B) = –7.3 ppm], 2.96
[br. s, 2 H, HB for δ(11B) = –11.4 ppm], 3.02 [br. s, 1 H, HB for
δ(11B) = –3.8 ppm], 3.09 [br. s, 2 H, HB for δ(11B) = –5.6,
–7.3 ppm], 3.40 [br. s, 1 H, HB for δ(11B) = –2.4 ppm], 3.87 [dsept,
2J(31P,1H) = 14.8 Hz, 3J(1H,1H) = 6.8 Hz, 1 H, PCH] ppm. 11B{1H}
NMR (160.5 MHz. CD2Cl2, 25 °C): δ = –11.4 (1 B), –9.0 (2 B),
–7.3 (3 B), –5.6 (2 B), –3.8 (1 B), –2.4 (1 B) ppm. EI-MS (70 eV)
c [pm]
β [°]
2232.2(5)
94.80(3)
4
Z
μ [mm–1]
7.893
Diffractometer
STOE IPDS II; Mo-Kα, λ = 71.073 pm
graphite monochromator
1.78–25.74
5116
3934
Measuring range (ϑ) [°]
Reflections collected
Independent reflections
[IՆ2σ(I)]
Absorption correction
Max./min. transmission
Refined parameters
wR2/R1 [IՆ2σ(I)]
for C15H32B10Cl2PSe2Rh (683.2): m/z (%) = 539 (100) [M+
–
Cl2PC3H7], 522 (3), 453 (6), 441 (5), 398 (40) [C10H15Se2Rh+], 269
(10), 238 (20) [C10H15Rh+].
numerical
0.5681/0.2675
280
0.108/0.043
2.941/–2.561
Reaction of 1 with [Cp*IrCl2]2: A solution of 1 (0.152 mmol) in
CD2Cl2 (0.6 mL) was cooled to 0 °C and added to degassed solid
[Cp*IrCl2]2 (60.5 mg, 0.075 mmol). The progress of the reaction
was monitored by 31P and 77Se NMR spectroscopy. After 3 h at
room temperature, the color of the solution changed from dark red
to yellowish brown, and the mixture contained 14 (M = Ir, R =
iPr) as the major product (ca. 75%) and two other unidentified
insertion Ir complexes (see Figure 6, A). After 24 h at room tem-
perature, the color of the solution changed to green, and the mix-
ture contained 14 (M = Ir, R = iPr) (60%) and one of the insertion
products (δ31P = 152.0 ppm) (35%) as the major products (see Fig-
ure 6, B). Volatile materials were removed under vacuum (3 h,
8ϫ10–3 torr), and the residue was dissolved in [D8]toluene. Single
orange crystals of 14 (M = Ir, R = iPr) for X-ray analysis were
grown from a solution in [D8]toluene after 1 week at room tempera-
ture; m.p. 235–245 °C (decomposition). Data for 14 (M = Ir, R =
iPr): 1H NMR (500.13 MHz, CD2Cl2, 25 °C): δ = 1.25 [dd,
3J(31P,1H) = 24.4 Hz, 3J(1H,1H) = 6.8 Hz, 3 H, CH3], 1.45 [dd,
3J(31P,1H) = 17.4 Hz, 3J(1H,1H) = 6.8 Hz, 3 H, CH3], 1.73 [d,
4J(31P,1H) = 3.4 Hz, 15 H, CH3], 3.40 [dsept, 2J(31P,1H) = 10.9 Hz,
Max./min. residual electron
density [epm–3 10–6]
Acknowledgments
Support of this work by the Deutsche Forschungsgemeinschaft
(DFG) is gratefully acknowledged.
[1] M. A. Pudovik, V. V. Ovchinnikov, R. A. Cherkasov, A. N. Pu-
dovik, Russ. Chem. Rev. 1983, 52, 361–376.
[2] a) K. B. Dillon, A. E. Goeta, P. K. Monks, H. J. Shepherd,
Polyhedron 2010, 29, 606–612; b) M. Freytag, J. Grunenberg,
P. G. Jones, R. Schmutzler, Z. Anorg. Allg. Chem. 2008, 634,
1256–1266; c) T. L. Schull, D. A. Knight, Tetrahedron: Asym-
metry 1999, 10, 207–211; d) R. Mendes Matos, R. F. F. da Co-
sta, B. de F. Trigo Passos, J. Braz. Chem. Soc. 1999, 10, 21–24;
e) M. E. Squires, D. J. Sardella, L. B. Kool, Organometallics
1994, 13, 2970–2978.
