Syntheses and structures of P-anilino-P-chalcogeno- and P-anilino-P-iminodiazasilaphosphetidines and their group 12 and 13 metal compounds

Article abstract of DOI:10.1021/ic010973f

The P-anilino-P-chalcogeno(imino)diazasilaphosphetidines [Me₂Si(μ-N^tBu)₂P=E(NHPh)] (E = O (3), S (4), Se (5), N-p-tolyl (6)) were synthesized by oxidizing the P-anilinodiazasilaphosphetidine [Me₂Si(N^tBu)₂P(NHPh)] (2) with cumene hydroperoxide, sulfur, selenium, and p-tolyl azide, respectively. The lithium salt of 4 reacted with thallium monochloride to produce {[Me₂Si(μ-N^tBu)₂P=S(NPh)-κ N-κS]Tl} (7), which features a two-coordinate thallium atom. Treatment of 4-6 with AlMe₃ gave the monoligand dimethylaluminum complexes {[Me₂Si(μ-N^tBu)₂P=E(NPh)-κ NκE]AlMe₂} (E = S (8), Se (9), N-p-tolyl (10)), respectively. In these complexes the aluminum atom is tetrahedrally coordinated by one chelating ligand and two methyl groups, as a single-crystal X-ray analysis of 8 showed. A 2 equiv amount of 4-6 reacted with diethylzinc to produce the homoleptic diligand complexes {[Me₂Si(μ-N^tBu)₂P=E(NPh)-κ N-κE]₂Zn} (E = S (11), Se (12), N-p-tolyl (13)). A crystal-structure analysis of 11 revealed a linear tetraspirocycle with a tetrahedrally coordinated, central zinc atom.

Full text of DOI:10.1021/ic010973f

Inorg. Chem. 2002, 41, 1245−1253
Syntheses and Structures of P-Anilino-P-chalcogeno- and
P-Anilino-P-iminodiazasilaphosphetidines and Their Group 12 and 13
Metal Compounds
Dana C. Haagenson, Daniel F. Moser, and Lothar Stahl*
Department of Chemistry, UniVersity of North Dakota, Grand Forks, North Dakota 58202-9024
Richard J. Staples
Department of Chemistry and Chemical Biology, HarVard UniVersity,
Cambridge, Massachusetts 02138
Received September 17, 2001
t
The P-anilino-P-chalcogeno(imino)diazasilaphosphetidines [Me2Si(µ-NBu)2PdE(NHPh)] (E ) O(3), S (4), Se (5),
t
N-p-tolyl (6)) were synthesized by oxidizing the P-anilinodiazasilaphosphetidine [Me2Si(NBu)2P(NHPh)] (2) with
cumene hydroperoxide, sulfur, selenium, and p-tolyl azide, respectively. The lithium salt of 4 reacted with thallium
t
monochloride to produce {[Me2Si(µ-NBu)2PdS(NPh)-κN-κS]Tl} (7), which features a two-coordinate thallium atom.
t
Treatment of 4−6 with AlMe3 gave the monoligand dimethylaluminum complexes {[Me2Si(µ-NBu)2PdE(NPh)-κN-
κE]AlMe2} (E ) S (8), Se (9), N-p-tolyl (10)), respectively. In these complexes the aluminum atom is tetrahedrally
coordinated by one chelating ligand and two methyl groups, as a single-crystal X-ray analysis of 8 showed. A 2
t
equiv amount of 4−6 reacted with diethylzinc to produce the homoleptic diligand complexes {[Me2Si(µ-NBu)2Pd
E(NPh)-κN-κE]2Zn} (E ) S (11), Se (12), N-p-tolyl (13)). A crystal-structure analysis of 11 revealed a linear
tetraspirocycle with a tetrahedrally coordinated, central zinc atom.
