Organolead(IV) derivatives of oxophosphorus ligands. X-ray structures of monomeric R2Pb[(OPPh2)2N]2 (R=Me, Ph) and tetrameric [Me3Pb(O2PPh2)]4

Article abstract of DOI:10.1016/S0022-328X(03)00229-8

The reaction of R_4-nPbCl_n with Na[(OPPh₂)₂N] or K[(OPPh₂) (SPPh₂)N] afforded isolation of Ph₂Pb [(OPPh₂)₂N]₂ (1), Ph₂Pb[(OPPh₂)(SPPh₂)N]₂ (2), Me₃Pb[(OPPh₂)₂N] (3) and Ph₃Pb[(OPPh₂)(SPPh₂)N] (4). Attempts to grow crystals of Me₃Pb[(OPPh₂)₂N] (3) led to isolation of Me₂Pb[(OPPh₂)₂N]₂ (5), as a result of decomposition. M e₃Pb(O₂PPh₂) (6) was obtained from Me₃PbCl and Na(O₂PPh₂). The compounds were characterized by IR and multinuclear NMR spectroscopy. The molecular structures of 1, 5 and 6 were determined by single-crystal X-ray diffraction. The crystal of 5 contains two independent molecules in the unit cell. In both compounds the imidodiphosphinato ligands act as monometallic biconnective units, resulting in a spiro -bicyclic system with six-membered PbO₂P₂N rings of distorted boat conformation. The coordination geometry around the metal atom is distorted octahedral, with C-Pb-C angles close to 180° [178.9(2)° for 1; 173.4(3)° and 178.7(4)° for molecules 5a and 5b, respectively]. The crystal of the trimethyllead(IV) phosphinate (6) contains discrete tetrameric units, [Me₃Pb(O₂PPh₂)]₄, with bridging phosphinato ligands [range: Pb-O 2.373(3)-2.402(6) A?, P-O 1.495(6)-1.512(6) A?], thus resulting in a sixteen-membered Pb₄O₈P₄ inorganic ring. The coordination geometry at lead atoms is distorted trigonal bipyramidal, with oxygen atoms in trans positions [range: O-Pb-O 174.7(2)-177.6(3)°].

Full text of DOI:10.1016/S0022-328X(03)00229-8

Journal of Organometallic Chemistry 675 (2003) 48ꢂ56
/
www.elsevier.com/locate/jorganchem
Organolead(IV) derivatives of oxophosphorus ligands.
X-ray structures of monomeric R2Pb[(OPPh2)2N]2 (RꢀMe, Ph) and
tetrameric [Me3Pb(O2PPh2)]4
/
Richard A. Varga a, John E. Drake b, Cristian Silvestru a,*
a Facultatea de Chimie si Inginerie Chimica, Universitatea ‘‘Babes-Bolyai’’, R-3400 Cluj-Napoca, Romania
b Department of Chemistry and Biochemistry, University of Windsor, Windsor, Ont., Canada N9B 3P4
Received 22 November 2002; received in revised form 20 February 2003; accepted 11 March 2003
Abstract
The reaction of R4ꢁnPbCln with Na[(OPPh2)2N] or K[(OPPh2)(SPPh2)N] afforded isolation of Ph2Pb[(OPPh2)2N]2 (1),
Ph2Pb[(OPPh2)(SPPh2)N]2 (2), Me3Pb[(OPPh2)2N] (3) and Ph3Pb[(OPPh2)(SPPh2)N] (4). Attempts to grow crystals of Me3P-
b[(OPPh2)2N] (3) led to isolation of Me2Pb[(OPPh2)2N]2 (5), as a result of decomposition. Me3Pb(O2PPh2) (6) was obtained from
Me3PbCl and Na(O2PPh2). The compounds were characterized by IR and multinuclear NMR spectroscopy. The molecular
structures of 1, 5 and 6 were determined by single-crystal X-ray diffraction. The crystal of 5 contains two independent molecules in
the unit cell. In both compounds the imidodiphosphinato ligands act as monometallic biconnective units, resulting in a spiro-bicyclic
system with six-membered PbO2P2N rings of distorted boat conformation. The coordination geometry around the metal atom is
distorted octahedral, with Cꢀ
/
PbꢀC angles close to 1808 [178.9(2)8 for 1; 173.4(3)8 and 178.7(4)8 for molecules 5a and 5b,
/
respectively]. The crystal of the trimethyllead(IV) phosphinate (6) contains discrete tetrameric units, [Me3Pb(O2PPh2)]4, with
˚
˚
1.512(6) A], thus resulting in a sixteen-membered
bridging phosphinato ligands [range: Pbꢀ
Pb4O8P4 inorganic ring. The coordination geometry at lead atoms is distorted trigonal bipyramidal, with oxygen atoms in trans
positions [range: OꢀPbꢀO 174.7(2)ꢂ177.6(3)8].
/
O 2.373(3)ꢂ
/
2.402(6) A, Pꢀ
/
O 1.495(6)ꢂ
/
/
/
/
# 2003 Elsevier Science B.V. All rights reserved.
Keywords: Organolead; Phosphorus ligands; Inorganic rings
1. Introduction
tallic biconnective dithiophosphinato ligand, trigonal
bipyramidal C3PbS2 core, planar C3Pb system) [3]. By
The structural investigation of organolead(IV) com-
pounds containing dithiophosphorus ligands has re-
vealed interesting patterns in the solid state (Scheme
1), i.e. monomeric Ph3PbS2P(OEt)2 (a: monometallic
monoconnective dithiophosphato ligand and tetrahedral
contrast, Ph2Pb(O2PR2)2 (RꢀMe, Ph) derivatives were
/
recently reported to exhibit a polymeric structure with
double-bridged phosphorus ligands between the lead
atoms (d: bimetallic biconnective phosphinato ligand,
octahedral C2PbO4 core, linear C2Pb system) [4]. A
similar double-bridging polymeric motif was also re-
ported for inorganic lead(II) diorganophosphinates,
C3PbS core) [1], Ph2Pb(S2PR2)2 (RꢀOCH2Ph [1], Ph
/
[2]) (b: monometallic biconnective dithiophosphorus
ligands, distorted octahedral C2PbS4 core, bent C2Pb
system), and chain polymeric [Ph3PbS2PMe2]n (c: bime-
[Pb(O2PR2)2]n (Rꢀ
Ph [5], But [6]) (e: bimetallic bicon-
nective phosphinato ligands and pseudo-trigonal bipyr-
/
amidal PbO4 core).
The
dichalcogenoimidodiphosphinato
ꢁ
anions,
significantly larger
* Corresponding author. Fax: ꢃ
E-mail address: cristi@chem.ubbcluj.ro (C. Silvestru).
/
98-40-64-190818.
?
?
