Phosphinimine complex of organotin(IV) compounds stabilized by O,C,O-chelating ligand

Article abstract of DOI:10.1016/j.jorganchem.2012.08.003

Oxidation of an intramolecularly coordinated phosphine ligand {2,6-( ^tBuOCH₂)₂C₆H₃}PPh ₂ (1) by Me₃SiN₃ provided novel silyl-phosphinimine {2,6-(^tBuOCH

Full text of DOI:10.1016/j.jorganchem.2012.08.003

Journal of Organometallic Chemistry 718 (2012) 38e42
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Note
Phosphinimine complex of organotin(IV) compounds stabilized
by O,C,O-chelating ligand
ꢀ
*
ꢀ
ꢀ
ꢀ ꢁꢀ ꢀ
Tomás Reznícek, Libor Dostál, Ales Ruzicka, Roman Jambor
Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice, Studentská 95, CZ-532 10 Pardubice, Czech Republic
a r t i c l e i n f o
a b s t r a c t
Oxidation of an intramolecularly coordinated phosphine ligand {2,6-(tBuOCH2)2C6H3}PPh2 (1) by
Me3SiN3 provided novel silyl-phosphinimine {2,6-(tBuOCH2)2C6H3}Ph2P]NSiMe3 (2), that can be easily
hydrolysed to give stable phosphiniminium azide [{2,6-(tBuOCH2)2C6H3}Ph2P]NH2]þ N3ꢀ (3).
Article history:
Received 13 June 2012
Received in revised form
31 July 2012
Compound
3 was used for the synthesis of novel intramolecularly coordinated phosphinimine
Accepted 2 August 2012
compound L1Ph2P]NH, that can be trapped by triorganotin(IV) compounds R3SnCl (R ¼ Me, Cy) as
organotin(IV)-phosphinimine complexes [{2,6-(tBuOCH2)2C6H3}Ph2P]NH]SnR3Cl (R ¼ Me(4), Cy(5)).
Compounds 2e5 were characterized by means of elemental analyses, 1H, 13C, 31P, 119Sn NMR spec-
troscopy, and compounds 3 and 4 by single crystal X-ray diffraction analysis.
Ó 2012 Elsevier B.V. All rights reserved.
Keywords:
Organotin
Phosphinimine
Intramolecular coordination
NMR
X-ray diffraction
1. Introduction
Here we report an oxidation reaction of 1 by Me3SiN3 that
provided novel silyl-phosphinimine ligand {2,6-(tBuOCH2)2C6H3}
The use of phosphinimine ligands (R3P]NSiMe3) as suitable
ligands for the stabilization of organometallic complexes has been
studied over the past few decades and applications of variety of
these compounds have been reported [1]. The chemistry of tran-
sition metal phosphinimine complexes has led to the development
of highly effective olefin polymerization catalysts [2,3]. The corre-
sponding main group phosphinimines complexes have drawn
some attention since 1970s, when Wolfsberger synthesized variety
of complexes of the formula t-Bu3PNMMe3 (M ¼ Si, Ge, Sn) [4].
Further studies of Stephan et al. have probed the structural and
chemical behaviour of Li [5], Mg [6], Si, Sn, and Ge [7] phosphini-
mine derivatives. Dehnicke and co-workers reported several boron-
phosphinimines derivatives of group 13-15 species [8]. In general,
the synthesis of phosphinimine ligands is based on easy oxidation
of phosphine ligands by Me3SiN3 and all given examples are limited
to study the effects of sterical demanding phosphinimine ligands,
while the synthesis of an intramolecularly coordinated phosphi-
nimine ligands is still unknown. Previously we have reported
synthesis of an ether functionalized phosphine ligand {2,6-
(tBuOCH2)2C6H3}PPh2 (1) and its coordination ability towards MCl2
(M is Pd, Pt) (Chart 1) [9].
Ph2P]NSiMe3 (2), that can be easily hydrolysed to give phosphini-
minium azide [{2,6-(tBuOCH2)2C6H3}Ph2P]NH2]þ Nꢀ3 (3).