[3] J. P. Dutasta, J. Martin, J. B. Robert, Heterocycles 1980, 14,
3J(1H,1H)
= 6.8 Hz, 1 H, PCH] ppm. EI-MS (70 eV) for
1631–1648.
C15H32B10Cl2PSe2Ir (772.5): m/z (%) = 774 (2) [MH+], 737 (100)
[M+ – Cl], 694 (20) [M+ – Se], 658 (6) [M+ – Se – Cl], 628 (35)
[M+ – Cl2PC3H7], 531 (10), 363 (50) [C10H15IrCl+].
[4] B. Wrackmeyer, E. V. Klimkina, W. Milius, Eur. J. Inorg. Chem.
2014, 233–246.
[5] a) P. Shejwalkar, S. L. Sedinkin, E. B. Bauer, Inorg. Chim. Acta
2011, 366, 209–218; b) S. Costin, S. L. Sedinkin, E. B. Bauer,
Tetrahedron Lett. 2009, 50, 922–925; c) C. E. Strasser, S.
Cronje, H. Schmidbaur, H. G. Raubenheimer, J. Organomet.
Chem. 2006, 691, 4788–4796; d) D. Seyferth, K. S. Brewer,
G. B. Womack, C. M. Archer, J. Organomet. Chem. 1993, 446,
167–175; e) J. Grobe, D. Le Van, J. Szameitat, J. Organomet.
Chem. 1985, 289, 341–355.
[6] a) B. Wrackmeyer, Z. García Hernández, R. Kempe, M. Herb-
erhold, Z. Anorg. Allg. Chem. 2007, 633, 851–857; b) Z.
García Hernández, B. Wrackmeyer, R. Kempe, M. Herberhold,
ARKIVOC (Gainesville, FL, U.S.) 2008, 65–80.
Crystal Structure Determination of 14 (M = Ir, R = iPr): Structure
solutions and refinements were carried out with the program pack-
age SHELXTL-PLUS v.5.1.[26] Details pertinent to the crystal
structure determination are listed in Table 4. Crystals of appropri-
ate size were sealed under argon in Lindemann capillaries, and the
data collections were carried out at 133 K.
CCDC-1005609 [14 (M = Ir, R = iPr), at –133 K] contains the
supplementary crystallographic data for this paper. These data can
be obtained free of charge from The Cambridge Crystallographic
Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
[7] B. Wrackmeyer, E. V. Klimkina, W. Milius, Eur. J. Inorg. Chem.
2014, 1929–1948.
[8] B. Wrackmeyer, E. V. Klimkina, W. Milius, Eur. J. Inorg. Chem.
2012, 2908–2915.
[9] a) H. Duddeck, Prog. Nucl. Magn. Reson. Spectrosc. 1995, 27,
1–323; b) H. Duddeck, Annu. Rep. NMR Spectrosc. 2004, 52,
105–166.
Supporting Information (see footnote on the first page of this arti-
cle): Calculated and experimental chemical shifts (δ77Se) of some
Rh and Ir complexes are compared, and the problems with the X-
ray analysis of 18 (M = Rh, R = iPr) are reported.
Eur. J. Inorg. Chem. 0000, 0–0
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FULL PAPER
[10] A. Staubitz, A. P. M. Robertson, M. E. Sloan, I. Manners,
Chem. Rev. 2010, 110, 4023–4078.
[11] B. Wrackmeyer, E. V. Klimkina, W. Milius, Polyhedron 2010,
29, 2324–2334.
[21] a) T. W. Keal, D. J. Tozer, Mol. Phys. 2005, 103, 1007–1011; b)
T. W. Keal, D. J. Tozer, J. Chem. Phys. 2004, 121, 5654–5660;
c) S. F. Machado, G. G. Camiletti, A. Canal Neto, F. E. Jorge,
R. S. Jorge, Mol. Phys. 2009, 107, 1713–1727.
[12] B. Wrackmeyer, Z. García Hernández, J. Lang, O. L. Tok, Z.
Anorg. Allg. Chem. 2009, 635, 1087–1093.
[13] B. Wrackmeyer, Z. García Hernández, R. Kempe, M. Herber-
hold, Eur. J. Inorg. Chem. 2007, 239–246.
[22] B. Wrackmeyer, E. V. Klimkina, W. Milius, Appl. Organomet.
Chem. 2010, 24, 25–32.