[(XPR2)(YPR?2)N] , exhibit
a
0022-328X/03/$ - see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0022-328X(03)00229-8

R.A. Varga et al. / Journal of Organometallic Chemistry 675 (2003) 48ꢂ
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56
49
(1)
(2)
(3)
sphorus ligand according to Eqs. (1)ꢂ
/(3):
Ph2PbCl2 ꢃ2M[(OPPh2)(YPPh2)N]
0 Ph2Pb[(OPPh2)(YPPh2)N]2ꢃ2MCl
MꢀNa; YꢀO (1)
MꢀK; YꢀS (2)
R3PbClꢃM[(OPPh2)(YPPh2)N]
0 R3Pb[(OPPh2)(YPPh2)N]ꢃMCl
RꢀMe;MꢀNa;YꢀO (3)
RꢀPh; MꢀK; YꢀS (4)
Me3PbClꢃNa(O2PPh2)
0 Me3Pb(O2PPh2)ꢃNaCl
(6)
The compounds were characterized by IR and multi-
nuclear NMR spectroscopy (1H, 13C, 31P). Although the
NMR spectra of a freshly prepared sample of the
trimethyllead(IV) complex 3 were consistent with the
presence of a PbC3 fragment, attempts to grow single
crystals suitable for X-ray diffraction studies led only to
isolation of Me2Pb[(OPPh2)2N]2 (5) due to a redistribu-
tion process. Similar behavior has already been reported
for triorganotin(IV) analogs, thus suggesting a tendency
for the ligand moiety to chelate a metal atom and to
form a six-membered ring [12,13]. The molecular
structures of 1, 5 and 6 have been determined by
single-crystal X-ray diffraction.
Scheme 1.
XÁ Á ÁY bite than the 1,1-dichalcogenophosphorus li-
gands and are usually found to be coordinated to a
metal center through both chalcogen atoms, thus
leading to six-membered MXYP2N inorganic chelate
(carbon-free) rings [7]. So far, some inorganic lead(II)
derivatives, Pb[(XPPh2)(YPPh2)N]2 (Xꢀ
[9]; XꢀO, YꢀS [10]), have been investigated by single-
crystal X-ray diffraction and were found to be basically
monomeric regardless of the nature of the chalcogen
atoms in the organophosphorus ligand moiety [7]. We
have reported some preliminary results on organolea-
d(IV) complexes of the type RnPb[(OPPh2)-
2.2. IR spectra
The IR spectra of compounds 1ꢂ
/
4 exhibit strong
1040 cmꢁ1
/
Yꢀ
/
S [8], Se
bands in the regions 1240ꢂ1230 and 1120ꢂ
/
/
,
/
/
which were assigned to n(P2N) and n(PO) vibrations,
respectively. In addition, absorptions of medium inten-
sities around 570 cmꢁ1 [n(PS)] and 770 cmꢁ1 [r(CH3)],
were observed in the spectra of compounds 2 and 4, and
the methyl derivative 3, respectively. The assignments
for the phosphorus-nitrogen, -oxygen and -sulfur
stretching vibrations were made by comparison with
the spectra of the free acids and their alkali salts, and
suggest bidentate coordination of the phophorus ligand
to lead through both chalcogen atoms.
(YPPh2)N]4ꢁn (Rꢀ
/
Me, Ph; nꢀ
/
2, 3; YꢀO, S) within
/
an extended abstract for a communication [11] and here
we report in detail on the synthesis and spectroscopic
characterization of Ph2Pb[(OPPh2)(YPPh2)N]2 [Yꢀ
(1), S (2)], R3Pb[(OPPh2)(YPPh2)N] [RꢀMe, Yꢀ
(3); RꢀPh, Yꢀ
/O
/
/O
/
/
S (4)] and Me3Pb(O2PPh2) (6), along
2.3. NMR spectra
with the crystal and molecular structures of 1, Me2P-
b[(OPPh2)2N]2 (5) and 6.
1
The H- and 13C-NMR spectra contain characteristic
resonance signals for equivalent organic groups bonded
to lead and phosphorus atoms and confirm the identity
2. Results and discussion
of the compounds obtained. The magnitude of the leadꢂ
/
proton and leadꢂcarbon coupling constants is consistent
/
2.1. Preparation
with the presence of diorganolead(IV) moieties in
compounds 1 [3J(PbH) 216.5 Hz, 2J(PbC) 131.0 Hz]
and 2 [3J(PbH) 186.5 Hz], and triorganolead(IV) groups
New organolead(IV) compounds were prepared as
white crystalline solids by reacting Ph2PbCl2 or R3PbCl
with the alkali metal salt of the appropriate organopho-
1
in compounds 3 [2J(PbH) 79.3 Hz, J(PbC) 341.4 Hz]
2
and 4 [3J(PbH) 113 Hz, J(PbC) 87.5 Hz], respectively.

50
R.A. Varga et al. / Journal of Organometallic Chemistry 675 (2003) 48ꢂ56
/
Scheme 2.
For compounds 1 and 3, which contain a symmetric
angles are listed in Table 1. Figs. 1 and 2 show the
ORTEP-like view of the molecular structures of 1 and 5,
with the atom numbering scheme.
dioxoimidodiphosphinato ligand, only one 31P reso-
nance is observed, suggesting the equivalence of the
phosphorus atoms present in the molecule. In the case of
the trimethyllead(IV) derivative 3, the presence of only
one broad 31P resonance suggests a fluxional process in
solution, i.e. a fast exchange of the oxygen atom
involved in the primary coordination to the metal center
(Scheme 2).
There are some common structural features:
1) the phosphorus ligands act as monometallic bicon-
nective units, leading to a spiro-bicyclic system with
six-membered PbO2P2N rings, with a planar PbO4
core and similar endocyclic-Oꢀ
/
Pbꢀ/O
angles
The 31P-NMR spectra of the monothioimidodipho-
sphinato complexes 2 and 4 contain, as expected, two
resonance signals for PO and PS atoms of a ligand
[84.8(1)/87.5(1)8 for 1, 84.1(2)/86.7(2)8 for 5a, and
85.4(2)/87.1(2)8 for 5b],
2) within a coordinated ligand unit the phosphorusꢂ
/
˚
oxygen [1.515(3)ꢂ
/
1.520(3)
1.519(6) A for 5a, and 1.503(6)ꢂ
and the phosphorusꢂ
for 1, 1.583(6)ꢂ
A
for 1, 1.505(6)ꢂ
/
moiety, but the phosphorusꢂ
could not be observed. The resonance assigned to PO
(dꢀ14.4 ppm) in the spectrum of the triphenyllead(IV)
/phosphorus couplings
˚
˚
1.516(6) A for 5b]
/
˚
1.589(4) A
/
nitrogen [1.584(4)ꢂ
1.598(7) A for 5a, and 1.580(7)ꢂ
1.600(7) A for 5b] bond distances, respectively, are
equivalent within experimental error. Their magni-
/
/
˚
/
/
derivative, Ph3Pb[(OPPh2)(SPPh2)N] (4), is shifted to
higher field compared with the diphenyllead(IV) com-
˚
pound 2 (dꢀ21.8 ppm) suggesting that the primary
/
tude suggests single phosphorusꢂ
Ph2P(ꢁO)OH: PꢀO 1.526(6), PꢁO 1.486(6) A] [14]
and considerable double bond character for the
phosphorusꢂnitrogen bonds [cf. [(Me3Si)2NꢀP(ꢁ
NBut)S]2: Pꢀ
/oxygen bonds [cf.
coordination of the monothioimidodiphosphinato li-
gand is achieved through the oxygen atom.