Compound 3, stabilized by the NeH/O hydrogen bonding with an
oxygen atom of the O,C,O-chelating ligand, was further used for
the synthesis of novel ether functionalized phosphinimine
compound [{2,6-(tBuOCH2)2C6H3}Ph2P]NH. The latter compound
was trapped by triorganotin(IV) compounds R3SnCl (R ¼ Me, Cy)
to provide the organotin(IV)-phosphinimine complexes [{2,6-
(tBuOCH2)2C6H3}Ph2P]NH]SnR3Cl (R ¼ Me(4), Cy(5)). Compounds
2e5 were characterized by means of elemental analyses, 1H, 13C, 31P,
119Sn NMR spectroscopy, and compounds 3 and 4 by single crystal X-
ray diffraction analysis.
2. Results and discussion
Reaction of L1PPh2 (1) (L1 is an abbreviation for 2,6-
(tBuOCH2)2C6Hꢀ3 ligand) with Me3SiN3 provided oxygen stabilized
silyl-phosphinimine ligand L1Ph2P]NSiMe3 (2) in high yield
(Scheme 1). Compound 2 was characterized by 1H, 13C and 31P NMR
spectroscopy. The 31P{1H} NMR spectrum showed a signal at
d
ꢀ7.4
with 2J(31P, 29Si) ¼ 104 Hz, that is shifted downfield compare with 1
(d
ꢀ20.3) [9]. The 1H NMR spectrum showed a singlet resonance at
d
4.36 for CH2O methylene groups and at d 0.35 ppm for Si(CH3)3
groups. Compound 2 is sensitive to water and the treatment of 2
* Corresponding author.
E-mail address: roman.jambor@upce.cz (R. Jambor).
with 2 equivalents of H2O in the presence of Me3SiN3 provided
0022-328X/$ e see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jorganchem.2012.08.003

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T. Reznícek et al. / Journal of Organometallic Chemistry 718 (2012) 38e42
39
t
t
BuO
O Bu
t
O Bu
Cl
M
Cl
PPh2
PPh2
PPh2
t
O Bu
t
t
BuO
1
O Bu
M = Pd, Pt
Chart 1.
t
t
O Bu
t
O Bu
O Bu
Ph
P
H2O, Me3SiN3
Ph
NSiMe3
Me3SiN3, 85°C
- N2
+
-
PPh2
N3
P
Ph
NH2
Ph
t
t
O Bu
t
O Bu
O Bu
1
2
3
Scheme 1. Synthesis of oxygen stabilized silyl-phosphinimine ligand 2 and its hydrolytic product 3.
phosphiniminium azide [L1Ph2P]NH2]þ Nꢀ3 (3), as the controlled
hydrolytic product of 2, in quantitative yield.
showed a specific ion at m/z 450 corresponding to [M ꢀ N3]þ
fragment.
Compound 3 was characterized by 1H, 13C and 31P NMR spec-
troscopy, mass spectrometry and molecular structure was deter-
mined by X-ray diffraction analysis. The 31P{1H} NMR spectrum
Single crystals of 3 suitable for X-ray diffraction analysis were
obtained by crystallization from toluene/hexane solution at þ 4 ꢁC.
The molecular structure of 3, selected bond lengths, and angles are
shown in Fig. 1, the crystallographic data are given in Table S1.
The central phosphorus atom is four coordinated with distorted
tetrahedral geometry as defined from bonding angles C1eP1eN1
(117.24(8)ꢁ), C1eP1eC17 (109.87(8)ꢁ) and C1eP1eC23 (109.42(8)ꢁ).
