The first [4+2]-coordinated tetraorganolead compound: Synthesis, structure and conversion into a triorganolead cation, a benzoxaphosphaplumbole, and diorganolead dihalides

Article abstract of DOI:10.1002/1521-3749(200211)628:11<2435::AID-ZAAC2435>3.0.CO;2-S

The syntheses and molecular structures, as determined by single-crystal X-ray diffraction analysis, of the first intramolecularly [4+2]-coordinated tetraorganolead compound {4-t-Bu-2,6-[P(O)(OEt)₂]₂C₆H ₂}PbPh₃ (2) and the triphenyllead chloride adduct of the first intramolecularly coordinated benzoxaphosphaplumbole {[1(Pb),3(P)-Pb(Ph)₂OP(O)(OEt)-5-t-Bu-7-P(O)-(OEt)₂]C ₆H₂·Ph₃PbCl} (3a) are reported. The reaction of 2 with [Ph₃C]⁺ [PF₆]^- and p-MeC₆H₄SO₃H, respectively, provides the triorganolead salts {4-t-Bu-2,6-[P(O)(OEt)₂]₂C₆H₂} PbPh₂⁺X^- (4, X = PF₆; 4a, X = p-MeC₆H₄SO₃). Reaction of 2 with bromine and hydrogen chloride, respectively, gives the diorganolead dihalides {4-t-Bu-2,6-[P(O)(OEt)₂]₂C₆H₂} PbPhX₂ (5, X = Br; 6, X = Cl).

Full text of DOI:10.1002/1521-3749(200211)628:11<2435::AID-ZAAC2435>3.0.CO;2-S

The First [4؉2]-Coordinated Tetraorganolead Compound: Synthesis, Structure
and Conversion into a Triorganolead Cation, a Benzoxaphosphaplumbole, and
Diorganolead Dihalides1)
Katja Peveling, Markus Schürmann, and Klaus Jurkschat*
Dortmund, Lehrstuhl für Anorganische Chemie II der Universität
Received May 6th, 2002.
Dedicated to Professor Dieter Fenske on the Occasion of his 60th Birthday
Abstract. The syntheses and molecular structures, as determined by
single-crystal X-ray diffraction analysis, of the first intramolecu-
larly [4ϩ2]-coordinated tetraorganolead compound {4-t-Bu-2,6-
[P(O)(OEt)2]2C6H2}PbPh3 (2) and the triphenyllead chloride
adduct of the first intramolecularly coordinated benzoxa-
phosphaplumbole {[1(Pb),3(P)-Pb(Ph)2OP(O)(OEt)-5-t-Bu-7-P(O)-
(OEt)2]C6H2·Ph3PbCl} (3a) are reported. The reaction of 2 with
[Ph3C]ϩ [PF6]Ϫ and p-MeC6H4SO3H, respectively, provides the
triorganolead salts {4-t-Bu-2,6-[P(O)(OEt)2]2C6H2}PbPh2ϩXϪ (4,
X ϭ PF6; 4a, X ϭ p-MeC6H4SO3). Reaction of 2 with bromine
and hydrogen chloride, respectively, gives the diorganolead dihalides
{4-t-Bu-2,6-[P(O)(OEt)2]2C6H2}PbPhX2 (5, X ϭ Br; 6, X ϭ Cl).
Keywords: Lead; Phosphorus; Intramolecular coordination; Crystal
structure; NMR spectroscopy (207Pb)
Die erste [4؉2]-koordinierte Tetraorganobleiverbindung: Synthese, Struktur und
Umwandlung in ein Triorganobleikation, ein Benzoxaphosphaplumbol und
Diorganobleidihalogenide
Inhaltsübersicht. Es wird über die Synthesen und Einkristallrönt-
genstrukturanalysen der ersten intramolekular [4ϩ2]-koordinierten
Tetraorganobleiverbindung {4-t-Bu-2,6-[P(O)(OEt)2]2C6H2}PbPh3
(2) und des Triphenylbleichlorid-Adduktes des ersten intramoleku-
richtet. Die Reaktion von 2 mit [Ph3C]ϩ [PF6]Ϫ bzw. p-MeC6H4-
SO3H führt zu den Triorganoblei-Salzen [{4-t-Bu-2,6-
[P(O)(OEt)2]2C6H2}PbPh2]ϩXϪ (4,
X
ϭ
PF6; 4a,
X ϭ p-
MeC6H4SO3).
Die
Diorganobleidihalogenide {4-t-Bu-2,6-
lar
koordinierten
Benzoxaphosphaplumbols
{[1(Pb),3(P)-
[P(O)(OEt)2]2C6H2}PbPhX2 (5, X ϭ Br; 6, X ϭ Cl) werden durch
die Reaktion von 2 mit Brom oder Chlorwasserstoff dargestellt.
Pb(Ph)2OP(O)(OEt)-5-t-Bu-7-P(O)(OEt)2]C6H2·Ph3PbCl} (3a) be-
Introduction
ity of these intramolecularly coordinated compounds. On
the other hand, so far only few articles dealing with
O,C,O-coordinating pincer-type ligands have been pub-
lished [35Ϫ41]. Recently, we have reported the phos-
phorus-containing O,C,O-coordinating pincer-type li-
gands {5-t-Bu-1,3-[P(O)(OR)2]2C6H2}Ϫ (A, R ϭ Et, AЈ ϭ
i-Pr) and their application to the synthesis of [4ϩ2]-coor-
dinated tetraorganosilicon [37, 42] and tetraorganotin [35]
compounds, of triorganosilicon [43] and triorganotin [38,
41, 44] cations, of benzoxasilaphospholes [43] and benzo-
xaphosphastannoles [38, 41], and of heteroleptic tin(II)
compounds [40].
Organolead compounds such as hexaethyldilead have
been known for almost 150 years [45, 46]. Tetraethyllead
had become an industrial commodity in the last century
but is now in the process of being banned because of the
negative environmental impact related to its toxicity [47,
48]. However, nowadays the interest to apply organolead
compounds as synthons in organic reactions is growing
[49Ϫ58] and their higher toxicity in comparison to the more
popular organotransition metal compounds being applied
in organic syntheses has been questioned [59]. Conse-
ECE-coordinating pincer-type ligands of the general type
[2,6-(ECH2)2C6H3]Ϫ containing mainly E ϭ nitrogen
[1Ϫ20], phosphorus [1, 20Ϫ31], and sulfur [1, 32Ϫ34] do-
nors have received great interest as result of their potential
(i) to stabilize organometallic compounds of both main
group and transition metals with the metal atoms having
unusual coordination numbers and (ii) to tune the reactiv-
1) This work contains part of the intended Ph.D. thesis of K. Peve-
ling.
Parts of the results were first presented at the 10th International
Conference on the Coordination and Organometallic Chemistry of
Germanium, Tin and Lead, ICCOC-GTL-10, July 8 to12, 2001,
Bordeaux, France, Book of Abstracts 2P26.
* Prof. Dr. K. Jurkschat
Lehrstuhl für Anorganische Chemie II der Universität Dortmund
D-44221 Dortmund
fax: ϩϩ49-(0)231-7553797
E-mail: kjur@platon.chemie.uni-dortmund.de
Z. Anorg. Allg. Chem. 2002, 628, 2435Ϫ2442  WILEY-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002 0044Ϫ2313/02/628/2435Ϫ2442 $ 20.00ϩ.50/0
2435

K. Peveling, M. Schürmann, K. Jurkschat
˚
Table 1 Selected Bond Lengths/A, Bond Angles/°, and Torsion
Angles/° for 2 and 3a.