Introduction
Bis(1°-amino)cyclodiphosph(V)azanes (B, C) are hetero-
cyclic molecules with two tetrasubstituted phosphorus(V)
atoms, each having an environment similar to that in A. As
ligands for main-group and transition metals,12-16 these
diphosphorus compounds have exhibited remarkable coor-
dinative flexibility by being able to chelate metal atoms either
as bis(amido) or as bis(chalcogenophosphoryl) ligands.17-20
The most common coordination mode for bis(amino)cyclo-
Amino(imino)- and amino(chalcogeno)phosphoranes (A;
Chart 1) are tetrasubstituted monophosphorus(V) compounds
with an established chemistry.1-3 The ready availability of
these molecules has contributed much to their popularity as
ligands, leading to numerous metal derivatives of chelating
N,N or N,E phosphoranes with desirable functions and
structures.4-11
(9) Witt, M.; Noltemeyer, M.; Schmidt, H.-G.; Lu¨bben, T.; Roesky, H.
W. J. Organomet. Chem. 1999, 591, 138-147.
* Corresponding author. E-mail: lstahl@chem.und.edu. Voice mail:
(701)777-2242. Fax: (701)777-2331.
(1) Paciorek, K. L.; Kratzer, R. H. J. Org. Chem. 1966, 31, 2426.
(2) Wolfsberger, W.; Hager, W. Z. Anorg. Allg. Chem. 1976, 425, 169-
175.
(10) Vollmerhaus, R.; Shao, R.; Taylor, N. J.; Collins, S. Organometallics
1999, 18, 2731-2733.
(11) Straub, B. F.; Eisentra¨ger, F.; Hofmann, P. Chem. Commun. (Cam-
bridge) 1999, 2507-2508.
(12) Hill, T. G.; Haltiwanger, R. C.; Thompson, M. L.; Katz, S. A.; Norman,
A. D. Inorg. Chem. 1994, 33, 1770.
(3) Wolfsberger, W.; Hager, W. Z. Anorg. Allg. Chem. 1977, 433, 247-
254.
(4) Steiner, A.; Stalke, D. Inorg. Chem. 1993, 32, 1977-1981.
(5) Chivers, T.; Parvez, M.; Seay, M. A. Inorg. Chem. 1994, 33, 2147-
2150.
(13) Keat, R.; Muir, K. W.; Thompson, D. G. Tetrahedron Lett. 1977, 3087.
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2000, 463-464.
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Chem. 2001, 40, 463-464.
(6) Roesky, H. W.; Voelker, H.; Witt, M.; Noltemeyer, M. Angew. Chem.,
Int. Ed. Engl. 1990, 29, 669-670.
(7) Raubold, T.; Freitag, S.; Herbst-Irmer, R.; Roesky, H. W. Z. Anorg.
Allg. Chem. 1993, 619, 951-953.
(8) Witt, M.; Roesky, H. W.; Stalke, D., Pauer, F.; Henkel, T.; Sheldrick,
G. M. J. Chem. Soc., Dalton Trans. 1989, 2173-2178.
10.1021/ic010973f CCC: $22.00 © 2002 American Chemical Society
Published on Web 02/09/2002
Inorganic Chemistry, Vol. 41, No. 5, 2002 1245

Haagenson et al.
Chart 1
phosphoranes. Having only one chelation site, they are unable
to form dinuclear and polymeric species and should therefore
have a much simpler reaction and coordination chemistry
than bis(amino)cyclodiphosph(V)azanes. Herein we report
syntheses and structures of new P-anilinodiazasilaphos-
phetidines and their metal complexes.
Results and Discussion
Diazasilaphosphetidines may be synthesized in a variety
of ways, the most unusual synthesis being the metal chloride-
induced cyclization of bis(bis(trimethylsilyl)amino)thio-
phosphoryl chlorides.31 This method, however, leads to
mixtures of diazasilaphosphetidines and azathiasilaphos-
phetidines, the former being the thermodynamic product. The
interactions of dimethyldichlorosilane with dilithiobis-
(amido)phosphines and of aminodichlorophosphines with
dilithiobis(amido)dimethylsilanes are conceptually cleaner
routes to the phosphorus(III) heterocycles.28-30 In our hands
even these reactions led to product mixtures, requiring
additional separation steps. The previously reported displace-
ment of PbCl2 by PCl3 from the diazasilaplumbetidine
[Me2Si(µ-NtBu)2Pb] is a much cleaner synthesis for the
P-chlorodiazasilaphosphetidine [Me2Si(µ-NtBu)2PCl] (1),
which serves as the starting material for the title com-
pounds.27
Many reported acyclic aminophosphoranes bear reactive
(trimethylsilyl)amino groups which cannot be tuned steri-
cally. Because steric variability is particularly easy to
introduce with aryl groups, we treated 1 with lithium anilide
to obtain quantitatively the P-anilinophosphetidine 2 (Scheme
1). The straightforward oxidations of 2 with chalcogens and
tolyl azide (Scheme 1) then furnished the corresponding P(V)
molecules [Me2Si(µ-NtBu)2PdE(NHPh)], E ) O (3), S (4),
Se (5), and N-p-tolyl (6), in crystalline form. Their NMR
spectra (1H, 13C, 31P, 29Si) are unremarkable and characteristic
of molecules with time-averaged Cs symmetry.