Compound 3 can be described as aminophosphonium salt with PeN
single bond and positive charge on phosphorus atom (see supporting
information, Scheme S1A) or as phosphiniminium salt where P]N
doublebondcontains positive charge on nitrogen atom (Scheme S1B).
showed a singlet resonance at
d
þ30.5 shifted downfield compare
with 2 (
d
ꢀ7.4 ppm). The 1H NMR spectrum revealed a singlet
resonance at
a resonance at
d
4.35 for CH2O methylene groups together with
8.00 assigned to NH2 groups. The ESI/MS spectrum
d
ꢁ
TheP1eN1(1.6314(14)A) bondlength is shorter thatPeN single bond
ꢁ
predictedbyPyykkö(Scov(P,N)¼ 1.82 A) [10]and provedtheexistence
of P]N double bond in
3 (for double bond covalent radii
ꢁ
S
cov(P,N) ¼ 1.62 A) [10]. The phosphiniminium form P]NH2 in 3 is
further stabilized by the O,C,O-chelating ligand L1, due to the exis-
ꢁ
tence an NeH/O hydrogen bonding [O2/N12.7387(19) A] with one
of the oxygen atom of ligand L1.
Treatment of 3 with equivalent of n-BuLi allowed an in situ
preparation of phosphinimine L1Ph2P]NH (Scheme 2). Subsequent
reaction of L1Ph2P]NH with triorganotin(IV) compounds R3SnCl
(R ¼ Me, Cy) provided organotin(IV)phosphinimine complexes
(L1Ph2P]NH)SnR3Cl (R ¼ Me(4), Cy(5)) (Scheme 2).
Compounds 4 and 5 were characterized by the 1H, 13C, 31P and
119Sn NMR spectroscopy, ESI-MS and molecular structure of 4 was
determined by diffraction analysis. The 31P{1H} NMR spectrum of 4
showed a resonance at
d
þ28.9 ppm ( þ28.0 ppm for 5) flanked by
d
119Sn satellites with coupling constant 2J(31P, 119Sn) ¼ 113 Hz (2J(31P,
119Sn) ¼ 100 Hz for 5). The 1H NMR spectrum of 4 revealed a reso-
nance at
and singlet at
d 4.48 ppm of methylene CH2O groups (d 4.50 ppm for 5)
Fig. 1. ORTEP view of 3. The thermal ellipsoids are drawn with 50% probabiliꢁty.
d
0.60 ppm of SnMe groups. The 1H NMR spectrum of
ꢁ
Hydrogen atoms are omitted for clarity. Selected bond distances (A) and angles ( ):
4 also showed a doublet of NH group at
d 4.19 ppm with coupling
P1eN1 1.6314(14), P1eN3 4.6221(16), C1eP1eN1 117.24(8), C17eP1eC23 115.08(8),
O2/N1 2.7387(19) A.
constant 2J(1H,31P) ¼ 101 Hz suggesting the presence of P]NH
ꢁ

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40
T. Reznícek et al. / Journal of Organometallic Chemistry 718 (2012) 38e42
t
O Bu
t
t
O Bu
O Bu
Ph
P
Ph
Ph
P
n-BuLi, -78°C
- BuH, LiN3
R3SnCl, -78°C
+
NH
-
P
NH
NH2 N3
Ph
Ph
Ph
SnR3Cl
t
O Bu
t
t
O Bu
O Bu
3
4: R = Me
5: R = Cy
Scheme 2. Synthesis of oxygen stabilized phosphinimine and its organotin(IV) complexes 4 and 5.
fragment (
d
4.28 ppm, 2J(1H,31P) ¼ 100 Hz for 5). The 119Sn{1H} NMR
The central tin atom is five coordinated. The geometry of tin
atom is best described as trigonal bipyramidal, with the methyl
groups occupying the equatorial plane and the phosphinimine and
the chlorine atom occupying the axial sites as defined from bonding
angles C29eSn1eC31 (110.64(13)ꢁ), C31eSn1eC30 (125.14(14)ꢁ),
C30eSn1eC29 (123.73(14)ꢁ) and N1eSneCl1 (172.27(8)ꢁ). The
spectrum of 4 revealed a resonance at d 24.7 ppm (d 35.5 ppm for 5).