2
3a
2
3a
116.8(4)
Pb(1)-C(1)
Pb(1)-C(11)
Pb(1)-C(21)
Pb(1)-C(31)
Pb(1)-O(1)
Pb(1)-O(2)
Pb(1)-O(2Ј)
P(1)-O(1)
2.269(3)
2.232 (3) 2.18(1)
2.214(3)
2.236(3)
3.090(2)
3.139(2)
2.20(1)
C(11)-Pb(1)-C(1)
C(21)-Pb(1)-C(1)
C(31)-Pb(1)-C(1)
C(21)-Pb(1)-C(11)
C(31)-Pb(1)-C(11)
C(21)-Pb(1)-C(31)
O(1)-Pb(1)-C(1)
O(2)-Pb(1)-C(1)
O(1)-Pb(1)-O(2)
O(2Ј)-Pb(1)-C(1)
C(11)-Pb(1)-O(1)
O(2Ј)-Pb(1)-C(11)
C(21)-Pb(1)-O(1)
O(2Ј)-Pb(1)-C(21)
O(2Ј)-Pb(1)-O(1)
O(1)-P(1)-C(2)
109.4(1)
118.63(9)
106.4(1)
111.9(1)
97.7(1)
110.7(1)
70.72(7)
69.12(7)
119.36(5)
124.1(4)
2.21(1)
119.1(4)
2.470(7)
Chart 1
2.300(7)
1.513(7)
1.475(6)
1.566(7)
1.567(7)
1.530(7)
1.599(7)
1.75(1)
77.6(3)
1.462(2)
1.460(2)
1.567(2)
1.590(2)
1.565(2)
1.584(2)
1.795(3)
1.802(3)
P(2)-O(2)
P(1)-O(1Ј)
P(1)-O(1Љ)
P(2)-O(2Ј)
P(2)-O(2Љ)
P(1)-C(2)
80.2(4)
90.8(3)
95.8(3)
100.6(4)
95.0(4)
157.5(2)
110.4(5)
112.2(4)
113.1(4)
70.54(8)
82.63(8)
P(2)-C(6)
Pb(2)-O(2)
1.81(1)
2.541(6)
114.0(1)
113.2(1)
98.51(9)
98.02(9)
O(2)-P(2)-C(6)
P(1)-O(1)-Pb(1)
P(2)-O(2)-Pb(1)
P(2)-O(2Ј)-Pb(1)
Pb(2)-O(2)-P(2)
O(2)-Pb(2)-Cl(1)
C(61)-Pb(2)-C(41)
C(51)-Pb(2)-C(41)
P(1)-C(2)-C(1)
P(1)-C(2)-C(3)
P(2)-C(6)-C(1)
P(2)-C(6)-C(5)
C(6)-C(1)-Pb(1)
C(2)-C(1)-Pb(1)
117.9(4)
145.5(4)
178.9(2)
108.2(4)
127.9(4)
117.2(9)
125.0(8)
120.2(8)
121.4(9)
116.6(8)
121.1(8)
Ϫ173.9(7)
Ϫ178.4(7)
122.3(2)
116.7(2)
122.3(2)
116.1(2)
121.8(2)
121.1(2)
Pb(1)-C(1)-C(2)-C(3) Ϫ168.0(2)
P(1)-C(2)-C(3)-C(4) 173.4(2)
Scheme 1
metrical data are given in Table 1 and relevant crystallo-
graphic parameters are listed in Table 2.
quently, efforts to accumulate more knowledge on organole-
ad(IV) compounds are welcome.
Similar to the silicon and tin atoms in the related organo-
silicon and organotin compounds, respectively, the lead
atom in compound 2 shows a strongly distorted tetrahedral
configuration with the CϪPbϪC angles ranging from
97.7(1)° to 118.63(9)°. For the related organosilicon [37]
and organotin [35] compounds {4-t-Bu-2,6-[P(O)-
(OEt)2]2C6H2}MPh3 (M ϭ Si, Sn) the corresponding
CϪSiϪC and CϪSnϪC angles range from 103.5(2)° to
116.6(2)° and 100.3(3)° to 125.2(3)°, respectively. The dis-
tortion in compound 2 from the ideal tetrahedral geometry
is the result of two intramolecular O···Pb distances of
Organolead compounds containing intramolecularly co-
ordinating ligands such as acetates or ligands of type B [60],
C [61], D [62], E [63], F [62], G [64], and H [65], respectively,
(Chart 1) have been published. All of these compounds con-
tain at least one electron-withdrawing substituent making
the lead atom sufficiently Lewis-acidic to allow intramol-
ecular coordination. To the best of our knowledge, no hyp-
ercoordinated tetraorganolead compound has been re-
ported so far.
In continuation of our systematic studies on main group
metal derivatives of the O,C,O-coordinating pincer-type li-
gand {5-t-Bu-1,3-[P(O)(OEt)2]2C6H2}Ϫ (A) we report here
the syntheses and reactivity of the first intramolecularly
[4ϩ2]-coordinated tetraorganolead compound and its con-
version into the first intramolecularly coordinated benzo-
xaphosphaplumbole, into a triorganolead cation, and into
diorganolead dihalides.
˚
˚
3.090(2) A and 3.139(2) A being shorter than the sum of
˚
the van der Waals radii of oxygen (1.50 A) [66] and lead
˚
(2.00 A) [66]. Slightly shorter intramolecular O···Pb dis-
˚
tances of 2.915(8) and 2.955(7) A were found for the
monoorganolead triacetate derivative [2-(MeO)C6H4]-
Pb(OAc)3 ([7ϩ1]-coordination) and the diorganolead di-
acetate derivative [2-(MeO)C6H4]2Pb(OAc)2 ([5ϩ1]-coordi-
nation), respectively [57]. Compound 2 is the first example
of a [4ϩ2]-coordinated tetraorganolead compound.
The IR spectra for a series of compounds {4-t-Bu-2,6-
[P(O)(OEt)2]2C6H2}MPh3 show ν˜ (PϭO) of 1254 cmϪ1
(M ϭ Si) [37], 1246 cmϪ1 (2, M ϭ Pb), and 1233 cmϪ1
(M ϭ Sn) [35] and suggest the strength of the intramolecu-
lar O···M coordination to increase in the sequence M ϭ Si
< M ϭ Pb < M ϭ Sn. Usually such comparisons are made
on the basis of Pauling-type bond orders [66-68] but in the
actual case this is not possible because a reliable covalent
Results and Discussion
The tetraorganolead compound 2 has been obtained in good
yield by reaction at low temperature of the corresponding
organolithium compound {4-t-Bu-2,6-[P(O)(OEt)2]2C6H2}Li
(1) with triphenyllead chloride (Scheme 1).
Compound 2 is a colorless crystalline solid being light-
and air-stable in the solid state as well as in solution. The
molecular structure of 2 is shown in Figure 1, selected geo-
2436
Z. Anorg. Allg. Chem. 2002, 628, 2435Ϫ2442

The First [4ϩ2]-Coordinated Tetraorganolead Compound
Table 2 Crystallographic Data for 2 and 3a.
˚
Pb(1)ϪC(31) (2.236(3) A) distances and indicates some re-
pulsion between the pincer ligand {5-t-Bu-1,3-
[P(O)(OEt)2]2C6H2}Ϫ and the Ph3Pb-moiety. The PbϪC
distance in tetraphenyllead, Ph4Pb, is shorter and amounts
2
3a
Formula
Fw
C36H46O6P2Pb
843.86
C46H51ClO6P2Pb2
1211.64
triclinic
˚
to 2.194(6) A [69].
cryst syst
cryst size, mm
space group
monoclinic
0.13 x 0.10 x 0.10
P2(1) /n
11.9246(2)
14.7827(2)
20.9297(3)
90
94.6307(7)
90
3677.4(1)
4
The P(O)(OEt)2-groups are displaced in one direction
and the lead atom is displaced in the opposite direction of
the plane defined by the aromatic ring of the ligand with
torsion angles P(1)ϪC(2)ϪC(3)ϪC(4) ϭ 173.4(2)° and
Pb(1)ϪC(1)ϪC(2)ϪC(3) ϭ Ϫ168.0(2)°. In the related or-
ganosilicon and organotin compounds {4-t-Bu-2,6-
[P(O)(OEt)2]2C6H2}MPh3 the corresponding torsion angles
(absolute values) are smaller (M ϭ Si [37]: P(1)ϪC(2)Ϫ
0.10 x 0.10 x 0.08
¯
P1
˚
a, A
11.8191(7)
12.0763(7)
17.2386(12)
75.724(3)
80.526(3)
78.413(3)
2318.7(3)
2
˚
b, A
˚
c, A
Ͱ, deg
β, deg
γ, deg
3
˚
V, A
Z
ρcalcd, Mg/m3
ρmes, g/cm3
µ, mmϪ1
F(000)
1.524
1.501(2)
4.716
1.735
1.700(2)
7.423
C(3)ϪC(4)
157.5(2)°);
ϭ
M
Ϫ168.0(3)°, Si(1)ϪC(1)ϪC(2)ϪC(3)
ϭ Sn [35]: P(1)ϪC(2)ϪC(3)ϪC(4)
ϭ
ϭ
1688
1172
167.8(4)°, Sn(1)ϪC(1)ϪC(2)ϪC(3) ϭ Ϫ157.3(5)°). The
C(1)ϪC(2)ϪP(1) and C(1)-C(6)-P(2) angles (α, αЈ angles
[70]) of 122.3(2) and 122.3(2)°, respectively, are rather simi-
lar to the corresponding angles in the related organosilicon
[37] and organotin compounds [35].