˚
/
/
/
1
The H- and 13C-NMR spectra of the diphenylpho-
sphinato derivative 6 are again consistent with the
/
/
/
˚
N 1.529(2) A] [15].
1
presence of a Me3Pb moiety [2J(PbH) 85.7 Hz, J(PC)
/
N 1.662(2), Pꢁ
/
391.7 Hz]. Its 31P-NMR spectrum shows a sharp singlet
3) the coordination geometry around the lead atom is
distorted octahedral with carbon atoms from the
organic groups attached to lead in trans positions.
(dꢀ
phosphorusꢂ
/
16.8 ppm), surrounded by satellites due to the
carbon coupling [1J(PC) 134.0 Hz].
/
However, there are also significant differences be-
tween the molecular structures of 1, 5a and 5b. Different
degrees of distortion of the C2PbO4 octahedral core are
2.4. Molecular structure of Ph2Pb[(OPPh2)2N]2 (1)
and Me2Pb[(OPPh2)2N]2 (5)
noticeable. Thus, in the molecule of 1 the leadꢂ
/oxygen
bond distances are similar within a PbO2P2N ring
The crystals of 1 and 5 consist of discrete molecules,
of similar structure, separated by normal van der Waals
distances. Two independent molecules (designated as 5a
and 5b in the subsequent discussion) are present in the
asymmetric unit of 5. Selected interatomic distances and
˚
[2.357(3)/2.368(3) and 2.347(3)/2.376(3) A] and well
within the range of those observed in the polymeric
Ph2Pb(O2PR2)2 (RꢀMe, Ph) derivatives [range:
/
˚
2.307(5)ꢂ
/
2.375(5) A] [4]. The trans-Cꢀ
/
Pbꢀ/C

R.A. Varga et al. / Journal of Organometallic Chemistry 675 (2003) 48ꢂ
/
56
51
Table 1
Selected bond lengths (A) and angles (8) for Ph2Pb[(OPPh2)2N]2 (1) and Me2Pb[(OPPh2)2N]2 (5)
˚
(1)
(5)
Molecule (5a)
Molecule (5b)
Bond lengths
Pb(1)ꢀ
Pb(1)ꢀ
Pb(1)ꢀ
Pb(1)ꢀ
Pb(1)ꢀ
Pb(1)ꢀ
/
C(1)
C(7)
O(1)
O(2)
O(3)
O(4)
2.162(5)
2.150(5)
2.357(3)
2.368(3)
2.347(3)
2.376(3)
Pb(1)ꢀ
Pb(1)ꢀ
Pb(1)ꢀ
Pb(1)ꢀ
Pb(1)ꢀ
Pb(1)ꢀ
/
C(1)
C(2)
O(1)
O(2)
O(3)
O(4)
2.168(9)
2.138(9)
2.342(5)
2.420(6)
2.462(5)
2.352(6)
Pb(2)ꢀ
Pb(2)ꢀ
Pb(2)ꢀ
Pb(2)ꢀ
Pb(2)ꢀ
Pb(2)ꢀ
/
C(51)
2.124(9)
2.13(1)
/
/
/
C(52)
O(5)
O(6)
O(7)
O(8)
/
/
/
2.432(5)
2.363(6)
2.382(5)
2.407(6)
/
/
/
/
/
/
/
/
/
P(1)ꢀ
P(1)ꢀ
P(2)ꢀ
P(2)ꢀ
P(3)ꢀ
P(3)ꢀ
P(4)ꢀ
P(4)ꢀ
/
O(1)
N(1)
O(2)
N(1)
O(3)
N(2)
O(4)
N(2)
1.518(3)
1.589(4)
1.520(3)
1.587(4)
1.515(3)
1.586(4)
1.517(3)
1.584(4)
P(1)ꢀ
P(1)ꢀ
P(2)ꢀ
P(2)ꢀ
P(3)ꢀ
P(3)ꢀ
P(4)ꢀ
P(4)ꢀ
/
O(1)
N(1)
O(2)
N(1)
O(3)
N(2)
O(4)
N(2)
1.511(6)
1.596(7)
1.505(6)
1.592(6)
1.513(6)
1.598(7)
1.519(6)
1.583(6)
P(5)ꢀ
P(5)ꢀ
P(6)ꢀ
P(6)ꢀ
P(7)ꢀ
P(7)ꢀ
P(8)ꢀ
P(8)ꢀ
/
O(5)
N(3)
O(6)
N(3)
O(7)
N(4)
O(8)
N(4)
1.516(6)
1.600(7)
1.512(6)
1.594(7)
1.513(6)
1.581(7)
1.503(6)
1.580(7)
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
Bond angles
C(1)ꢀPb(1)ꢀ
/
/
C(7)
178.9(2)
C(1)ꢀ
O(1)ꢀ
O(1)ꢀ
O(1)ꢀ
O(2)ꢀ
O(2)ꢀ
O(3)ꢀ
C(1)ꢀ
C(2)ꢀ
C(1)ꢀ
C(2)ꢀ
C(1)ꢀ
C(2)ꢀ
C(1)ꢀ
C(2)ꢀ
O(1)ꢀ
O(2)ꢀ
O(3)ꢀ
O(4)ꢀ
P(1)ꢀN(1)ꢀ
P(3)ꢀN(2)ꢀ
Pb(1)ꢀ
Pb(1)ꢀ
Pb(1)ꢀ
Pb(1)ꢀ
/
Pb(1)ꢀ
Pb(1)ꢀ
Pb(1)ꢀ
Pb(1)ꢀ
Pb(1)ꢀ
Pb(1)ꢀ
Pb(1)ꢀ
Pb(1)ꢀ
Pb(1)ꢀ
Pb(1)ꢀ
Pb(1)ꢀ
Pb(1)ꢀ
Pb(1)ꢀ
Pb(1)ꢀ
Pb(1)ꢀ
/
C(2)
173.4(3)
C(51)ꢀ
O(5)ꢀPb(2)ꢀ
O(5)ꢀPb(2)ꢀ
O(6)ꢀPb(2)ꢀ
O(6)ꢀPb(2)ꢀ
O(5)ꢀPb(2)ꢀ
O(7)ꢀPb(2)ꢀ
C(51)ꢀPb(2)ꢀ
C(52)ꢀPb(2)ꢀ
C(51)ꢀPb(2)ꢀ
C(52)ꢀPb(2)ꢀ
C(51)ꢀPb(2)ꢀ
C(52)ꢀPb(2)ꢀ
C(51)ꢀPb(2)ꢀ
C(52)ꢀPb(2)ꢀ
O(5)ꢀP(5)ꢀ
O(6)ꢀP(6)ꢀ
O(7)ꢀP(7)ꢀ
O(8)ꢀP(8)ꢀ
P(5)ꢀN(3)ꢀ
P(7)ꢀN(4)ꢀ
Pb(2)ꢀ
Pb(2)ꢀ
Pb(2)ꢀ
Pb(2)ꢀ
/
Pb(2)ꢀ
/
C(52)
178.7(4)
O(1)ꢀPb(1)ꢀ
O(1)ꢀPb(1)ꢀ
O(1)ꢀPb(1)ꢀ
O(2)ꢀPb(1)ꢀ