This value is shifted upfield compare with the value found for
Me3SnCl (þ160 ppm) [11] but is similar to Me3SnCl$py (ꢀ9 ppm)
[11] and indicates the presence of five coordinated tin atom in
solution of 4. This was further corroborate from 13C NMR spectrum
of 4, where the value of CeSneC bond angle 121ꢁ was calculated
from the 1J(119Sn,13C) ¼ 558 Hz [12] (for comparison the value of
1J(119Sn,13C) for Me3SnCl is 379.7 Hz) [13]. An interestingly, the fact
that the 31P{1H} NMR spectrum of compounds 4 and 5 revealed
2J(31P,119Sn) at room temperature suggests that both complexes are
kinetically inert and it contrasts with organotin(IV) complexes of
HMPA. The later complexes are kinetically more labile and similar
2J(31P,119Sn) couplings were observed at low temperature only [14]
suggesting that the R3P]NH group is a stronger ligand towards
R3SnCl moiety in comparison to HMPA.
ꢁ
P1eN1 (1.594(2) A) bond length proved the existence of P]N
double bond in the phosphinimine L1Ph2P]NH (for double bond
ꢁ
ꢁ
covalent radii Scov(P,N) ¼ 1.62 A) [10]. The N1eSn1 (2.258(3) A)
bond length is longer than the sum of covalent radii of both atoms
P
ꢁ
(
cov(N,Sn) ¼ 2.11 A) [10] and suggests the presence of strong
N / Sn intermolecular interaction of phosphinimine L1PPh2P]NH
to Me3SnCl. This interaction also resulted to a substantive elonga-
tion of SneCl bond in Me3SnCl, as indicated from the Sn1eCl1 bond
ꢁ
length (2.7093(10) A) being longer than the sum of covalent radii of
P
ꢁ
both atoms ( cov(Sn,Cl) ¼ 2.39 A) [10]. Compound 4 is related to
Single crystals of 4 suitable for X-ray diffraction analysis were
obtained by crystallization from toluene/hexane solution at þ4 ꢁC.
The molecular structure of 4, selected bond lengths, and angles are
shown in Fig. 2 (for the crystallographic data see Table S1).
the adduct (i-Pr3P]NH)SnMe3Cl, where the similar arrangement of
central tin atom was found [15] and is similar to the related plu-
tonyl(VI) chloride complex of triphenyl phosphinimine [16]. It is
noteworthy, that related reaction of t-Bu3PNH with Me3SnCl does
not result in the Lewis base adduct [15]. Stabilization of monomeric
form of 4 is supported by the presence of ligand L1, since the
ammonium P]NH group is involved in a NeH/O hydrogen
bonding with one of the oxygen atom of ligand L1[O1/N1
ꢁ
2.789(3) A]. This contrasts with a molecular structure of (i-Pr3P]
NH)SnMe3Cl, where an extended polymeric chain was observed
in the solid state due the presence of NHeCl hydrogen bonding [15].
3. Conclusion
We have demonstrated that compound 1 is useful starting
material for synthesis silyl-phosphinimine ligand {2,6-
(tBuOCH2)2C6H3}Ph2P]NSiMe3 (2). Thy hydrolysis of 2 provided an
oxygen stabilized phosphiniminium azide [{2,6-(tBuOCH2)2C6H3}
Ph2P]NH2]þ N3ꢀ (3) and phosphinimine compound L1Ph2P]NH.
The later compound can be trapped by triorganotin(IV) compounds
R3SnCl (R ¼ Me, Cy) as organotin(IV)-phosphinimine complexes
[{2,6-(tBuOCH2)2C6H3}Ph2P]NH]SnR3Cl (R ¼ Me(4), Cy(5)).
4. Experimental
4.1. General methods
The starting compound [2,6-(tBuOCH2)2C6H3]PPh2 (1) was
prepared according to literature [9], Me3SiN3, Me3SnCl and Cy3SnCl
were purchased by Sigma Aldrich. All reactions were carried out
underargon, using standard Schlenk techniques. Solvents were dried
Fig. 2. ORTEP view of 4. The thermal ellipsoids are drawn with 50% probabiliꢁty.