The 207Pb NMR spectrum of the tetraorganolead com-
pound 2 exhibits a triplet resonance at δ 207Pb ϭ Ϫ231
(J(207Pb-31P) ϭ 39 Hz) which is shifted to lower frequency
as compared to tetraphenyllead, Ph4Pb (δ 207Pb ϭ Ϫ166)
[71], suggesting the intramolecular O···Pb coordination in
the former compound to persist in solution. As was demon-
strated by 1H NMR studies, no intramolecular N···Pb coor-
dination seems to exist in [2-(CH2NMe2)C6H4]Pb(p-Tol)3
[65] which indicates a poorer coordinating capacity of the
nitrogen-containing ligand in the latter compound.
θ range, deg
index ranges
2.92 to 27.48
Ϫ15 Յ h Յ 15
Ϫ19 Յ k Յ 19
Ϫ27 Յ l Յ 27
33539
99.7
8405/0.037
5634
3.04 to 25.30
Ϫ14 Յ h Յ 14
Ϫ13 Յ k Յ 14
Ϫ20 Յ l Յ 20
19775
98.1
8295/0.082
3376
no. of reflns collcd
completeness to θmax
no. of indep reflns/Rint
no. of reflns obsd with
(I > 2σ(I))
no. of refined Params
406
0.832
0.0247
0.0405
0.001
514
0.694
0.0446
0.0846
0.001
GooF (F2)
R1 (F) (I > 2σ(I))
wR2 (F2) (all Data)
(∆/σ)max
3
˚
Largest diff. peak/hole, e/A
0.632/Ϫ0.936
1.242/Ϫ1.633
The 31P NMR spectrum of 2 shows a single resonance at
δ ϭ 19.9 which is shifted to slightly higher frequency as
compared to the signal of the phosphonate precursor {5-t-
Bu-1,3-[P(O)(OEt)2]2C6H3} (A-H) (δ31P ϭ 18.9) [35]. This
shift is similar to the related organosilicon [37] (δ31P ϭ
19.1) and organotin compound [35] (δ31P ϭ 20.7), respec-
tively.
The 31P NMR spectrum of a benzene solution of com-
pound 2 to which had been added three molar equivalents
triphenyllead chloride showed after 30 days two doublet
resonances at δ31P ϭ 21.0 (J(31P-31P) ϭ 3.1 Hz) and δ31P ϭ
31.2 (J(31P-31P) ϭ 3.1 Hz) (total integral 82 %) which are
assigned to the hypercoordinated benzoxaphosphaplumbole
[1(Pb),3(P)-Pb(Ph)2OP(O)(OEt)-5-t-Bu-7-P(O)(OEt)2]C6H2
(3). Also present was a singlet resonance at δ31P ϭ 18.2
(integral 18 %) belonging to (A-H). Compound 3 was not
isolated from this reaction mixture but was obtained as its
triphenyllead chloride adduct {[1(Pb),3(P)-Pb(Ph)2OP(O)-
(OEt)-5-t-Bu-7-P(O)(OEt)2]C6H2·Ph3PbCl} (3a) from reac-
tion of the tetraorganolead derivative 2 with two molar
amounts of triphenyllead chloride (Scheme 1).
Figure 1 General view (SHELXTL) of a molecule of 2 showing
30 % probability displacement ellipsoids and the atom numbering.
Furthermore, the benzoxaphosphaplumbole [1(Pb),3(P)-
Pb(Ph)2OP(O)(OEt)-5-t-Bu-7-P(O)(OEt)2]C6H2
(3) was
radius for lead is apparently not available in the literature
[66].
also formed in situ in approximately 68 % by reaction at
low temperature of {4-t-Bu-2,6-[P(O)(OEt)2]2C6H2}Li (1)
with diphenyllead dichloride, Ph2PbCl2 (eq. (1)). In ad-
dition to the signals assigned to compound 3 (δ31P ϭ 23.6,
˚
The Pb(1)ϪC(1) distance of 2.269(3) A is longer than the
˚
˚
Pb(1)ϪC(11) (2.232(3) A), Pb(1)ϪC(21) (2.214(3) A), and
Z. Anorg. Allg. Chem. 2002, 628, 2435Ϫ2442
2437

K. Peveling, M. Schürmann, K. Jurkschat
The lead-carbon distances show only slight variations
˚
(2.18(1) Ϫ 2.21(1) A) and are similar with the PbϪC dis-
˚
tances of 2.18(2) A in pentacoordinated Ph3PbOH [76].
˚
The Pb(1)ϪO(1) distance of 2.470(7) A is only slightly
˚
longer than the Pb(1)ϪO(2Ј) distance of 2.300(7) A. The
difference between the two MϪO distances in the related
organotin [38] and organosilicon [43] compounds amounts
˚
to 0.27 and 0.96 A, respectively. One interpretation of these
findings is given in reference [43].
The O(2)-atom is coordinated to an additional tri-
phenyllead chloride molecule resulting in a distorted trig-
onal bipyramidal configuration (geometrical goodness
[73Ϫ75] ∆Σ(θ) ϭ 77.3°) for the Pb(2)-atom with O(2) and
Cl (1) occupying the axial and C(41), C(51), C(61) occupy-
ing the equatorial positions. The O(2)-Pb(2)-Cl(1) angle
amounts to 178.9(2)° and the lead atom is displaced by
˚
0.143(6) A in direction of Cl(1) from the trigonal plane de-
fined by C(41), C(51) and C(61). In comparison to the
˚
PbϪCl bond distance of 2.706(1) A found for polymeric
˚
Ph3PbCl [77] the Pb(2)-Cl(1) distance (2.612(3) A) in com-
pound 3a is 3.5 % shorter. A similar trend holds for the
Pb-Br distance in Ph3PbBr·OϭPPh3 [78] when compared
with the corresponding distance in polymeric Ph3PbBr [77]
(shortening 3.4 %).
Figure 2 General view (SHELXTL) of 3·Ph3PbCl (3a) showing
30 % probability displacement ellipsoids and the atom numbering.
The IR spectrum of compound 3a shows PϭO absorp-
tions at 1170 and 1203 cmϪ1
. They correspond to
P(1)ϪO(1) and P(2)ϪO(2) distances of 1.513(7) and
˚
1.475(6) A. For related organotin [38] and organosilicon
d, integral 34 %; δ31P ϭ 31.4, d, integral 34 %) the 31P
NMR spectrum of the crude reaction mixture showed sin-
gle resonances at δ31P ϭ 19.0 (integral 24 %), belonging
to {5-t-Bu-1,3-[P(O)(OEt)2]2C6H3} (A-H) and δ31P ϭ 20.2
(integral 8 %, not assigned).
Tetracoordinated benzoxaplumboles have been prepared
by oxidation of triphenyl-o-carboxyphenyllead with potass-
ium permanganate [64, 72].
The molecular structure of the triphenyllead chloride ad-
duct {[1(Pb),3(P)-Pb(Ph)2OP(O)(OEt)-5-t-Bu-7-P(O)(OEt)2]-
C6H2·Ph3PbCl} (3a) is shown in Figure 2, selected struc-
tural data are given in Table 1 and relevant crystallographic
parameters are listed in Table 2.
[43] derivatives the corresponding PϭO absorptions
amount to 1172 and 1242 cmϪ1, and 1223 and 1256 cmϪ1
respectively.
,
At 20 °C the 207Pb NMR spectrum of compound 3a
shows one resonance at δ207Pb Ϫ157(ν1/2 ϭ 91 Hz). The
corresponding 31P NMR spectrum shows two resonances
of equal integral at δ31P ϭ 22.0 and δ31P ϭ 31.4 with 31P-
207Pb couplings of 42 Hz and 20 Hz, respectively. At
Ϫ85 °C the 207Pb NMR spectrum shows two resonances at
δ207Pb Ϫ144 (ν1/2 ϭ 124 Hz) and Ϫ218 (ν1/2 ϭ 161 Hz).