O(2)ꢀPb(1)ꢀ
O(3)ꢀPb(1)ꢀ
C(1)ꢀPb(1)ꢀ
C(1)ꢀPb(1)ꢀ
C(1)ꢀPb(1)ꢀ
C(1)ꢀPb(1)ꢀ
C(7)ꢀPb(1)ꢀ
C(7)ꢀPb(1)ꢀ
C(7)ꢀPb(1)ꢀ
C(7)ꢀPb(1)ꢀ
O(1)ꢀ
O(2)ꢀ
O(3)ꢀ
O(4)ꢀ
P(2)ꢀN(1)ꢀ
P(4)ꢀN(2)ꢀ
Pb(1)ꢀ
Pb(1)ꢀ
Pb(1)ꢀ
Pb(1)ꢀ
/
/
O(2)
O(4)
O(3)
O(3)
O(4)
O(4)
84.8(1)
177.8(1)
93.0(1)
177.7(1)
94.8(1)
87.5(1)
/
/
O(2)
O(3)
O(4)
O(4)
O(3)
O(4)
84.1(2)
174.2(2)
88.5(2)
/
/
O(6)
O(7)
O(7)
O(8)
O(8)
O(8)
85.4(2)
176.5(2)
91.9(2)
178.7(2)
95.6(2)
87.1(2)
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
172.6(2)
100.7(2)
86.7(2)
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
O(1)
O(2)
O(3)
O(4)
O(1)
O(2)
O(3)
O(4)
90.0(2)
88.4(1)
92.0(2)
92.1(2)
90.1(2)
90.6(2)
89.0(2)
87.8(2)
/
/
O(1)
O(1)
O(2)
O(2)
O(3)
O(3)
O(4)
O(4)
90.3(3)
94.1(3)
86.0(3)
89.6(3)
86.8(3)
89.3(3)
93.3(3)
91.7(3)
/
/
O(5)
O(5)
O(6)
O(6)
O(7)
O(7)
O(8)
O(8)
87.4(3)
91.3(3)
87.8(3)
91.8(3)
90.2(3)
91.1(3)
91.3(3)
89.1(3)
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
P(1)ꢀ
P(2)ꢀ
P(3)ꢀ
P(4)ꢀ
/
N(1)
N(1)
N(2)
N(2)
116.7(2)
117.3(2)
118.0(2)
118.7(2)
/
P(1)ꢀ
P(2)ꢀ
P(3)ꢀ
P(4)ꢀ
/
N(1)
N(1)
N(2)
N(2)
118.4(4)
119.2(4)
117.2(3)
117.4(4)
/
/
N(3)
N(3)
N(4)
N(4)
115.7(3)
117.8(4)
117.5(4)
117.7(4)
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/P(1)
127.7(2)
135.4(3)
/
/
P(2)
130.8(5)
130.8(5)
/
/P(6)
127.3(5)
135.3(5)
/
/P(3)
/
/
P(4)
/
/P(8)
/
O(1)ꢀ
O(2)ꢀ
O(3)ꢀ
O(4)ꢀ
/
P(1)
125.7(2)
125.4(2)
130.4(2)
128.5(2)
/
O(1)ꢀ
O(2)ꢀ
O(3)ꢀ
O(4)ꢀ
/
P(1)
126.0(3)
128.8(3)
125.9(3)
127.6(3)
/
O(5)ꢀ
O(6)ꢀ
O(7)ꢀ
O(8)ꢀ
/
P(5)
126.2(3)
126.3(3)
126.8(3)
128.0(3)
/
/
P(2)
P(3)
P(4)
/
/
P(2)
P(3)
P(4)
/
/
P(6)
P(7)
P(8)
/
/
/
/
/
/
/
/
/
/
/
/
[178.9(2)8] and trans-Oꢀ
gles are close to 1808, while the exocyclic-Oꢀ
almost equal [93.0(1), 94.8(1)8]. The C2PbO4 core in 5b
also exhibits very similar trans-bond angle parameters
/
Pbꢀ
/
O [177.7(1), 177.8(1)8] an-
is smaller than that between the longer ones [95.6(2)8].
The distortion of the C2PbO4 octahedral core in 5a
towards a bicapped tetrahedraon as observed for
/
PbꢀO are
/
C2PbS4 in Ph2Pb(S2PR2)2 (Rꢀ
even more pronounced. The difference between the Pbꢀ
O bond lengths formed by a ligand moiety [2.342(5)/
/OCH2Ph [1], Ph [2]) is
[trans-Cꢀ
178.7(2)8]. However, the leadꢂ
within a PbO2P2N ring are significantly different
/
Pbꢀ
/
C
178.7(4)8, trans-Oꢀ
/
Pbꢀ/O
176.5(2),
/
/
oxygen bond distances
˚
2.420(6) and 2.352(6)/2.462(5) A] is even greater than in
˚
[2.363(6)/2.432(5) and 2.382(5)/2.407(6) A] and the Oꢀ
/
5b and the deviation of the trans-bond angles at the
PbꢀO angle between the shorter PbꢀO bonds [91.9(2)8]
/
/
central metal atom is considerable [trans-Cꢀ
/
Pbꢀ/C

52
R.A. Varga et al. / Journal of Organometallic Chemistry 675 (2003) 48ꢂ56
/
PbO2P2N ring (Table 1) and the variable bite of a ligand
˚
3.30 A] support the high
unit [OÁ Á ÁO range: 3.18ꢂ
/
flexibility of the OPNPO skeleton which might account
for the differences observed in the PbO2P2N ring
conformation.
2.5. Molecular structure of [Me3Pb(O2PPh2)]4 (6)
The crystal of the trimethyllead(IV) phosphinate (6)
contains discrete tetrameric units, [Me3Pb(O2PPh2)]4
(Fig. 3). The tetramer exhibits a crystallographic mirror
plane passing through Pb(2) and Pb(3). Selected intera-
tomic distances and angles are listed in Table 2.