Three of these (3, 4, and 6) were analyzed X-ray
crystallographically, and their solid-state structures are shown
in Figures 1 and 2. Data collection and selected bond
parameters of 3, 4, and 6 are listed in Tables 1 and 2,
respectively. The crystal structures consist of hydrogen-
bonded dimers, arranged about either inversion centers (3
and 4) or 2-fold rotation axes (6) of their space groups.
Possibly due to the intermolecular hydrogen bonding, the
phenyl ring is canted toward the heterocycle and rotated out
of the Si-P-N(anilido) plane. The differences between these
molecules are limited to the exocyclic phosphorus substit-
uents, allowing their structures to be discussed collectively
below.
diphosph(V)azanes appears to be one in which they chelate
metal atoms laterally, similar to aminophosphoranes (A).18-20
The inclusion of the P(V) atoms in a heterocycle renders
both, the ligands more compact and the phosphorus atoms
more electron rich than those in acyclic aminophosphoranes,
because the imido lone-pair electrons are now perfectly
aligned with the empty d-orbitals of the phosphorus atoms.
Due to their bifunctionality bis(amino)cyclodiphospha-
zanes may coordinate either one (D) or two (E) metal
fragments, thereby allowing the syntheses of monomeric
mono- and dinuclear species and of extended structures. As
with most ligands the coordination number can, to some
degree, be controlled by the ligand’s bulk. Structure control
by steric bulk has limits, however, and to prevent bilateral
coordination of bis(amino)cyclodiphosphazanes we have
capped one end of the heterocycle with an unreactive
dimethylsilyl group. This modification leads to P-amino-
diazasilaphosphetidines (F),21-31 which are monofunctional
analogues of B and C and heterocyclic analogues of amino-
(19) Moser, D. F.; Carrow, C. J.; Stahl, L.; Staples, R. J. J. Chem. Soc.,
Dalton Trans. 2001, 1246-1252.
(20) Lief, G. R.; Carrow, C. J.; Stahl, L.; Staples, R. J. Organometallics
2001, 20, 1629-1635.
(21) The nomenclature employed in the text for these nitrogen-silicon-
phosphorus heterocycles is not systematic. Systematic names appear
in the Experimental Section.
(22) Scherer, O. J.; Quintus, P.; Kaub, J.; Sheldrick, W. S. Chem. Ber.
1987, 120, 1463-1470.
(23) Tsuyoshi, K.; Gornitzka, H.; Baceiredo, A.; Savin, A.; Betrand, G. J.
Am. Chem. Soc. 2000, 122, 998-999.
Compounds 4-6 are almost planar Si(µ-N)2P heterocycles
of tetrahedral silicon and phosphorus(V) atoms, connected
by trigonal-planar tert-butylimido groups. The silicon-
nitrogen (1.731(5)-1.745(2) Å), the endocyclic phosphorus-
nitrogen (1.652(4)-1.674(3) Å), and the phosphorus-aniline
(24) Frank, W.; Petry, V.; Gerwalin, W.; Reiss, G. J. Angew. Chem., Int.
Ed. Engl. 1996, 35, 1512-1514.
(25) Veith, M.; Kruhs, W.; Huch, V. Phosphorus, Sulfur Silicon Relat. Elem.
1995, 105, 217-220.
(26) Veith, M.; Bertsch, B.; Huch, V. Z. Anorg. Allg. Chem. 1988, 559,
73-88.