[23] M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria,
M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B.
Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li,
H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Son-
nenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hase-
gawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai,
T. Vreven, J. A. Montgomery Jr., J. E. Peralta, F. Ogliaro, M.
Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Starov-
erov, T. Keith, R. Kobayashi, J. Normand, K. Raghavachari,
A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N.
Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V.
Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Strat-
mann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W.
Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski,
G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D.
Daniels, O. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski,
D. J. Fox, Gaussian 09, revision A.02, Gaussian, Inc., Wall-
ingford CT, USA, 2010.
[14] a) A. D. Becke, J. Chem. Phys. 1993, 98, 5648–5652; b) C. Lee,
W. Yang, R. G. Parr, Phys. Rev. B 1988, 41, 785–789; c) P. J.
Stevens, F. J. Devlin, C. F. Chablowski, M. J. Frisch, J. Phys.
Chem. 1994, 98, 11623–11627; d) D. McLean, D. G. S. Chan-
dler, J. Chem. Phys. 1980, 72, 5639–5648; e) R. Krishnan, J. S.
Blinkley, R. Seeger, J. A. Pople, J. Chem. Phys. 1980, 72, 650–
654.
[15] a) K. Bourumeau, A.-C. Gaumont, J.-M. Denis, J. Organomet.
Chem. 1997, 529, 205–213; b) K. Bourumeau, A.-C. Gaumont,
J.-M. Denis, Tetrahedron Lett. 1997, 38, 1923–1926.
[16] M. Herberhold, G.-X. Jin, H. Yan, W. Milius, B. Wrackmeyer,
J. Organomet. Chem. 1999, 587, 252–257.
[17] L. Jain, V. K. Jain, N. Kushwah, M. K. Palb, A. P. Wadawale,
V. I. Bregadze, S. A. Glazun, Coord. Chem. Rev. 2014, 258–259,
72–118.
[18] M. Herberhold, G.-X. Jin, H. Yan, W. Milius, B. Wrackmeyer,
Eur. J. Inorg. Chem. 1999, 873–875.
[24] K. Wollinski, J. F. Hinton, P. J. Pulay, J. Am. Chem. Soc. 1990,
[19] a) P. J. Hay, W. R. Wadt, J. Chem. Phys. 1985, 82, 270–283; b)
W. R. Wadt, P. J. Hay, J. Chem. Phys. 1985, 82, 284–298; c) P. J.
Hay, W. R. Wadt, J. Chem. Phys. 1985, 82, 299–310.
[20] a) M. Bühl, W. Thiel, U. Fleischer, W. Kutzelnigg, J. Phys.
Chem. 1995, 99, 4000–4007; b) M. Bühl, J. Gauss, J. F. Stanton,
112, 8251–8260.
[25] a) T. Helgaker, M. Jaszunski, M. Pecul, Prog. Nucl. Magn. Re-
son. Spectrosc. 2008, 53, 249–268; b) R. H. Contreras, V. Ba-
rone, J. C. Facelli, J. E. Peralta, Annu. Rep. NMR Spectrosc.
2003, 51, 167–260.
Chem. Phys. Lett. 1995, 241, 248–252; c) A. V. Afonin, D. V. [26] G. M. Sheldrick, SHELX-97, Program for Crystal Structure
Pavlov, I. A. Ushakov, E. Yu. Schmidt, A. I. Mikhaleva, Magn.
Reson. Chem. 2009, 47, 879–884; d) B. A. Demko, K. Eichele,
R. E. Wasylishen, J. Phys. Chem. A 2006, 110, 13537–13550.
Analysis, release 97-2, University of Göttingen, Germany, 1998.
Received: May 30, 2014
Published Online: ᭿
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Diselenaphospholanes
B. Wrackmeyer,* E. V. Klimkina,
W. Milius ........................................ 1–13
Reactions of 1,3,2-Diselenaphospholanes
with Lewis Acids: Borane and (Penta-
methylcyclopentadienyl)rhodium and -irid-
ium Dichloride
Keywords: Main-group elements
/ Sel-
enium / Phosphorus / Boron / Carboranes /
Lewis acids
Borane reagents as well as Cp*MCl2 (Cp*
= pentamethylcyclopentadienyl; M = Rh,
Ir) react with 1,3,2-diselenaphospholanes
by the formation of adducts, followed by
ring insertion, and finally by exchange.
Eur. J. Inorg. Chem. 0000, 0–0
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