ꢁ
Hydrogen atoms are omitted for clarity. Selected bond distances (A) and angles ( ):
P1eN1 1.594(2), N1eSn1 2.258(3), Sn1eCl1 2.7093(10), P1eN1eSn1 136.77(18),
N1eSn1eCl1 172.27(8), C29eSn1eC31 110.64(13), C30eSn1eC29 123.73(14),
ꢁ
C29eSn1eCl1 90.95(9), O1/N1 2.789(3) A.

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T. Reznícek et al. / Journal of Organometallic Chemistry 718 (2012) 38e42
41
by standard methods, distilled prior to use. The 1H, 13C{1H}, 31P{1H}
4.5. Synthesis of {[2,6-(tBuOCH2)2C6H3]Ph2PNH}Cy3SnCl (5)
and 119Sn{1H} NMR spectra were recorded on a Bruker Avance 400
spectrometerat300KinC6D6 orCDCl3. The1H,13C, 31Pand119SnNMR
0.36 mL (0.57 mmol) of n-BuLi was added drop-wise to the
toluene solution (10 mL) of 3 (0.28 g, 0.57 mmol) at ꢀ78 ꢁC and
resulting dark red solution was stirred for 30 min at ꢀ78 ꢁC. The
Cy3SnCl (0.23 g, 0.57 mmol) was added in one portion and reaction
mixture was stirred for additional 17 h at r.t. Solid was filtered off
and solvent was evaporated and resulting light yellow oil was
washed with hexane (6 mL) to give colourless solid of 5 (yield
0.44 g, 92%). For 5: mp 125e127 ꢁC; Anal. Calcd for C31H45ClNO2PSn
(853.18 g/mol): C, 64.59; H, 8.22. Found: C, 64.68; H, 8.26. 1H NMR
chemical shifts d are given in ppm and referenced to internal Me4Si
(1H and 13C) and external H3PO4 (31P) and Me4Sn (119Sn). Elemental
analyses were performed on an LECO-CHNS-932 analyzer.
4.2. Synthesis of [2,6-(tBuOCH2)2C6H3]Ph2PNSiMe3 (2)
0.11 mL of Me3SiN3 (0.85 mmol) was added to toluene solution
(10 mL) of 1 (0.24 g; 0.56 mmol) and reaction mixture was heated to
85 ꢁC. The reaction was monitored by 31P NMR spectroscopy and
the reaction was complete in 7 days. The solvent was evaporated in
reduced pressure to form orange viscous oil of 2 (yield 0.61 g; 97%).
For 2: Anal. Calcd for C31H44NO2PSi (521.74 g/mol): C, 71.36; H, 8.50.