The diphenylphosphinato ligands act as a bimetallic
biconnective (bridging) moieties between Me3Pb units,
thus resulting in a sixteen-membered Pb4O8P4 inorganic
ring. A similar tetrameric macrocyclic structure was
reported previously for the tin analogue, [Me3S-
n(O2PPh2)]4 [16]. The Pb4O8P4 ring is not planar, but
of chair conformation, with the Pb(1)P2O2 and
Pb(3)P2O2 fragments above and below the plane formed
by the O(1)Pb(1)O(3)/O(1?)Pb(1?)O(3?) system. Two of
the methyl groups at each lead atom protrude into the
Pb4O8P4 ring, while the phenyl groups at the phospho-
rus atoms are orientated outside the ring, thus providing
a lipophilic protection to the tetramer.
Fig. 1. ORTEP plot of the molecule Ph2Pb[(OPPh2)2N]2 (1). The
atoms are drawn with 25% probability ellipsoids. Hydrogen atoms are
omitted for clarity.
The lead atoms exhibit a distorted trigonal bipyrami-
dal geometry, with the carbon atoms of the methyl
groups in equatorial positions and two oxygen atoms in
the axial positions. The C3Pb moieties are planar and
˚
the Pbꢀ
/
C [2.16(1)ꢂ
/
2.22(1) A] and Pbꢀ
/
O [2.373(6)ꢂ
/
˚
2.402(6) A] bond lengths are equivalent within experi-
mental error. The differences in the CꢀPbꢀC angles
[115.7(6)ꢂ130.1(7)8] and the deviation of the OꢀPbꢀ
fragment from linearity [OꢀPbꢀO 174.7(2)ꢂ177.6(3)8]
/
/
/
/
/O
/
/
/
Fig. 2. ORTEP plot of the one of the two molecules in the asymmetric
unit of Me2Pb[(OPPh2)2N]2 (5). The atoms are drawn with 25%
probability ellipsoids. Hydrogen atoms are omitted for clarity.
173.4(3)8, trans-Oꢀ
moiety is bent towards the opened Oꢀ
[100.7(2)8] formed by the longer PꢀO bonds.
/
Pbꢀ
/
O 172.6(2), 174.2(2)8]. The C2Pb
/
PbꢀO angle
/
/
Although some delocalization of the p-electrons over
the OPNPO systems is suggested by the magnitude of
the bonds, the PbO2P2N rings are not planar but exhibit
variable conformations. Thus, the six-membered rings in
1 exhibit a chair (almost flattened) and a boat con-
formation, respectively, both with the metal and the
nitrogen atoms in the apices. In 5a and 5b, the PbO2P2N
rings exhibit boat conformation of variable distortion
and with different atom types in the apices: O(1)/P(2)
and O(3)/P(4) atoms in 5a, and Pb(2)/N(3) and O(8)/P(7)
atoms in 5b. The differences in the bond angles within a
Fig. 3. ORTEP plot of the tetrameric [Me3Pb(OPPh2)2N]4 (6). The
atoms are drawn with 25% probability ellipsoids. Hydrogen atoms are
omitted for clarity.

R.A. Varga et al. / Journal of Organometallic Chemistry 675 (2003) 48ꢂ
/
56
53
Table 2
Selected bond lengths (A) and angles (8) for [Me3Pb(OPPh2)2N]4 (6) a
˚
Bond lengths
Pb(1)ꢀ
Pb(1)ꢀ
Pb(1)ꢀ
/
C(1)
C(2)
C(3)
2.20(1)
2.197(9)
2.18(1)
Pb(2)ꢀ
Pb(2)ꢀ
Pb(2)ꢀ
/
C(4)
C(5)
C(6)
2.18(2)
2.17(2)
2.22(1)
Pb(3)ꢀ
Pb(3)ꢀ
Pb(3)ꢀ
/
C(7)
C(8)
C(9)
2.16(1)
2.19(2)
2.21(1)
/
/
/
/
/
/
Pb(1)ꢀ
/
O(1)
2.402(6)
2.380(6)
Pb(2)ꢀ
/
O(2)
O(2)?
2.373(6)
2.373(6)
Pb(3)ꢀ
/
O(4)
2.396(5)
2.396(5)
Pb(1)ꢀ
/
O(3)
Pb(2)ꢀ
/
Pb(3)ꢀ
/
O(4)?
P(1)ꢀ
P(1)ꢀ
/
O(1)
1.495(6)
1.501(6)
P(2)ꢀ
P(2)ꢀ
/
O(3)
1.509(7)
1.512(6)
/O(2)
/O(4)
Bond angles
O(1)ꢀPb(1)ꢀ
/
/
O(3)
174.7(2)
O(2)ꢀ
C(4)ꢀ
C(4)ꢀ
C(5)ꢀ
C(4)ꢀ
C(5)ꢀ
C(6)ꢀ
/
Pb(2)ꢀ
Pb(2)ꢀ
Pb(2)ꢀ
Pb(2)ꢀ
Pb(2)ꢀ
Pb(2)ꢀ
Pb(2)ꢀ
/
O(2)?
177.6(3)
O(4)ꢀ
C(7)ꢀ
C(7)ꢀ
C(8)ꢀ
C(7)ꢀ
C(8)ꢀ
C(9)ꢀ
/
Pb(3)ꢀ
Pb(3)ꢀ
Pb(3)ꢀ
Pb(3)ꢀ
Pb(3)ꢀ
Pb(3)ꢀ
Pb(3)ꢀ
/
O(4)?
176.5(3)
C(1)ꢀPb(1)ꢀ
C(1)ꢀPb(1)ꢀ
C(2)ꢀPb(1)ꢀ
C(1)ꢀPb(1)ꢀ
C(2)ꢀPb(1)ꢀ
C(3)ꢀPb(1)ꢀ
C(1)ꢀPb(1)ꢀ
C(2)ꢀPb(1)ꢀ
C(3)ꢀPb(1)ꢀ
O(1)ꢀP(1)ꢀ
C(10)ꢀP(1)ꢀ
P(1)ꢀO(1)ꢀ
P(2)ꢀO(3)ꢀ
/
/
C(2)
C(3)
C(3)
117.1(4)
121.6(6)
121.2(5)
/
/
C(5)
C(6)
C(6)
119.7(9)
118.4(8)
121.8(8)
/
/
C(8)
C(9)
C(9)
130.1(7)
114.2(6)
115.7(6)
/
/
/
/
/
/
/
/
/
/
/
/
/
/
O(1)
O(1)
O(1)
O(3)
O(3)
O(3)
91.7(3)
93.4(3)
88.6(3)
93.4(4)
85.3(3)
87.7(3)
/
/
O(2)
O(2)
O(2)
90.4(2)
90.8(2)
88.8(2)
/
/
O(4)
O(4)
O(4)
88.3(2)
91.2(2)
90.6(2)
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/O(2)
117.6(4)
103.6(4)
O(3)ꢀ
/
P(2)ꢀ
P(2)ꢀ
/
O(4)
117.6(4)
106.3(4)
/
/
C(16)
C(22)ꢀ
/
/C(28)
/
/Pb(1)
135.6(3)
156.8(5)
P(1)ꢀO(2)ꢀ
/
/
Pb(2)
173.4(4)
P(2)ꢀ
/
O(4)ꢀ
/
Pb(3)
132.3(3)
/
/Pb(1)
a
Symmetry equivalent atoms (x, ꢁ
/
yꢃ(1/2), z) given by a prime.