(27) Veith, M.; Grosser, M.; Huch, V. Z. Anorg. Allg. Chem. 1984, 513,
89-102.
(28) Neemann, J.; Klingebiel, U. Chem. Ber. 1981, 114, 527-535.
(29) Eichhorn, B.; No¨th, H. Z. Naturforsch. 2000, 55b, 352-360.
(30) Scherer, O. J.; Pu¨ttmann, M.; Kru¨ger, C., Wolmersha¨user, G. Chem.
Ber. 1982, 115, 2076-2124.
(31) (a) Burford, N.; Spence, R. E. v. H.; Whalen, J. M.; Rogers, R. D.;
Richardson, J. F. Organometallics 1990, 9, 2854-2856. (b) Burford,
N.; Mason, S.; Spence, R. E. v. H.; Whalen, J. M.; Richardson, J. F.;
Rogers, R. D. Organometallics 1992, 11, 2241-2250.
1246 Inorganic Chemistry, Vol. 41, No. 5, 2002

Diazasilaphosphetidines and Their Metal Compounds
Scheme 1
Figure 1. Solid-state structure of 3 (35% probability thermal ellipsoids).
The sulfur analogue (4) has the same structure.
bonds (1.644(5)-1.658(2) Å) of 3, 4, and 6 are equidistant,
while the PdO (1.4767(18) Å), PdS (1.938(2) Å), and PdN
bonds (1.561(3) Å) show the expected lengths and variations.
The very similar exocyclic phosphorus substituents of 6
(anilino and p-tolylimino) render the molecule almost C2V
symmetric, leading to a statistical disorder in the solid state,
which caused somewhat larger uncertainties in the bond
lengths and the thermal parameters of the affected atoms.
The exocyclic N-P-E bite angles in 3 and 4 are identical
but ca. 6° larger than the corresponding N-P-N angle in
6.
The sulfur derivative 4 is particularly suitable for a
structural comparison with C because the phosphorus
environments in both compounds are formally identical. For
example, the PdS bonds (1.938(2) Å in 4 and 1.9240(10) Å
in C), the P-N(anilino) bonds (1.644(5) and 1.648(2) Å),
and the P-N(imino) bonds (1.684(2) and 1.685(2) Å) are
all equidistant within experimental error. Even the somewhat
larger endocyclic N-P-N angle of 4 (87.0(2)° versus
83.60(1)° in C) does little to detract from the suitability of
the silicon-phosphorus ligands as analogues.
Figure 2. Solid-state structure of 6 (30% probability thermal ellipsoids).
The solvent molecule (toluene) is not shown.
and their solid-state structures have to our knowledge not
been reported. To test the chelating ability of these ligands
we synthesized simple complexes of diamagnetic mono-, di-,
and trivalent metals. True to the model character of this study
we chose metals for which bis(amido)cyclodiphosphazane
derivatives were known, with particular emphasis on catalysis
and the modeling of solid-state phosphates.
Although Lewis acid-base adduct of diazasilaphosphet-
idines with group 13 metal chlorides are known,31 complexes
in which these molecules function as chelating N,E ligands
Inorganic Chemistry, Vol. 41, No. 5, 2002 1247

Haagenson et al.
Table 1. Crystal Data for Compounds 3, 4, 6-8, and 11
param
3
4
6
7
8
11
chem formula
fw
C16H30N3OPSi
339.49
C16H30N3PSSi
355.55
C26.5H41N4PSi
474.65
C16H29N3PSSiTl
558.91
C18H35N3AlPSSi
411.59
C32H58N6P2S2Si2Zn
774.45
space group
T (°C)
a, Å
b, Å
c, Å
R, deg
â, deg
γ, deg
V, Å3
P1h (No. 2)
P21/n (No. 14)
22
10.3241(19)
13.803(2)
14.806(4)
P2/n (No. 13)
21
15.297(6)
9.486(3)
20.172(9)
P21/n (No. 14)
-60
13.5033(7)
9.4370(4)
17.6696(9)
P21/n (No. 14)
22
16.916(2)
8.8658(8)
18.1264(16)
C2/c (No. 15)
-60
21
9.1646(9)
9.3112(10)
11.6963(13)
85.713(2)
88.744(2)
78.111(2)
990.57(18)
2
1.138
0.710 73
2.05
0.0512
0.1506
38.0(2)
14.72(8)
17.16(10)
93.964(18)
93.66(3)
109.0550(10)
115.131(6)
116.07(11)
2105.0(7)
4
1.122
0.710 73
2.88
0.0613
0.1671
2921(2)
4
1.080
0.710 73
1.55
2128.27(18)
4
1.744
0.710 73
78.21
0.0240
0.0634
2461.4(4)
4
1.111
0.710 73
2.87
0.0429
0.1279
8630(88)
8
1.192
0.710 73
8.24
Z
F
calc, g cm-1
λ, Å
µ, cm-1
R(F)a [I > 2σ(I)]
wR2(F2)b (all data)
0.0608
0.1847
0.0376
0.1088
a R ) ∑|Fo - Fc|/∑|Fo|. b Rw ) {[∑w(Fo - Fc)2]/[∑w(Fo )2]}1/2; w ) 1/[σ2(Fo)2 + (xP)2 + yP], where P ) (Fo + 2Fc )/3.