(C6D6, 400 MHz):
d
0.97 (s, 18H, OtBu); 1.32 (bs, 4H, CyH); 1.69 (bs,
2H, CyH); 1.85 (bs, 4H, CyH); 2.05 (bs, 1H, CyH); 4.28 (d, 1H, PNH)
(2J(1H,31P) ¼ 100 Hz); 4.50 (s, 4H, CH2O); 7.04e7.91 (m, 13H, ArH);
13C NMR (C6D6, 100 MHz):
d 27.2 (CH3); 28.9 (C(1)-Cy;
Found: C, 71.29; H, 8.39. 1H NMR (C6D6, 400 MHz):
SiMe3); 1.04 (s, 18H, OtBu); 4.36 (s, 4H, CH2O); 7.07e8.01 (m, 13H,
d
0.35 (s, 9H,
1J(13C,119Sn) ¼ 560 Hz); 31.2 (C(2,6)-Cy; 2J(13C,119Sn) ¼ 17.0 Hz);
32.4 C(3,5)-Cy; 34.8 C(4)-Cy; 63.4 (CH2O, 3J(13C,31P) ¼ 5 Hz); 72.9
ArH); 13C NMR (C6D6, 100 MHz)
d
(ppm): 2.1 (SiMe3); 27.9 (CH3);
(OCMe3); 126.5 (C(10), 1J(13C,31P)
¼
95 Hz); 127.0 (C(20,60),
63.5 (CH2O, 3J(13C,31P) ¼ 27 Hz); 73.3 (OCMe3); 127.8 (C(30,50),
3J(13C,31P) ¼ 11 Hz); 128.9 (C(3,5), 3J(13C,31P) ¼ 23 Hz); 129.6 C(40);
130.7 C(4); 131.3 (C(20,60), 2J(13C,31P) ¼ 22 Hz); 136.2 (C(10),
1J(13C,31P) ¼ 32 Hz); 140.5 (C(1), 1J(13C,31P) ¼ 100 Hz); 144.5 (C(2,6),
2J(13C,31P) ¼ 10 Hz); 128.1 C(40); 128.3 (C(30,50), 3J(13C,31P) ¼ 12 Hz);
128.9 C(4); 131.5 (C(3,5), 3J(13C,31P)
¼
10 Hz); 135.8 (C(1),
1J(13C,31P) ¼ 100 Hz); 145.1 (C(2,6), 2J(13C,31P) ¼ 13 Hz); 31P NMR
(C6D6, 162 MHz):
186 MHz): d 35.5 (bs).
d
28.0 (2J(31P, 119Sn) ¼ 100 Hz); 119Sn NMR (C6D6,
2J(13C,31P) ¼ 13 Hz); 31P NMR (C6D6, 162 MHz):
29Si) ¼ 104 Hz).
d
ꢀ7.4 (2J(31P,
4.6. Crystallography
4.3. Synthesis of {[2,6-(tBuOCH2)2C6H3]Ph2PNH2}þNꢀ3 (3)
Compounds 3 and 4 were dissolved in toluene/hexane solution,
put to the freezer and let to crystallize at 4 ꢁC. The obtained
materials were suitable for X-ray analysis and characterized as
compounds 3 and 4.
The X-ray data (Table S1) for colourless crystals of 3 and 4 were
obtained at 150 K using Oxford Cryostream low-temperature
0.52 g (1.05 mmol) of 2 was dissolved in toluene (10 mL),
Me3SiN3 (0.27 mL, 2.10 mmol) and distilled water (0.04 mL,
2.1 mmol) were added via syringe. Reaction mixture was stirred for
3 days. The solvent was evaporated and resulting orange oil was
washed with hexane (6 mL) to give light orange solid of 3 (yield
0.49 g, 95%). For 3: mp 127.8e129.7 ꢁC; Anal. Calcd for C28H37N4O2P
(492.59 g/mol): C, 68.12; H, 7.76. Found: C, 68.08; H, 7.70. 1H NMR
device on a Nonius KappaCCD diffractometer with MoKa radiation
ꢁ
(l
¼ 0.71073 A), a graphite monochromator, and the
f and c scan
(C6D6, 400 MHz):
d
0.97 (s, 18H, OtBu); 4.35 (s, 4H, CH2O); 7.10e7.85
27.0
mode. Data reductions were performed with DENZO-SMN [17]. The
absorption was corrected by integration methods [18]. Structures
were solved by direct methods (Sir92) [19] and refined by full
matrix least-square based on F2 (SHELXL97) [20]. Hydrogen atoms
were mostly localized on a difference Fourier map, however to
ensure uniformity of the treatment of the crystal, all hydrogen
atoms were recalculated into idealized positions (riding model) and
assigned temperature factors Hiso(H) ¼ 1.2 Ueq(pivot atom) or of
(m, 13H, ArH); 8.00 (bs, 2H, NH2); 13C NMR (CDCl3, 90 MHz):
d
(CH3); 59.6 (CH2O, 3J(13C,31P) ¼ 5 Hz); 73.2 (OCMe3); 120.6 (C(10);
1J(13C,31P) ¼ 90 Hz]; 125.4 C(40); 126.5 C(4); 129.4 (C(30,50),
3J(13C,31P) ¼ 14 Hz); 129.8 (C(20,60), 2J(13C,31P) ¼ 11 Hz); 132.5
(C(3,5), 3J(13C,31P) ¼ 12 Hz); 135.3 (C(1), 1J(13C,31P) ¼ 99 Hz); 145.5
(C(2,6); 2J(13C,31P) ¼ 11 Hz); 31P NMR (CDCl3, 162 MHz):
ESIþ: m/z 450 [M ꢀ N3]þ (100%).