/
account for the distortion of the C3PbO2 core from an
ideal polyhedron.
and different conformations of the six-membered
PbO2P2N inorganic rings. For the trimethyllead(IV)
Within a phosphinato ligand, the phosphorusꢂ
/
oxygen
1.512(6) A] and their
magnitude suggests intermediate character between
single PꢀO and double PꢁO bonds [cf. Ph2P(ꢁO)OH:
PꢀO 1.526(6), PꢁO 1.486(6) A] [14]. The OꢀPꢀO and
CꢀPꢀC angles (Table 2) are normal for a tetrahedral
C2PO2 core, but the bond angles at the oxygen atoms
cover a wide range, from angular [P(2)ꢀO(4)ꢀPb(3)
Pb(2) 173.4(4)8],
phosphinate (6)
a
tetrameric structure, [Me3P-
˚
bonds are equivalent [1.495(6)ꢂ
/
b(O2PPh2)]4, with a sixteen-membered Pb4O8P4 macro-
cyclic system is established. The bridging nature of the
phosphorus ligands results in distorted trigonal bipyr-
amidal C3PbO2 cores.
/
/
/
˚
/
/
/
/
/
/
/
/
132.3(3)8] to almost linear [P(1)ꢀ
/
O(2)ꢀ
/
4. Experimental
to allow for the formation of the macrocycle.
4.1. Materials and procedures
3. Conclusions
Organolead(IV) chlorides were commercial products.
Na[O2PPh2] was obtained by reacting Ph2P(O)OH [17]
with MeONa, while the other starting materials
were prepared according to literature methods:
Na[(OPPh2)2N] [18], K[(OPPh2)(SPPh2)N] [12]. Infrared
New R2Pb[(OPPh2)(XPPh2)N]2 and R3Pb[(OPPh2)-
(XPPh2)N] (Rꢀ
/
Me, Ph; XꢀO, S) derivatives were
/
prepared and characterized using IR and NMR (1H,
13C, 31P) spectroscopy. The molecular structures of
R2Pb[(OPPh2)2N]2 [RꢀPh (1), Me (5)] were investi-
/
spectra were recorded in the range 4000ꢂ
400 cmꢁ1 in
nujol on a SPECORD IR UR 2 (Carl-Zeiss Jena, DDR)
/
gated by X-ray diffraction. The larger bite of the
imidodiphosphinato ligands accounts for the mono-
meric nature of both compounds. The formation of a
spiro-bicyclic (NP2O2)PbC2(O2P2N) system is in con-
trast to the polymeric ring-chain structures with
1
instrument. The H-, 13C- and 31P-NMR spectra were
recorded on a VARIAN GEMINI 300S instrument
operating at 299.5, 75.4 and 121.4 MHz, respectively,
using solutions in dried CDCl3. The chemical shifts are
reported in ppm relative to TMS and H3PO4 85%,
respectively.
Pb2O4P2 eight-membered rings of Ph2Pb(O2PR2)2 (Rꢀ
/
Me, Ph) derivatives. The compounds exhibit different
degrees of distortion for the octahedral C2PbO4 core

54
R.A. Varga et al. / Journal of Organometallic Chemistry 675 (2003) 48ꢂ56
/
4.2. Preparation of bis(tetraphenylimidodiphosphinato)-
diphenyllead(IV), Ph2Pb[(OPPh2)2N]2 (1)
CH2Cl2. The reaction mixture was stirred for 3 h at
room temperature and then filtered to remove the
resulting NaCl. The filtrate was evaporated under
reduced pressure to obtain 3 as a white microcrystalline
Na[(OPPh2)2N] (0.5858 g, 1.33 mmol) was added to a
solution of Ph2PbCl2 (0.2882 g, 0.66 mmol) in 40 ml
CH2Cl2. The reaction mixture was stirred for 3 h at
room temperature and then filtered to remove the
resulting NaCl. The filtrate was evaporated under
reduced pressure to obtain 1 as a white crystalline
product. X-ray quality crystals were grown from
product. Yield: 0.74 g (95%), m.p. 145ꢂ147 8C. Anal.
/
Found: C, 48.2; H, 4.1; N, 2.2. Calc. for
C27H29NO2P2Pb: C, 48.5; H, 4.4; N, 2.1%. IR (nujol,
cmꢁ1): 1240vs [nas(P2N)], 1110vs, 1040s [n(PO)], 770m
[r(CH3)]. 1H-NMR: d 1.30s [9H, Pbꢀ
79.3 Hz], 7.29m (8H, Pꢀ
C6H5-para, 3J(HH) 7.1 Hz], 7.68dd [8H, Pꢀ
/
CH3, 2J(PbH)
C6H5-meta), 7.37t [4H, Pꢀ
C6H5-ortho,
3J(HH) 7.4, J(PH) 12.4 Hz]. 13C-NMR: d 19.61s [Pbꢀ
CH3, 1J(PbC) 341.4 Hz], 127.95d [Cm, PꢀC6H5, 3J(PC)
13.4 Hz], 130.55s (Cp, PꢀC6H5), 131.31d [Co, PꢀC6H5,
2J(PC) 10.7 Hz], 137,23d (Ci, Pꢀ
C6H5), J(PC) 132.3
Hz]. 31P-NMR: d 13.8s,br.