The 31P NMR spectrum at Ϫ85 °C exhibits again two res-
onances at δ31P 21.6 and 31.7. Most remarkably, the low
frequency signal shows an additional J(31P-207Pb) of 74 Hz
(Table 3). The temperatur-dependent 31P and 207Pb NMR
spectra reveal the triphenyllead chloride complex 3a to be
kinetically labile at room temperature and kinetically inert
at low temperature on the 31P and 207Pb NMR time scales,
respectively. Furthermore, lowering the temperature shifts
the equilibrium toward the complex 3a. A similar obser-
vation was reported for the adduct [Ph2Sn(2-
OC6H4C(CH3)ϭNCH2COO)·Ph3SnCl] [79].
In compound 3a the lead atom Pb(1) belonging to the
benzoxaphosphaplumbole moiety adopts a distorted trig-
onal bipyramidal configuration (geometrical goodness
[73Ϫ75] ∆Σ(θ) ϭ 89.0°) with O(1) and O(2Ј) occupying the
axial positions and C(1), C(11), and C(21) occupying the
equatorial positions. The O(1)ϪPb(1)ϪO(2Ј) angle
amounts to 157.5(2)° which is 2.7° and 10.7° smaller than
the corresponding angles in the related tin [38] and silicon
[43] derivatives, respectively. The equatorial angles range
from 116.8(4)° for C(1)ϪPb(1)ϪC(11) to 124.1(4)° for
C(1)ϪPb(1)ϪC(21). The corresponding angles in the re-
lated organotin [38] and organosilicon [43] compounds
show smaller differences and amount to 116.3(4)° Ϫ
121.7(3)° and 115.0(2)° Ϫ 119.0(2)°, respectively. The lead
Reaction of the tetraorganolead derivative 2 with tri-
phenylcarbonium hexafluorophosphate and p-toluene sul-
fonic acid, respectively, gave the corresponding ionic trior-
ganolead derivatives 4 and 4a (Scheme 2).
Compound 4 is a colorless solid which is stable on expo-
sure to light and atmosphere for several hours. Compound
˚
atom is displaced by 0.011(7) A in direction of O(2Ј) from
4a was not isolated and was identified only in situ by its 31
resonance at δ 33.3 (s, J(31P-207Pb) ϭ 68 Hz).
P
the trigonal plane defined by C(1), C(11) and C(21).
2438
Z. Anorg. Allg. Chem. 2002, 628, 2435Ϫ2442

The First [4ϩ2]-Coordinated Tetraorganolead Compound
Table 3 Selected NMR Data for AϪH, 2, 3a, 4, 4a, 5, and 6.
δ (31P)
δ (207Pb)
AϪHa) [35]
18.9
19.9
2b)
J(31P-207Pb) ϭ 36 Hz Ϫ231
J(31P-207Pb)
ϭ 39 Hz
3a
22.0a)
31.4a)
21.6
4J(31P-31P) ϭ 5 Hz
J(31P-207Pb) ϭ 42 Hz
4J(31P-31P) ϭ 5 Hz
J(31P-207Pb) ϭ 20 Hz
4J(31P-31P) ϭ 3 Hz
Ϫ157c) (ν1/2 ϭ 91 Hz)
(T ϭ 20 °C)
3ac)
(T ϭ Ϫ85°C)
Ϫ144
(ν1/2 ϭ 124 Hz)
(ν1/2 ϭ 161 Hz)
J(31P-207Pb) ϭ 39 Hz Ϫ218
J(31P-207Pb) ϭ 74 Hz
31.7
34.0
Ϫ142.8
33.3
29.0
4J(31P-31P) ϭ 3 Hz
4b)
J(31P-207Pb) ϭ 58 Hz Ϫ90
J(31P-207Pb)
ϭ 64 Hz
4aa)
5a)
J(31P-207Pb) ϭ 68 Hz
Ϫ365
Ϫ500
(ν1/2 ϭ 57 Hz)
(ν1/2 ϭ 48 Hz)
6a)
29.4
a) CDCl3, b) C6D6, c) CD2Cl2
The PϭO absorption in the IR spectrum of 4 at ν˜
1182 cmϪ1 indicates the strength of the intramolecular
O···Pb coordination to be similar to that in the benzo-
xaphosphaplumbole derivative 3a (ν˜ (PϭO) 1170 cmϪ1).
The 31P and 207Pb NMR spectra (Table 3) of 4 show sig-
nals at δ31P ϭ 34.0 (J(31P-207Pb) ϭ 58 Hz) and at δ207Pb ϭ
Ϫ90 (J(207Pb-31P) ϭ 64 Hz). The 31P NMR resonance is
high-frequency shifted with respect to those of the or-
ganotin cation [{4-t-Bu-2,6-[P(O)(O-i-Pr)2]2C6H2}SnPh2]ϩ
[PF6]Ϫ (δ31P ϭ 26.1) [44] and the related organosilicon
cation {4-t-Bu-2,6-[{P(O)(OEt)2]2C6H2}SiPh2]ϩ [PF6]Ϫ
(δ31P ϭ 29.6) [43], respectively.
(OEt)2]2C6H2}Ϫ (A) in particular are a useful concept for
the synthesis of novel organolead compounds such as the
first [4ϩ2]-coordinated tetraorganolead compound 2 and
the first hypercoordinated benzoxaphosphaplumbole, as its
triphenyllead chloride adduct 3a, as well as a hypercoordin-
ated triorganolead cation 4 and hypercoordinated dior-
ganolead dihalides 5, 6.
This concept proved also to be successful for the syn-
thesis of novel organolead(II) compounds which will be
demonstrated in a forthcoming paper.
Reaction of the tetraorganolead compound 2 with bro-
mine and hydrogen chloride, respectively, gave the intramol-
ecularly coordinated diorganolead dihalides 5 and 6 in
high yields.
Experimental Section
All solvents were dried and purified by standard procedures. All
reactions were carried out under argon atmosphere using Schlenk
techniques.
Both compound 5 and 6 are light- and air-stable solids.
According to the PϭO frequencies from the infra red spec-
tra, the strength of the intramolecular PϭO···Pb coordi-
Bruker DPX-300 and DRX-400 spectrometers were used to obtain
1H, 13C, 31P, and 207Pb NMR spectra. 1H, 13C, 31P, and 207Pb NMR
chemical shifts δ are given in ppm and were referenced to Me4Si,
H3PO4 (85 %), and PbCl2 in D2O (saturated), respectively. NMR
spectra were recorded at room temperature unless otherwise stated.
IR spectra were recorded on a Bruker IFS 28 spectrometer. UV
spectra were performed on a Varian Cary 100. Elemental analyses
were recorded on a LECO-CHNS-932 analyser.
nation in the diorganolead dihalides 5 (ν˜ (PϭO) 1186 cmϪ1
)
and 6 (ν˜ (PϭO) 1188 cmϪ1) is rather similar to that in the
triorganolead cation 4 (ν˜ (PϭO) 1182 cmϪ1). The corre-
sponding intramolecularly coordinated diorganotin dihal-
ides [35] show absorptions at 1178 cmϪ1 and 1176 cmϪ1
suggesting a slightly stronger PϭO···Sn coordination.
Although the intramolecular PϭO···Pb coordination is
likely to be retained in solution, the 207Pb NMR chemical
shifts of δ Ϫ365 (5) and δ Ϫ500 (6) cannot be taken as
unambiguous evidence for this because the corresponding
data for Ph2PbX2 (X ϭ Br, Cl) are not available in the lit-
erature and our own attempts to measure their 207Pb chemi-
cal shifts failed.
{4-t-Bu-2,6-[P(O)(OEt)2]2C6H2}Li (1) was prepared as previously
reported [35].
Crystallography
Intensity data for the colorless crystals were collected on a Nonius
The 31P NMR spectra (Table 3) reveal broad resonances
for which no 207Pb satellites were detected.