2
2
2
2
Table 2. Selected Bond Lengths (Å) and Angles (deg) for 3, 4, and 6
Table 3. Selected Bond Lengths (Å) and Angles (deg) for 7 and 8
3
4
6
7
8
Bond Lengths
1.4767(18)
1.658(2)
1.655(2)
1.663(2)
1.743(2)
1.755(2)
1.848(3)
Bond Lengths
2.8861(9)
PdE
1.938(2)
1.644(5)
1.653(4)
1.652(4)
1.741(4)
1.731(5)
1.854(6)
1.561(3)
1.653(3)
1.666(3)
1.674(3)
1.741(3)
1.736(4)
1.860(4)
M(1)-S
2.3518(10)
1.9117(19)
1.958(3)
P(1)-N(3)
P(1)-N(1)
P(1)-N(2)
Si(1)-N(1)
Si(1)-N(2)
Si(1)-Me(av)
M(1)-N(3)
Al-C(3)
2.534(3)
Al-C(4)
P-S
1.953(4)
2.0017(12)
1.609(3)
1.683(3)
1.682(3)
1.737(3)
1.739(3)
1.857(4)
2.0192(8)
1.6198(18)
1.6546(19)
1.6545(18)
1.7515(19)
1.752(2)
P(1)-N(3)
P(1)-N(1)
P(1)-N(2)
Si(1)-N(1)
Si(1)-N(2)
Si(1)-Me(av)
Bond Angles
106.03(10)
87.85(11)
82.29(10)
108.34(15)
95.03(12)
N(3)-P(1)-E
106.9(2)
87.0(2)
81.9(2)
109.6(3)
95.0(2)
95.4(2)
100.07(16)
86.33(16)
82.16(14)
107.2(2)
95.80(15)
95.68(15)
N(1)-P(1)-N(2)
N(1)-Si(1)-N(2)
Me-Si(1)-Me
P(1)-N(1)-Si(1)
P(1)-N(2)-Si(1)
1.848(3)
Bond Angles
C(3)-Al-C(4)
N(3)-M(1)-S(1)
M(1)-N(3)-P(1)
M(1)-S(1)-P(1)
N(3)-P(1)-S
N(1)-P(1)-N(2)
N(1)-Si(1)-N(2)
Me-Si(1)-Me
P(1)-N(1)-Si(1)
P(1)-N(2)-Si(1)
116.25(17)
80.17(6)
103.16(9)
78.34(3)
98.34(7)
88.02(10)
82.04(9)
110.09(14)
94.68(9)
94.68(10)
94.27(11)
63.44(6)
104.6(7)
84.55(4)
105.84(14)
86.13(14)
82.75(13)
108.57(18)
95.13(13)
95.23(14)
Scheme 2
lack of reactivity gave some indication that 7 might be an
oligomer, the high solubility suggested a monomeric deriva-
tive.
A single-crystal X-ray diffraction study confirmed the
spectroscopic findings. Crystal data and bond parameters for
7 are collected in Tables 1 and 3, respectively, and its solid-
state structure is depicted in Figure 3. The crystal structure
consists of zigzag chains of molecules, loosely connected
by weak intermolecular thallium-sulfur bonds (3.599(2) Å).