d 30.5; MS:
ꢁ
1.5 Ueq for the methyl moiety with CeH ¼ 0.96, 0.97, and 0.93 A for
4.4. Synthesis of {[2,6-(tBuOCH2)2C6H3]Ph2PNH}Me3SnCl (4)
methyl, methylene and hydrogen atoms in aromatic rings, respec-
ꢁ
tively, and 0.97 A for NeH groups.
0.29 mL (0.46 mmol) of n-BuLi was added drop-wise to the
toluene solution (10 mL) of 3 (0.22 g, 0.46 mmol) at ꢀ78 ꢁC and
resulting dark red solution was stirred for 30 min at ꢀ78 ꢁC. The
Me3SnCl (0.09 g, 0.46 mmol) was added at one portion and reaction
mixture was stirred for additional 17 h at r.t. Solid was filtered off
and solvent was evaporated and resulting light yellow oil was
washed with hexane (6 mL) to give colourless solid of 4 (yield
0.49 g, 90%). For 4: mp 125e127 ꢁC; Anal. Calcd for C31H45ClNO2PSn
(648.83 g/mol): C, 57.39; H, 6.99. Found: C, 58.08; H, 7.15. 1H NMR
Acknowledgement
The authors wish to thank the Grant Agency of the Czech
Republic (project no. P207/10/0215) and The Ministry of Education
of the Czech Republic for financial support.
Appendix A. Supplementary material
(C6D6, 400 MHz):
d
0.60 (s, 9H, Me3Sn, 2J(119Sn,1H) ¼ 68.5 Hz); 0.94
(s, 18H, OtBu); 4.19 (d, 1H, PNH, 2J(1H,31P) ¼ 101 Hz); 4.48 (s, 4H,
CCDC 882967 and 882968 contain the supplementary crystal-
lographic 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.
CH2O); 6.94e7.65 (m, 13H, ArH); 13C NMR (C6D6, 125 MHz):
d 1.1
(SnCH3; 1J(13C,119Sn)
¼
558 Hz); 27.4 (CH3); 63.5 (CH2O;
3J(13C,31P) ¼ 5 Hz); 73.0 (OCMe3); 126.1 (C(10), 1J(13C,31P) ¼ 100 Hz);
127.2 (C(30,50), 3J(13C,31P) ¼ 11 Hz); 128.4 C(40); 128.7 (C(3,5),
3J(13C,31P) ¼ 11 Hz); 131.4 C(4); 131.4 (C(20,60), 2J(13C,31P) ¼ 20 Hz);
135.6 (C(1); 1J(13C,31P) ¼ 100 Hz); 145.3 (C(2,6); 2J(13C,31P) ¼ 21 Hz);
Appendix B. Supplementary material
31P NMR (C6D6,162 MHz):
d
28.9 (2J(31P, 119Sn) ¼ 113 Hz); 119Sn NMR
(C6D6, 186 MHz):
(100%).
d
24.7 (bs); MS: ESIþ: m/z 450 [M-Me3SnCl þ H]þ
Supplementary material related to this article can be found at
http://dx.doi.org/10.1016/j.jorganchem.2012.08.003.

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T. Reznícek et al. / Journal of Organometallic Chemistry 718 (2012) 38e42
[7] (a) D.A. Evans, D.W.C. MacMillan, K.R. Campos, J. Am. Chem. Soc. 119 (1997)
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