The attempt to obtain suitable crystals for X-ray
diffraction from CH2Cl2ꢂn-hexane (1:3) mixture re-
/
/
CH2Cl2ꢂ
/
n-hexane (1:3) mixture. Yield: 0.70 g (88%),
229 8C. Anal. Found: C, 60.2; H, 4.1; N,
2.5. Calc. for C60H50N2O4P4Pb: C, 60.4; H, 4.2; N,
/
3
m.p. (dec.) 228ꢂ
/
/
/
2.4%. IR (nujol, cmꢁ1): 1240vs [nas(P2N)], 1120vs,
/
/
1
1
1080vs, 1060vs [n(PO)]. H-NMR: d 6.94dd [4H, Pbꢀ
/
/
3
C6H5-meta, J(HH) 7.1 Hz], 7.08t [2H, Pbꢀ
3J(HH) 7.3 Hz], 7.14ddd [16H, Pꢀ
C6H5-meta, J(HH)
7.4, 4J(PH) 2.5 Hz], 7.27t [8H, P-C6H5-para, 3J(HH) 7.4
/
C6H5-para,
3
/
/
3
3
Hz], 7.49dd [16H, Pꢀ
12.4 Hz], 7.93d [4H, Pbꢀ
3J(PbH) 216.5 Hz]. 13C-NMR: d 127.51d [Cm, Pꢀ
C6H5, 3J(PC) 13.3 Hz], 128.76s (Cm, Pbꢀ
C6H5),
128.93s (Cp, PbꢀC6H5), 130.02s (Cp, PꢀC6H5),
131.24d [Co, Pꢀ
C6H5, 2J(PC) 10.5 Hz], 134.16s [Co,
Pbꢀ C6H5,
C6H5, 2J(PbC) 131.0 Hz], 137.27d [Ci, Pꢀ
C6H5). 31P-NMR: d
/
C6H5-ortho, J(HH) 7.5, J(PH)
sulted in isolation of the redistribution product, Me2P-
b[(OPPh2)2N]2 (5), following a decomposition process
(see Section 2).
/
C6H5-ortho, 3J(HH) 7.4,
/
/
/
/
4.5. Preparation of
/
(tetraphenylthioimidodiphosphinato)triphenyllead(VI),
Ph3Pb[(OPPh2)(SPPh2)N] (4)
/
/
1J(PC) 140.0 Hz], 169.96s (Ci, Pbꢀ
/
19.7s.
K[(OPPh2)(SPPh2)N] (0.5239 g, 1.11 mmol) was
added to a solution of Ph3PbCl (0.5267 g, 1.11 mmol)
in 40 ml anhydrous benzene. The reaction mixture was
stirred for 3 h at room temperature and then filtered to
remove the resulting KCl. The filtrate was evaporated
under reduced pressure to obtain 4 as a white solid.
4.3. Preparation of
bis(tetraphenylthioimidodiphosphinato)diphenyllead-
(IV), Ph2Pb[(OPPh2)(SPPh2)N]2 (2)
K[(OPPh2)(SPPh2)N] (0.7858 g, 1.66 mmol) was
added to a solution of Ph2PbCl2 (0.3603 g, 0.83 mmol)
in 40 ml anhydrous benzene. The reaction mixture was
stirred for 3 h at room temperature and then filtered to
remove the resulting KCl. The filtrate was evaporated
under reduced pressure to obtain 2 as a white micro-
crystalline solid. Yield: 0.91 g (89%), m.p. (dec.) 190 8C.
Anal. Found: C, 58.7; H, 4.2; N, 2.5. Calc. for
C60H50N2O2P4PbS2: C, 58.8; H, 4.1; N, 2.3%. IR (nujol,
cmꢁ1): 1240vs [nas(P2N)], 1110vs, 1040s [n(PO)], 570m
Yield: 0.81 g (82%), m.p. 112ꢂ114 8C. Anal. Found: C,
/
58.2; H, 4.3; N, 1.4. Calc. for C42H35NOP2PbS: C, 57.9;
H, 4.1; N, 1.6%. IR (nujol, cmꢁ1): 1230s [nas(P2N)],
1
1120s, 1080s, 1060s [n(PO)], 570m [n(PS)]. H-NMR: d
7.3m [25H, Pbꢀ
/
C6H5-metaꢃ
/
para, Pꢀ
/
C6H5-metaꢃ
C6H5-ortho,
C6H5-ortho,
/
para, (O)PꢀC6H5-ortho], 7.49m [4H, Pbꢀ
/
/
3J(PbH) 113 Hz], 7.61dd [4H, (S)Pꢀ
/
3J(HH) 7.6, 3J(PH) 14.0 Hz]. 13C-NMR: d 127.35d
3
[Cm, Pꢀ
/
C6H5, J(PC) 13.2 Hz], 127.69d [Cm, Pꢀ
/
C6H5,
C6H5), 129.58s (Cp,
3J(PC) 13.7 Hz], 129.22s (Cp, Pbꢀ
/
[n(PS)]. 1H-NMR: d 7.5m (46H, Pbꢀ
PꢀC6H5), 8.05d [4H, Pbꢀ
C6H5-ortho, 3J(HH) 7.6,
3J(PbH) 186.5 Hz]. 13C-NMR: d 128.09d [Cm, (O)Pꢀ
/
C6H5-metaꢃ
/
para,
Pꢀ
130.28s (Cp, Pꢀ
12.0 Hz], 131.54d [Co, Pꢀ
/
C6H5), 129.84s [Cm, Pbꢀ
C6H5), 131.32d [Co, Pꢀ
C6H5, 2J(PC) 11.1 Hz],
C6H5, J(PbC) 87.5 Hz], 157.16s [Ci,
/C6H5, J(PbC) 107.1 Hz],
3
/
/
/
/
C6H5, 2J(PC)
/
/
3
2
C6H5ꢃ
Cp, Pbꢀ
/
(S)Pꢀ
/
C6H5, J(PC) 12.9 Hz], 129.83s,br (Cmꢃ
Cp, (O)PꢀC6H5ꢃ(S)Pꢀ
C6H5) (resonance signals for
/
136.88s [Co, Pbꢀ
/
/
C6H5), 131.46s,br [Coꢃ
/
/
/
/
Pbꢀ
/
C6H5] (resonance signals for ipso carbons of Pꢀ
/
C6H5], 135.02s (Co, Pbꢀ
/
C6H5 could not be observed). 31P-NMR: d 14.4s (PO),
31.6s (PS).
ipso carbons could not be observed). 31P-NMR: d 21.8s
(PO), 31.8s (PS).
4.6. Preparation of
(diphenylphosphinato)trimethyllead(VI),
Me3Pb(O2PPh2) (6)
4.4. Preparation of (tetraphenylimidodiphosphinato)-
trimethyllead(VI), Me3Pb[(OPPh2)2N] (3)
Na[(OPPh2)2N] (0.7323 g, 1.66 mmol) was added to a
solution of Me3PbCl (0.4796 g, 1.66 mmol) in 40 ml
Ph2PO2Na (0.4803 g, 2 mmol) was added to a solution
of Me3PbCl (0.5755 g, 2 mmol) in 40 ml CH3Cl. The

R.A. Varga et al. / Journal of Organometallic Chemistry 675 (2003) 48ꢂ
/
56
55
reaction mixture was stirred for 3 h at room temperature
and then filtered to remove the resulting NaCl. The
filtrate was evaporated under reduced pressure to obtain
6 as a white solid. X-ray quality crystals were grown
to triclinic (1 and 5) and orthorhombic (6) cells whose
dimensions are given in Table 3 along with other
experimental parameters and relevant information per-
taining to structure solution and refinement. Semiempi-
rical absorption corrections were applied.
from CH3Clꢂ
(88%), m.p. 216ꢂ
Calc. for C15H19O2PPb: C, 38.4; H, 4.1%. H-NMR: d
/n-hexane (1:3) mixture. Yield: 0.83 g
/
218 8C. Anal. Found: C, 38.2; H, 4.2.