This spirocyclic thallium compound, with its central P(V)
atom, is terminated by a dimethylsilyl group on one end and
a highly exposed thallium(I) atom on the other. While the
Si(µ-N)2P ring is almost planar, the P-N-Tl-S metallacycle
exhibits extensive puckering due to the incorporation of the
large thallium atom. Heavy main-group elements are known
for their ability to support small bond angles, but the
N-Tl-S bond angle (63.44(6)°) is small even for thallium.
The thallium-nitrogen (2.534(3) Å) and thallium-sulfur
Amidodiazasilaphosphetidines are most conveniently in-
troduced in the form of their lithium salts, but the tendency
of such salts to coordinate donor solvents causes analytical
problems. Related alkali-metal salts of acyclic phosphoranes,
for example, were invariably isolated as THF adducts or ate
complexes.4 Thallium(I) derivatives are good analogues of
alkali-metal salts, with the added advantage that they do not
form etherates and are hydrolytically more stable than alkali-
metal compounds; cf. TlC5H5 and NaC5H5.
When 4 was treated with n-butyllithium, followed by
thallium monochloride (Scheme 2), crystalline {[Me2Si(µ-
NtBu)2PdS(NPh)-κN-κS]Tl} (7) formed. Like cyclopenta-
dienylthallium, but in stark contrast to the extremely air-
sensitive dithallium bis(amido)cyclodiphosph(III)azane [P(µ-
NtBu)2P(tBuN-κN3Tl)2],32 this colorless compound is sur-
prisingly air stable in the solid state, showing decomposition
only after lengthy exposure to the atmosphere. Although its
(32) Grocholl, L.; Schranz, I.; Stahl, L.; Staples, R. J. Inorg. Chem. 1998,
37, 2496-2499.
1248 Inorganic Chemistry, Vol. 41, No. 5, 2002

Diazasilaphosphetidines and Their Metal Compounds
Figure 3. Solid-state structure of 7 (35% probability thermal ellipsoids).
Figure 4. Solid-state structure of 8 (35% probability thermal ellipsoids).
Scheme 3
(2.8861(9) Å) bonds are similar to those in related com-
pounds.33-49 Thus for example, the four Tl-N bonds in the
heterocubic [P(µ-NtBu)2P(tBuN-κN3Tl)2] range from 2.559(3)
to 2.587(3) Å,32 while the Tl-S bonds in thallium dithio-
carbamate dimers of the formula {[(C3H7)2NCS2-κS2]Tl]}2,
due to the higher coordination number (4), vary from 2.88(1)
to 3.12(1) Å.33,34
The low dimensionality of 7 is surprising, because, as the
disubstituted zinc compounds 11-13 show (see below), the
ligand is not particularly bulky and one might, therefore, have
expected stronger intermolecular interactions, possibly even
between thallium atoms. The exposedness of the thallium
atom and consequently that of its lone pair of electrons
suggest that this compound may have ligand properties
toward low-valent transition metals.
While the thallium(I) salt 7 is mainly of structural interest,
the aluminum dialkyl derivatives of 3-6, suitably activated,
may polymerize ethylene to high polymers, as had been
demonstrated for the structurally related dimethylaluminum-
amidinates and -guanidinates.50-54 In bimetallic E the
presence of two aluminum atoms had introduced complica-
tions in mechanistic studies, which are not expected for
similar monoaluminum complexes. When the monofunc-
tional 4-6 were treated with 1 equiv of AlMe3 (Scheme 3),
the corresponding dimethylaluminum complexes 8-10 formed.
Of these, one (8) was subjected to an X-ray structure
analysis. Its crystal and data collection parameters, as well
as selected bond lengths and angles, are listed in Tables 1
and 3, respectively. A thermal-ellipsoid plot (Figure 4) shows
that the aluminum atom is tetrahedrally coordinated by the
N-P-S moiety of the chelating ligand and its remaining
two methyl groups. The structural similarity of this com-
pound with E is reflected in almost identical bond param-
eters. The coordination environment about aluminum is
(33) Hesse, R.; Nilson, L. Acta Chem. Scand. 1969, 23, 1951-1965.