KappaCCD diffractometer with graphite-monochromated MoKα
˚
(0.71073 A) radiation at 173(1) K. The data collection covered al-
most the whole sphere of reciprocal space with 3 sets at different
κ-angles with 287 (2) and 311 (3a) frames via ω-rotation (∆/ω ϭ
1°) at two times 20s per frame. The crystal-to-detector distances
were 3.4 cm. Crystal decays were monitored by repeating the initial
frames at the end of data collection. The data were not corrected
for absorption effects. Analyzing the duplicate reflections there
were no indications for any decay. The structures were solved by
Conclusion
The results presented here demonstrate that intramolecular
coordination in general and the application of the O,C,O-
coordinating
pincer-type
ligand
{5-t-Bu-1,3-[P(O)-
Z. Anorg. Allg. Chem. 2002, 628, 2435Ϫ2442
2439

K. Peveling, M. Schürmann, K. Jurkschat
CH2], 128.4 [s, 4J(13C-207Pb) ϭ 24 Hz, Cp (Ph3PbCl)], 129.3 [s, 3J(13C-
207Pb) ϭ 113 Hz, Cm (Ph3PbCl)], 129.8 / 140.2 [dd / dd, 1J(13C-31P) ϭ
189 Hz / 1J(13C-31P) ϭ 178 Hz, 3J(13C-31P) ϭ 15 Hz / 3J(13C-31P) ϭ 14 Hz,
C7,8], 130.0 (s, Cp), 130.1 (s, Cm), 130.3 (s, Cm), 131.1 / 134.3 [dd / dd, 2J(13C-
31P) ϭ 11 Hz / 2J(13C-31P) ϭ 11 Hz, 4J(13C-31P) ϭ 3 Hz / 4J(13C-31P) ϭ 3 Hz,
C4,6], 135.3 [s, 2J(13C-207Pb) ϭ 95 Hz, Co], 136.5 [s, 2J(13C-207Pb) ϭ 90 Hz,
Co (Ph3PbCl)], 153.9 [AXY-pattern, 3J(13C-31P) ϭ 12 Hz, C5], 156.7 (s, Ci),
157.7 (s, Ci), 160.5 [s, 1J(13C-207Pb) ϭ 716 Hz, Ci (Ph3PbCl)], 166.2 [AXY-
pattern, 2J(13C-31P) ϭ 15 Hz, C9]; 31P{1H} NMR (161.98 MHz, CDCl3) δ
22.0 [d, 4J(31P-31P) ϭ 5 Hz , J(31P-207Pb) ϭ 42 Hz], 31.4 [d, 4J(31P-31P) ϭ
5 Hz, J(31P-207Pb) ϭ 20 Hz]; 31P{1H} NMR (161.98 MHz, CD2Cl2, Tϭ
Ϫ85 °C) δ 21.6 [d, 4J(31P-31P) ϭ 3 Hz , J(31P-207Pb) ϭ 39 Hz, J(31P-207Pb) ϭ
74 Hz], 31.7 [d, 4J(31P-31P) ϭ 3 Hz]; 207Pb{1H} NMR (83.72 MHz, CD2Cl2)
δ Ϫ157 (ν1/2 ϭ 91 Hz); 207Pb{1H} NMR (83.72 MHz, CD2Cl2, T ϭ Ϫ85 °C)
δ Ϫ144 (ν1/2 ϭ 124 Hz), Ϫ218 (ν1/2 ϭ 161 Hz); IR (KBr): ν˜ (PϭO)
1203 cmϪ1, 1170 cmϪ1, ν˜ (Pb-C) 447 cmϪ1; UV-vis (hexane) λm ϭ 222 nm
(ε ϭ 8374 L molϪ1 cmϪ1); MS: m/z (%) 662 (1, M Ϫ Ph3PbCl Ϫ Ph ϩ H),
439 (22, M Ϫ Ph3PbCl Ϫ 2Ph Ϫ t-Bu Ϫ 2OEt ϩ 2H).
direct methods SHELXS97 [80] and successive difference Fourier
syntheses. Refinements applied full-matrix least-squares methods
SHELXL97 [81].
The H atoms were placed in geometrically calculated positions
using a riding model with isotropic temperature factors constrained
at 1.2 for non-methyl and at 1.5 for methyl groups times Ueq of the
carrier C atom.
Atomic scattering factors for neutral atoms and real and imaginary
dispersion terms were taken from International Tables for XϪray
Crystallography [82]. The figures were created by SHELXTL [83].
Crystallographic data are given in Table 2, selected bond distances
and angles in Table 1. Crystallographic data (excluding structure
factors) for the structures in this paper have been deposited at the
Cambridge Crystallographic Data Centre as supplementary publi-
cation nos. CCDC 184286 (2) and CCDC 184287 (3a). Copies of
the data can be obtained, free of charge, on application to CCDC,
12 Union Road, Cambridge CB2 1EZ, UK (Fax: ϩ 44-(0)12 23-33
60 33 or e-mail: deposit@ccdc.cam.ac.uk)
Method B: To a solution of [2,6-bis(diethoxyphosphonyl)-4-tert-bu-
tyl]phenyllithium (1) (2.55 g, 6.18 mmol) in 110 mL THF was ad-
ded portionwise, at Ϫ55 °C, diphenyllead dichloride (2.80 g,
6.48 mmol). After the reaction mixture had been stirred for 16 h
(Ϫ55 °C to room temperature) the solvent was evaporated. The yel-
low residue was characterised by NMR-spectroscopy.
{[2,6-Bis(diethoxyphosphonyl)-4-tert-butyl]phenyl}triphenyl-
plumbane (2).
31P NMR (161.98 MHz, CDCl3)
δ
19.0 (s, 24 %, {5-t-Bu-1,3-
To a solution of [2,6-bis(diethoxyphosphonyl)-4-tert-butyl]phen-
yllithium (1) (2.73 g, 6.62 mmol) in 50 mL THF was added portion-
wise, at Ϫ60 °C, triphenyllead chloride (4.86 g, 10.25 mmol). After
the reaction mixture had been stirred for 16 h (Ϫ60 °C to room
temperature) the solvent was evaporated. Column chromatography
(SiO2/EtOAc) of the residue and crystallization from Et2O afforded
3.89 g (70 %) of 2 as colorless crystals, mp. 118-120 °C.
Anal. Calcd for C36H46O6PbP2: C, 51.2; H, 5.5. Found: C, 51.2;
H, 5.4 %
1H NMR (400.13 MHz, C6D6) δ 0.90 (t, 12H, CH3), 1.18 (s, 9H, CH3), 3.40
Ϫ 3.51 (complex pattern, 4H, CH2), 3.63 Ϫ 3.73 (complex pattern, 4H, CH2),
7.11 (t, 3H, aromatics), 7.28 (complex pattern, 6H, aromatics), 8.13 (d, 6H,
aromatics), 8.46 (complex pattern, 2H, aromatics); 13C{1H} NMR
(100.61 MHz, C6D6) δ 16.2 [complex pattern, 3J(13C-31P) ϭ 3 Hz, J(13C-
207Pb) ϭ 17 Hz, CH3], 30.9 (s, CH3), 34.7 [s, 5J(13C-207Pb) ϭ 7 Hz, C], 61.7
(complex pattern, CH2), 127.2 [s, 4J(13C-207Pb) ϭ 19 Hz, Cp], 128.7 (s, Cm),
134.3 (complex pattern C3,5), 138.3 [s, 2J(13C-207Pb) ϭ 70 Hz, Co], 139.4 [dd,
1J(13C-31P) ϭ 193 Hz, 3J(13C-31P) ϭ 20 Hz, C2,6], 150.5 [t, 3J(13C-31P) ϭ
13 Hz, C4], 161.6 [s, 1J(13C-207Pb) ϭ 570 Hz, Ci], 164.2 [t, 2J(13C-31P) ϭ
21 Hz, C1]; 31P{1H} NMR (161.98 MHz, C6D6) δ 19.9 [s, J(31P-207Pb) ϭ
36 Hz]; 207Pb{1H} NMR (83.72 MHz, C6D6) δ Ϫ231 [t, J(207Pb-31P) ϭ
39 Hz]; IR (KBr): ν˜ (PϭO) 1246 cmϪ1, ν˜ (Pb-C) 453, 443 cmϪ1; UV-vis (hex-
ane) λm ϭ 223 nm (ε ϭ 27721 L molϪ1 cmϪ1); MS: m/z (%) 768 (63, M Ϫ
Ph ϩ H), 767 (32, M Ϫ Ph), 614 (100, M Ϫ 3Ph ϩ H), 613 (48, M Ϫ 3Ph),
483 (34, M Ϫ 3Ph Ϫ OEt Ϫ Et Ϫ t-Bu ϩ H).
[P(O)(OEt)2]2C6H3}), 20.2 (s, 8 %), 23.6 [d, 4J(31P-31P) ϭ 3 Hz, 34 %, 3], 31.4
[d, 4J(31P-31P) ϭ 3 Hz, 34 %, 3].