The structures were solved by direct methods [19]. All
of the non-hydrogen atoms were treated anisotropically.
Hydrogen atoms were included in idealized positions
with isotropic thermal parameters set at 1.2 times that of
the carbon atom to which they were attached. The final
cycle of full-matrix least-squares refinement [20] was
based on 11799 for 1, 21294 for 5, and 7762 for 6 [7940
1
2
1.34s [9H, Pbꢀ
/
CH3, J(PbH) 85.7 Hz], 7.33m (6H, Pꢀ
C6H5-ortho, 3J(HH)
7.7, J(HH) 1.4, J(PH) 11.5 Hz]. 13C-NMR: d 14.37s
[Pbꢀ C6H5,
CH3, 1J(PC) 391.7 Hz], 122.59d [Cm, Pꢀ
3J(PC) 12.2 Hz], 124.79s (Cp, Pꢀ
C6H5), 125.81d [Co, Pꢀ
C6H5, 1J(PC)
/
C6H5-metaꢃpara), 7.57dm [4H, Pꢀ
/
/
4
3
/
/
/
/
C6H5, 2J(PC) 9.7 Hz], 133.41d [Ci, Pꢀ
/
for 1, 9032 for 5, and 4521 for 6, F2ꢀ2s(F2)]
/
134.5 Hz]. 31P-NMR: d 16.8s [1J(PC) 134.0 Hz].
independent reflections and 630 for 1, 1103 for 5, and
364 for 6 variable parameters and converged (largest
parameter shift was 0.001 times its estimated S.D.).
4.7. X-ray structure determination
A colourless plate crystal of Me2Pb[(OPPh2)2N]2 (5)
and block colourless crystals of Ph2Pb[(OPPh2)2N]2 (1)
and [Me3Pb[(O2Ph2)]4 (6) were mounted on glass fibres
and sealed with epoxy glue. Data were collected on a
Siemens SMART/CCD system at McMaster University
5. Supplementary material
Crystallographic data for the structural analysis of
compounds 1, 5 and 6 have been deposited with the
Cambridge Crystallographic Data Centre, CCDC Nos.
182709 (1), 182708 (5), 182710 (6). Copies of the
with graphite-monochromated MoꢂKa radiation, oper-
/
ating at 50 kV and 35 mA. Cell constants corresponded
Table 3
Crystal data and structure refinement for Ph2Pb[(OPPh2)2N]2 (1), Me2Pb[(OPPh2)2N]2 (5), and [Me3Pb(OPPh2)2N]4 (6)
(1)
(5)
(6)
Empirical formula
Formula weight
Temperature (8C)
Wavelength (A)
Crystal system
C60H50N2O4P4Pb
1194.09
26(2)
C100H92N4O8P8Pb2
2139.92
26(2)
C60H76O8P4Pb4
1877.85
26(2)
˚
0.71073
Triclinic
¯
P1
0.71073
Triclinic
¯
P1
0.71073
Orthorhombic
Pnma
Space group
˚
/
/
a (A)
˚
10.689(2)
10.824(2)
24.782(4)
86.17(1)
79.69(1)
69.54(1)
2643(3)
2
11.015(1)
19.044(1)
22.943(2)
81.86(1)
87.75(2)
84.79(1)
4743.0(8)
2
15.256(4)
29.633(7)
14.736(1)
90
b (A)
˚
c (A)
a (8)
b (8)
g (8)
Volume (A )
Z
90
90
3
˚
6661(1)
4
1.872
Density (calculated) (g cmꢁ3
Absorption coefficient (mmꢁ1
F(0 0 0)
)
1.500
3.362
1196
1.498
3.737
2136
)
10.222
3552
Crystal size (mm3)
u range for data collection (8)
Index ranges
0.34ꢄ
2.01ꢂ27.52
125h 5
315l 532
24 163
11 799 [Rint
0.6153/0.3944
/
0.16ꢄ
/
0.18
0.19ꢄ
1.31ꢂ27.51
145h 5
295l 529
43 104
21 294 [Rint
/
0.10ꢄ
/
0.04
0.28ꢄ
1.37ꢂ27.48
195h 5
195l 518
46 004
7762 [Rint
/
0.25ꢄ
/
0.20
/
/
/
ꢁ/
/
/13, ꢁ
/
145
/
k 5
/
13, ꢁ
/
ꢁ/
/
/
13, ꢁ245
/
/
k 5
/
24, ꢁ
/
ꢁ/
/
/19, ꢁ385
/
/
k 5
/
16, ꢁ
/
/
/
/
/
/
/
Reflections collected
Independent reflections
Max./min. transmission
Refinement method
ꢀ
/
0.0538]
ꢀ
/
0.1114]
ꢀ/0.1071]
0.8649/0.5370
0.2343/0.1620
Full-matrix least-squares on F2
Data/restraints/parameters
Goodness-of-fit on F2
11 799/0/630
0.936
21 294/0/1103
0.935
7762/0/364
1.001
Final R indices [F2ꢀ
/
2s(F2)]
R1ꢀ
R1ꢀ
Largest difference peak and hole 1.039 and ꢁ
/
0.0462, wR2ꢀ
0.0917, wR2ꢀ
0.781
/
0.0700
R1ꢀ
R1ꢀ
0.758 and ꢁ
/
0.0718, wR2ꢀ
0.2118, wR2ꢀ
0.765
/
0.0880
R1ꢀ
R1ꢀ
1.612 and ꢁ
/
0.0515, wR2ꢀ
0.1159, wR2ꢀ
1.251
/
0.0839
0.0998
R indices (all data)
/
/0.0802
/
/0.1169
/
/
/
/
/
3
˚
(e A )

56
R.A. Varga et al. / Journal of Organometallic Chemistry 675 (2003) 48ꢂ56
/
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information may be obtained free of charge from The
Director, CCDC, 12 Union Road, Cambridge CB2 1EZ,
R.R. Holmes, Phosphorus, Sulfur
125.
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UK (Fax: ꢃ44-1223-336033; e-mail: deposit@ccdc.cam.
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ac.uk or www: http://www.ccdc.cam.ac.uk).
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Acknowledgements
This work was supported by the National University
Research Council (grants 45/312/2000 and 58/112/2002).
J.E.D thanks the Natural Sciences and Engineering
Research Council of Canada for financial support and
Jim Britten of the McMaster Chemistry X-ray Facility
for providing help and facilities.
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