(34) Jennische, P.; Olin, Å; Hesse, R. Acta Chem. Scand. 1972, 26, 2799-
2812.
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859.
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Inorganic Chemistry, Vol. 41, No. 5, 2002 1249

Haagenson et al.
Scheme 4
Figure 5. Solid-state structure of 11 (35% probability thermal ellipsoids).
distorted tetrahedral, with an acute N-Al-S bond angle of
80.17(6)° and a more normal tetrahedral Me-Al-Me angle
of 116.25(17)°. The aluminum-methyl bonds are equidistant
(1.955(4) Å), while the Al-N (1.9117(19) Å) and Al-S
(2.3518(10) Å) bonds are comparatively short and long,
respectively, similar to those in E.
Table 4. Selected Bond Lengths (Å) and Angles (deg) for 11
Bond Lengths
Zn-S(av)
Zn-N(av)
P-S(av)
2.408(12)
2.020(9)
2.068(10)
1.638(8)
P-imido(av)
1.694(8)
1.777(8)
1.888(9)
Si-N(av)
Si-Me(av)
P-anilido(av)
Bond Angles
Sterically encumbered zinc amides are efficient poly-
merization catalysts for lactides and related monomers.55-58
Although mono(ethylzinc) complexes, like D, may have
catalytic properties, here we were interested solely in the
structural aspects of these zinc amidodiazasilaphosphetidines.
Because NR and NR2 are isoelectronic with O and O-,
respectively, bis(amino)cyclodiphosph(V)azanes may be con-
sidered hydrocarbon-soluble analogues of diphosphates. We
had attempted to connect bis(amido)cyclodiphosph(V)azanes
to one-dimensional metallapolyphosph(V)azanes, or quasi-
polymetallaphosphates, using divalent metal ions. Zinc and
magnesium are the most obvious metals for this purpose,
because of their size, diamagnetism, and the commercial
availability of their dialkyls.
S(1)-Zn-S(2)
N(1)-Zn-N(4 )
S(1)-Zn-N(1 )
S(1)-Zn-N(4 )
S(2)-Zn-N(1 )
120.6(4)
131.7(3)
80.9(3)
125.8(3)
123.1(4)
S(2)-Zn-N(4 )
80.6(3)
101.5(2)
87.9(2)
82.9(2)
94.3(3)
N-P-S(av)
N-P-N(endoc)
N-Si-N(av)
P-N-Si(av)
These reactions are similar to those of acyclic amino-
(chalcogeno)phosphoranes with zinc reagents, where treat-
ment of [R2PdE(NHR′)] with Zn[N(SiMe3)2]2 or ZnEt2 had
yielded complexes of the type {[R2P(S)NR′]2Zn}.59,60
The crystal data and selected bond metrics of 11 are
collected in Tables 1 and 4, respectively. As Figure 5 shows,
the molecule is a linear tetraspirocycle, having a central zinc
atom, flanked by two P-anilido-P-thiodiazasilaphosphet-
idines. This compound is structurally related to the bis-
(aminophosphoranate) complexes {Et2PdE(NMe)-κN-κE]2Zn}
and {[tBu2PdE(NiPr)-κN-κE]2Zn},59,60 E ) S and Se,
discussed above. In 11 the coordination geometry about zinc
is distorted tetrahedral, with large N-Zn-N, N-Zn-S, and
S-Zn-S angles (120.6(4)-131.7(3)°) between donor atoms
from different ligands but small N-Zn-S angles (80.8(3)°)
between donor atoms from the same ligand. None of the bond
lengths of the Si(µ-N)2P ligand changed significantly upon
coordination, but the phosphorus-sulfur bond lengthened
from 1.938(2) Å in 4 to 2.068(10) Å in the complex.
While the monothallium compound 7 is the only plausible
stoichiometric product of the title ligands, diethylzinc and
trimethylaluminum can react with up to 2 or 3 equiv of these
diazasilaphosphetidines, respectively. The differing reactivity
of alkylaluminum and -zinc reagentssstrictly monoligand
complexes for the former but diligand complexes for the
latterstherefore deserves an additional comment. The re-
luctance of aluminum to coordinate more than one ligand is
likely due to its smaller size and higher valence, because an
In the course of these studies we discovered that bis-
(anilino)dithiacyclodiphosph(V)azane C reacts with 1 equiv
of diethylzinc to form a precipitate, whose lack of solubility
made its structure elucidation impossible.