Method C: To a solution of {[2,6-bis(diethoxyphosphonyl)-4-tert-
butyl]phenyl}triphenylplumbane (2) (7 mg, 8.2·10Ϫ6 mol) in 0.5 mL
C6D6 was added, at 20 °C, triphenyllead chloride (12 mg,
25.3·10Ϫ6 mol). After the reaction mixture had been stirred for 30
days the solution was characterised by NMR-spectroscopy.
31P NMR (161.98 MHz, C6D6)
δ
18.2 (s, 18 %, {5-t-Bu-1,3-
[P(O)(OEt)2]2C6H3}), 21.0 [d, 4J(31P-31P) ϭ 3 Hz, 41 %, 3], 31.2 [d, 4J(31P-
31P) ϭ 3 Hz, 41 %, 3].
{[2,6-Bis(diethoxyphosphonyl)-4-tert-butyl]phenyl}diphenylplumbonium
hexafluorophosphate (4). To
a solution of {[2,6-bis(diethoxy-
phosphonyl)-4-tert-butyl]phenyl}triphenylplumbane (2) (0.43 g,
0.51 mmol) in toluene (12 mL) was added, at 38 °C, triphenylcar-
boniumhexafluorophosphat (0.20 g, 0.52 mmol). After the reaction
mixture had been stirred at this temperature for 2 days the solvent
was evaporated. The brown oil was extracted four times with 10 mL
hexane. Extraction with 5 mL benzene afforded 0.36 g (77 %) 4 as
a colorless oil which solidified after one week. mp.: 110 °C.
Anal. Calcd for C30H41O6PbP3F6: C, 39.5; H, 4.5. Found: C, 39.4;
H, 4.6 %
1H NMR (400.13 MHz, C6D6) δ 1.06 (t, 12H, CH3), 1.35 (s, 9H, CH3), 3.94
Ϫ 4.03 (complex pattern, 4H, CH2), 4.09 Ϫ 4.19 (complex pattern, 4H, CH2),
7.11 (t, 2H, aromatics), 7.42 (t, 4H, aromatics), 7.93 (d, 4H, aromatics), 8.37
(complex pattern, 2H, aromatics); 13C{1H} NMR (100.61 MHz, C6D6) δ
16.1 [complex pattern, 3J(13C-31P) ϭ 3 Hz, CH3], 30.8 (s, CH3), 35.6 (s, C),
65.7 [complex pattern, 2J(13C-31P) ϭ 2 Hz, CH2], 131.4 [s, 4J(13C-207Pb) ϭ
29 Hz, Cp], 131.4 [s, 3J(13C-207Pb) ϭ 124 Hz, Cm], 132.1 [dd, 1J(13C-31P) ϭ
188 Hz, 3J(13C-31P) ϭ 17 Hz, C2,6], 135.6 (complex pattern C3,5), 136.0 [s,
2J(13C-207Pb) ϭ 102 Hz, Co], 156.6 [t, 3J(13C-31P) ϭ 12 Hz, C4], 157.0 (s, Ci),
169.9 [t, 2J(13C-31P) ϭ 17 Hz, C1]; 31P{1H} NMR (161.97 MHz, C6D6) δ
34.0 [s, J(31P-207Pb) ϭ 58 Hz], Ϫ142.8 (septett, PF6Ϫ); 207Pb{1H} NMR
(83.72 MHz, C6D6) δ Ϫ90 [t, J(207Pb-31P) ϭ 64 Hz]; IR (KBr): ν˜ (PϭO)
5-tert-Butyl-7-diethoxyphosphonyl-3-ethoxy-3-oxo-1,1-diphenyl-
2,3,1-benzoxaphosphaplumbole-triphenyllead chloride adduct (3a).
Method A: To a solution of {[2,6-bis(diethoxyphosphonyl)-4-tert-
butyl]phenyl}triphenylplumbane (2) (0.51 g, 0.60 mmol) in 50 mL
THF was added, at 20 °C, triphenyllead chloride (0.57 g,
1.20 mmol). After the reaction mixture had been stirred for 26 days
the solvent was evaporated. Crystallization of the residue from
EtOAc afforded 0,31 g Ph4Pb, which was separated by filtration.
The filtrate was again evaporated and the residue was recrystallized
from CHCl3/hexane (1:1) to give 0.50 g (69 %) 3a as colorless crys-
tals, mp 125-127 °C.
1182 cmϪ1
3053 L molϪ1 cmϪ1), 254 nm (ε
,
ν˜ (Pb-C) 442 cmϪ1
;
UV-vis (hexane) λm
ϭ
ϭ
221 nm (ε
ϭ
ϭ
1292 L molϪ1 cmϪ1), 260 nm (ε
1271 L molϪ1 cmϪ1); MS: m/z (%) 766 (5, M Ϫ PF6 Ϫ H), 708 (100, M Ϫ
PF6 Ϫ tBu Ϫ 2H), 612 (21, M Ϫ PF6 Ϫ 2Ph Ϫ H), 584 (16, MϪ PF6 Ϫ 2Ph
Ϫ Et).
Anal. Calcd for C46H51O6Pb2P2Cl: C, 45.6; H, 4.2. Found: C, 45.8;
H, 4.2
1H NMR (400.13 MHz, CDCl3) δ 1.21 (t, 9H, CH3), 1.29 (s, 9H, CH3), 3.78
Ϫ 4.07 (complex pattern, 6H, CH2), 7.33 (complex pattern, 5H, aromatics),
7.46 (t, 10H, aromatics), 7.80 (d, 10H, aromatics), 7.81 (d, 1H, aromatics),
8.16 (d, 1H, aromatics); 13C{1H} NMR (100.61 MHz, CDCl3) δ 16.1 [d,
3J(13C-31P) ϭ 6 Hz, CH3], 16.4 [d, 3J(13C-31P) ϭ 7 Hz, CH3], 30.9 (s, CH3),
35.0 (s, C), 60.9 [d, 2J(13C-31P) ϭ 6 Hz, CH2], 63.7 [d, 2J(13C-31P) ϭ 6 Hz,
{[2,6-Bis(diethoxyphosphonyl)-4-tert-butyl]phenyl}diphenylplumbonium
p-toluenesulfonate (4a). To
a
solution {[2,6-bis(diethoxyphos-
(2) (3.4 mg,
phonyl)-4-tert-butyl]phenyl}triphenylplumbane
4.03·10Ϫ6 mol) in CDCl3 (0.45 mL) was added, at 20 °C, p-toluene
2440
Z. Anorg. Allg. Chem. 2002, 628, 2435Ϫ2442

The First [4ϩ2]-Coordinated Tetraorganolead Compound
sulfonic acid (25.5 mg, 148.08·10Ϫ6 mol). After 5 minutes the reac-
tion mixture was characterised by NMR-spectroscopy. 31P NMR
(121.49 MHz, CDCl3) δ 33.3 [s, J(31P-207Pb) ϭ 68 Hz].
[2] J. T. B. H. Jastrzebski, P. A. van der Schaaf, J. Boersma, G.
van Koten, M. C. Zoutberg, D. Heijdenrijk, Organometallics
1989, 8, 1373.
[3] G. van Koten Pure Appl. Chem. 1989, 61, 1681.
[4] G. van Koten Pure Appl. Chem. 1990, 62, 1155.
[5] G. van Koten, J. Terheijden, J. A. M. van Beek, I. C. M. Weh-
man-Ooyevaar, F. Muller, C. H. Stam, Organometallics 1990,
9, 903.
[6] H. C. L. Abbenhuis, N. Feiken, D. M. Grove, J. T. B. H. Jastrz-
ebski, H. Kooijman, P. van der Sluis, W. J. J. Smeets, A. L.
Spek, G. van Koten, J. Am. Chem. Soc. 1992, 114, 9773.
{[2,6-Bis(diethoxyphosphonyl)-4-tert-butyl]phenyl}dibromophenylplum-
bane (5). To
a solution {[2,6-bis(diethoxyphosphonyl)-4-tert-
butyl]phenyl}triphenylplumbane (2) (0.15 g, 0.178 mmol) in tolu-
ene / MeOH (30 mL, 1:1) was added dropwise, at Ϫ20 °C, 1.82 mL
of a solution of Br2 in MeOH (0.195 M). After the reaction mixture
was stirred for 4 d at room temperature the solvent was evaporated.
A mixture of CHCl3/hexane (20 mL,1:1) was added to the residue
and the resulting suspension was stirred for 30 minutes. The super-
natend solution was then decantated from insoluble residue. Evap-
oration of the solvent afforded 0.12 g (79 %) 5 as colorless solid
which decomposes at 168 °C.
´
[7] C. Chuit, R. J. P. Corriu, A. Mehdi, C. Reye, Angew. Chem.
1993, 105, 1372; Angew. Chem. Int. Ed. Engl. 1993, 32, 1311.
´
´
[8] F. Carre, C. Chuit, R. J. P. Corriu, A. Mehdi, C. Reye, Angew.
Chem. 1994, 106, 1152; Angew. Chem. Int. Ed. Engl. 1994,
33, 1097.
Anal. Calcd for C24H36O6PbP2Br2: C, 33.9; H, 4.3. Found: C, 34.1;
H, 4.1 %
´
´
[9] F. Carre, C. Chuit, R. J. P. Corriu, A. Mehdi, C. Reye, Or-
1H NMR (400.13 MHz, CDCl3) δ 1.32 (t, 12H, CH3), 1.39 (s, 9H, CH3),
4.22 Ϫ 4.32 (complex pattern, 4H, CH2), 4.39 Ϫ 4.49 (complex pattern, 4H,
CH2), 7.45 (t, 1H, aromatics), 7.61 (t, 2H, aromatics), 8.06 (d, 2H, aro-
matics), 8.54 (complex pattern, 2H, aromatics); 13C{1H} NMR
(100.63 MHz, CDCl3) δ 16.1 [complex pattern, 3J(13C-31P) ϭ 3 Hz, CH3],
31.0 (s, CH3), 35.3 (s, C), 62.3 (s, CH2), 125.2 [dd, 1J(13C-31P) ϭ 184 Hz,
3J(13C-31P) ϭ 14 Hz, C2,6], 130.2 [s, 3J(13C-207Pb) ϭ 238 Hz, Cm], 131.0 [s,
4J(13C-207Pb) ϭ 46 Hz, Cp], 133.1 [s, 2J(13C-207Pb) ϭ 156 Hz, Co], 134.1
(complex pattern C3,5), 154.1 [t, 3J(13C-31P) ϭ 12 Hz, C4], 160.7 (Ci), 183.7
ganometallics 1995, 14, 2754.
´
[10] F. Carre, C. Chuit, R. J. P. Corriu, A. Fanta, A. Mehdi, C.
´
Reye, Organometallics 1995, 14, 194.
´
[11] M. Chauhan, C. Chuit, R. J. P. Corriu, A. Mehdi, C. Reye,
Organometallics 1996, 15, 4326.
[12] M. Chauhan, C. Chuit, R. J. P. Corriu, C. Reye, Tetrahedron
´
Letters 1996, 37, 845.
(C1); 31P{1H} NMR (161.98 MHz, CDCl3)
δ
29.0; 207Pb{1H} NMR
[13] J.-P. Sutter, S. L. James, P. Steenwinkel, T. Karlen, D. M.
Grove, N. Veldman, W. J. J. Smeets, A. L. Spek, G. van Koten,
Organometallics 1996, 15, 941.
[14] R. Schlengermann, J. Sieler, S. Jelonek, E. Hey-Hawkins,
Chem. Commun. 1997, 197.
(83.72 MHz, CDCl3) δ Ϫ365 (ν1/2 ϭ 57 Hz); IR (KBr): ν˜ (PϭO) 1186 cmϪ1
,
ν˜ (Pb-C) 442 cmϪ1; UV-vis (hexane) λm ϭ 221 nm (ε ϭ 5632 L molϪ1 cmϪ1),
254 nm (ε ϭ 2575 L molϪ1 cmϪ1); MS: m/z (%) 767 (23, M Ϫ Br Ϫ 2H),
611 (100, M Ϫ 2Br Ϫ Ph Ϫ H).
´
´
[15] F. Carre, M. Chauhan, C. Chuit, R. J. P. Corriu, C. Reye, J.
{[2,6-Bis(diethoxyphosphonyl)-4-tert-butyl]phenyl}dichlorophenylplum-
Organomet. Chem. 1997, 540, 175.
[16] J. A. M. Brandts, R. A. Gossage, J. Boersma, A. L. Spek, G.
van Koten, Organometallics 1999, 18, 2642.
[17] M. R. Meneghetti, M. Grellier, M. Pfeffer, A. De Cian, J.
Fischer, Eur. J. Inorg. Chem. 2000, 1539.
[18] M. Albrecht, S. L. James, N. Veldman, A. L. Spek, G. van
Koten, Can. J. Chem. 2001, 79, 709.
bane (6).
A solution of {[2,6-bis(diethoxyphosphonyl)-4-tert-
butyl]phenyl}triphenylplumbane (2) (0.14 g, 0.166 mmol) in diethyl
ether (25 mL) was treated with gaseous hydrogen chloride at 0 °C
for 2 h. After the reaction mixture had been stirred for 3 d at room
temperature the solvent was evaporated. A mixture of CHCl3/hex-
ane (25 mL, 1:1) was added to the residue and the mixture was
stirred for 30 minutes. The supernatend solution was decantated
from insoluble residue. Evaporation of the solvent afforded 0.11 g
(87 %) 6 as colorless solid which decomposes at 180 °C.
Anal. Calcd for C24H36O6PbP2Cl2: C, 37.9; H, 4.8. Found: C, 38.1;
H, 4.6 %
[19] M. Albrecht, B. M. Kocks, A. L. Spek, G. van Koten, J. Or-
ganomet. Chem. 2001, 624, 271.
´
[20] G. Rodrıguez, M. Lutz, A. L. Spek, G. van Koten, Chem. Eur.
J. 2002, 8, 46.
[21] C. J. Moulton, B. L. Shaw, J. Chem. Soc., Dalton Trans.
1976, 1020.
[22] F. Gorla, L. M. Venanzi, A. Albinati, Organometallics 1994,
13, 43.
[23] A. Pape, M. Lutz, G. Müller, Angew. Chem. 1994, 106, 2375;
Angew. Chem. Int. Ed. Engl. 1994, 33, 2281.
[24] T. Karlen, P. Dani, D. M. Grove, P. Steenwinkel, G. van Koten,
Organometallics 1996, 15, 5687.
[25] M. Gupta, C. Hagen, R. J. Flesher, W. C. Kaska, C. M. Jensen,
Chem. Commun. 1996, 2083.
[26] G. Müller, M. Waldkircher, A. Pape, “Phosphine Coordi-
nation to Silicon Revisited” in Organosilicon Chemistry III;
Auner, N., Weis, J. (eds), Wiley-VCH, 1998, p. 452.
[27] J. C. Grimm, C. Nachtigal, H.-G. Mack, W. C. Kaska, H. A.
Mayer, Inorg. Chem. Commun. 2000, 3, 511.
[28] P. Dani, M. A. M. Toorneman, G. P. M. van Klink, G. van
Koten, Organometallics 2000, 19, 5287.
1H NMR (400.13 MHz, CDCl3) δ 1.31 (t, 12H, CH3), 1.37 (s, 9H, CH3),
4.16 Ϫ 4.26 (complex pattern, 4H, CH2), 4.37 Ϫ 4.46 (complex pattern, 4H,
CH2), 7.47 (t, 1H aromatics), 7.62 (t, 2H, aromatics), 8.05 (d, 2H, aromatics),
8.56 (complex pattern, 2H, aromatics); 13C{1H} NMR (100.63 MHz, CDCl3)
δ 16.2 [complex pattern, 3J(13C-31P) ϭ 3 Hz, CH3], 31.2 (s, CH3), 35.5 (s, C),
65.3 (s, CH2), 126.0 [dd, 1J(13C-31P) ϭ 183 Hz, 3J(13C-31P) ϭ 15 Hz, C2,6],
130.6 [s, 3J(13C-207Pb) ϭ 240 Hz, Cm], 131.4 [s, 4J(13C-207Pb) ϭ 48 Hz, Cp],
133.7 [s, 2J(13C-207Pb) ϭ 159 Hz, Co], 134.3 (complex pattern C3,5), 154.4 [t,
3J(13C-31P) ϭ 12 Hz, C4], 160.1 [t, J(13C-31P) ϭ 5 Hz, Ci], 182.3 [t, 2J(13C-
31P) ϭ 12 Hz, C1]; 31P{1H} NMR (161.99 MHz, CDCl3) δ 29.4; 207Pb{1H}
NMR (83.72 MHz, CDCl3) δ Ϫ500 (ν1/2 ϭ 48 Hz); IR (KBr): ν˜ (PϭO)
1188 cmϪ1 ν˜ (Pb-C) 444 cmϪ1
, ; UV-vis (hexane) λm ϭ 221 nm (ε ϭ
3784 L molϪ1 cmϪ1), 254 nm (ε ϭ 2363 L molϪ1cmϪ1); MS: m/z (%) 723
(100, M Ϫ Cl Ϫ 2H), 681 (68, M Ϫ Ph Ϫ 2H), 646 (25, MϪ Ph Ϫ Cl Ϫ 2H).
Acknowledgement. We thank the Deutsche Forschungsgemeinschaft
and the Fonds der Chemischen Industrie for financial support.
[29] R. P. Hughes, A. Williamson, C. D. Incarvito, A. L. Rheing-
old, Organometallics 2001, 20, 4741.
References
[1] M. Albrecht, G. van Koten, Angew. Chem. 2001, 113, 3866;
Angew. Chem. Int. Ed. Engl. 2001, 40, 3750.
[30] D. G. Gusev, F. M. Dolgushin, M. Y. Antipin, Organometallics
2001, 20, 1001.
Z. Anorg. Allg. Chem. 2002, 628, 2435Ϫ2442
2441

K. Peveling, M. Schürmann, K. Jurkschat
[31] E. J. Farrington, E. M. Viviente, B. S. Williams, G. van Koten,
[56] J. E. H. Buston, H. J. Howell, M. G. Moloney, V. C. Manson,
R. M. Thompson, Main Group Met. Chem. 1998, 21, 51.
[57] J. E. H. Buston, R. G. Compton, M. A. Leech, M. G. Mo-
loney, J. Organomet. Chem. 1999, 585, 326.
J. M. Brown, Chem. Commun. 2002, 308.
[32] J. Errington, W. S. McDonald, B. L. Shaw, J. Chem. Soc., Dal-
ton Trans. 1980, 2312.
[58] G. I. Elliott, J. P. Konopelski, Tetrahedron 2001, 57, 5683.
[59] M. G. Moloney,„Lead(IV) Carboxylates: An under-estimated
class of reagents in synthesis” at 10th International Conference
on the Coordination and Organometallic Chemistry of Ger-
manium, Tin and Lead, ICCOC-GTL-10, July 8 to 12, 2001,
Bordeaux, France, Book of Abstracts IL5.
[60] A.-F. Shihada, F. Weller, Z. Anorg. Allg. Chem. 2001, 627, 638.
[61] A. Silvestru, C. Silvestru, I. Haiduc, J. E. Drake, J. Yang, F.
Caruso, Polyhedron 1997, 16, 949.
[33] J. Dupont, N. Beydoun, M. Pfeffer, J. Chem. Soc., Dalton
Trans. 1989, 1715.
[34] W. T. S. Huck, L. J. Prins, R. H. Fokkens, N. M. M. Nibbering,
F. C. J. M. van Veggel, D. N. Reinhoudt, J. Am. Chem. Soc.
1998, 120, 6240.
[35] M. Mehring, M. Schürmann, K. Jurkschat, Organometallics
1998, 17, 1227.
[36] J. Vicente, A. Arcas, M.-A. Blasco, J. Lozano, M. C. R. de
Arellano, Organometallics 1998, 17, 5374.
[37] M. Mehring, K. Jurkschat, M. Schürmann, Main Group Met.
Chem. 1998, 21, 635.
[62] R. A. Varga, C. Silvestru, I. Haiduc, Synth. React. Inorg. Met.-
Org. Chem. 2000, 30, 485.
´
[63] S. N. Olafsson, C. Flensburg, P. Andersen, J. Chem. Soc., Dal-
[38] M. Mehring, C. Löw, M. Schürmann, K. Jurkschat, Eur. J.
Inorg. Chem. 1999, 887.
[39] J. Vicente, M.-T. Chicote, M.-D. Abrisqueta, P. G. Jones, Or-
ganometallics 2000, 19, 2629.
ton Trans. 2000, 4360.
[64] H. Gilman, D. S. Melstrom, J. Am. Chem. Soc. 1950, 2953.
[65] H. O. van der Kooi, J. Wolters, A. van der Gen, Recueil, J. R.
Neth. Chem. Soc. 1979, 98, 353.
[66] J. Huheey, E. A. Keiter, R. L. Keiter, Anorganische Chemie:
Prinzipien von Struktur und Reaktivität, 2nd ed., de Gruyter,
New YorkϪBerlin, 1995.
[67] L. Pauling, The Nature of the Chemical Bond, 3rd ed., Cornell
University Press: Ithaca, New York, 1960.
[68] J. D. Dunitz, X-Ray Analysis and the Structure of Organic Mol-
ecules, Cornell University Press: Ithaca, New York, 1979.
[69] H. Preut, F. Huber, Acta Cryst. 1993, C49, 1372.
[70] M. Henn, K. Jurkschat, R. Ludwig, M. Mehring, K. Peveling,
M. Schürmann, Organometallics 2002, submitted.
[71] E. Capek, K. E. Schwarzhans, Monatsh. Chem. 1987, 118, 419.
[72] D. S. Melstrom, Iowa State Coll. J. Sci. 1943, 18, 65.
[73] U. Kolb, M. Beuter, M. Gerner, M. Dräger, Organometallics
1994, 13, 4413.
[40] M. Mehring, C. Löw, M. Schürmann, F. Uhlig, K. Jurkschat,
Organometallics 2000, 19, 4613.
[41] M. Mehring, I. Vrasidas, D. Horn, M. Schürmann, K. Jurk-
schat, Organometallics 2001, 20, 4647.
[42] K. Peveling, M. Schürmann, K. Jurkschat, Main Group Met.
Chem. 2001, 24, 251.
[43] K. Peveling, M. Schürmann, R. Ludwig, K. Jurkschat, Or-
ganometallics 2001, 20, 4654.
[44] M. Henn, Jurkschat, K.; Löw, C.; Mehring, M.; Peveling, K.;
Schürmann, M. unpublished results.
[45] C. Löwig, J. Pract Chem. 1853, 60, 304.
[46] C. Löwig, Liebigs Ann. Chem. 1853, 88, 318.
[47] G. Calingaert, Chem. Rev. 1925, 2, 43.
[74] U. Kolb, M. Beuter, M. Dräger, Inorg. Chem. 1994, 33, 4522.
[75] U. Kolb, M. Dräger, Jousseaume, B. Organometallics 1991,
10, 2737.
[76] C. Glidewell, D. C. Liles, Acta Crystallogr. 1978, B34, 129.
[77] H. Preut, F. Huber, Z. Anorg. Allg. Chem. 1977, 435, 234.
[78] H. J. Eppley, J. L. Ealy, C. H. Yoder, J. N. Spencer, A. L.
Rheingold, J. Organomet. Chem. 1992, 431, 133.
[79] D. Dakternieks, T. S. Basu Baul, S. Dutta, E. R. T. Tiekink,
Organometallics 1998, 17, 3058.
[80] G. M. Sheldrick, Acta Cryst. 1990, A46, 467.
[81] G. M. Sheldrick, University of Göttingen, 1997.
[82] International Tables for Crystallography, Kluwer Academic:
Dortrecht 1992, Vol C.
[48] J. Sarapuk, K. Bielecki, H. Kleszczynska, A. Dziamska, S.
Przestalski, Appl. Organomet. Chem. 2001, 15, 56.
[49] D. M. X. Donnelly, J.-P. Finet, B. A. Rattigan, J. Chem. Soc.,
Perkin Trans. 1 1995, 1679.
[50] J. T. Pinley, Pure Appl. Chem. 1996, 68, 819.
[51] M. G. Moloney, R. M. Thompson, E. Wright, Main Group
Met. Chem. 1996, 19, 133.
[52] S.-K. Kang, U. Shivkumar, C. Ahn, S.-C. Choi, J.-S. Kim,
Synth. Commun. 1997, 27, 1893.
[53] S.-K. Kang, H.-C. Ryu, S.-C. Choi, Chem. Commun. 1998,
1317.
[54] S.-K. Kang, H.-C. Ryu, H.-J. Son, Synlett 1998, 771.
[55] M. G. Moloney, D. R. Paul, R. M. Thompson, E. Wright, J.
Organomet. Chem. 1998, 560, 77.
[83] G. M. Sheldrick, SHELXTL, Release 5.1 Software Reference
Manual, Bruker AXS, Inc.: Madison, Wisconsin, USA, 1997.
2442
Z. Anorg. Allg. Chem. 2002, 628, 2435Ϫ2442