To gain insight into the coordination environment about
zinc in such polymeric species, we treated the identically
substituted, but monofunctional, P-anilino-P-thiodiazasila-
phosphetidine (4) with diethylzinc. As expected, and in
distinct contrast to the monosubstitution of trimethylalumi-
num, diethylzinc reacted with 2 equiv of 4 (Scheme 4) to
give a colorless product (11). The NMR spectra revealed
unambiguously the loss of both ethyl groups, and this
disubstitution could be prevented neither by lowering the
reaction temperature nor by using ligands bearing the larger
selenium (5) or tolylimino (6) phosphorus substituents. Thus
the addition of 4-6 to ZnEt2, both at low (-78 °C) and
ambient temperatures, yielded analogous diligand complexes.
(55) Dinger, M. B.; Scott, M. J. Inorg. Chem. 2001, 40, 1029-1036.
(56) Chamberlain, B. M.; Cheng, M.; Moore, D. R.; Ovitt, T. M.;
Lobkovsky, E. B.; Coates, G. W. J. Am. Chem. Soc. 2001, 123, 3229-
3238.
(57) Cheng, M.; Darling, N. A.; Lobkovsky, E. B.; Coates, G. W. Chem.
Commun. (Cambridge) 2000, 2007-2008.
(58) Chisholm, M. H.; Eilerts, N. W.; Huffmann, J. C.; Iyver, S. S.; Pacold,
M.; Phomprai, K. J. Am. Chem. Soc. 2000, 122, 11845-11854.
(59) Fuchs, M.; Kuchen, W.; Peters, W. Z. Anorg. Allg. Chem. 1987, 545,
75-82.
(60) Bochmann, M.; Bwembya, G. C.; Hursthouse, M. B.; Coles, S. J. J.
Chem. Soc., Dalton Trans. 1995, 2813-2817.
1250 Inorganic Chemistry, Vol. 41, No. 5, 2002

Diazasilaphosphetidines and Their Metal Compounds
was allowed to stir at room temperature for 18 h. The tan-colored
solution was concentrated in vacuo and stored at -21 °C until clear,
colorless crystals had precipitated. These were redissolved in hot
hexanes, and the flask was left to cool at room temperature until
clear, colorless plates had formed. Yield: 0.394 g, 77%.
Mp: 200-202 °C. 1H NMR (500.13 MHz, benzene-d6, 26 °C):
δ ) 9.15 (s, 1 H), 7.60 (d, 2 H, JHH ) 8.0 Hz), 7.18 (t, 2 H, JHH
) 7.8 Hz), 6.83 (t, 1 H, JHH ) 7.3 Hz), 1.30 (s, 18 H), 0.38 (s, 3
H), 0.35 (s, 3 H). 13C{1H} NMR (125.76 MHz, benzene-d6, 26
°C): δ ) 144.0 (s); 128.8 (s), 120.4 (s), 118.6 (d, JPC ) 6.8 Hz),
51.9 (s), 31.9 (d, JPC ) 6.1 Hz), 4.0 (s), 2.1 (d, JPC ) 6.4 Hz).
31P{1H} NMR (202.46 MHz, benzene-d6, 26 °C): δ ) 3.1 (d, JPH
) 5.5 Hz). 29Si NMR (99.35, benzene-d6, 26 °C): δ ) -2.2 (s).
Anal. Calcd for C16H30N3OPSi: C, 55.61; H, 8.91; N, 12.38.
Found: C, 55.63; H, 9.08; N, 12.43.
[Me2Si(µ-NtBu)2PdS(NHPh)] (4) (1,3-Di-tert-butyl-2,2-di-
methyl-4-anilino-4-thio-1,3,2,4-diazasilaphosphetidine). A mix-
ture of sublimed sulfur (0.600 g, 18.7 mmol) and 2 (6.05 g, 18.7
mmol) in 60 mL of toluene was stirred for 18 h at 50 °C,
concentrated in vacuo, and then stored at -21 °C. Several fractions
of white crystals yielded 6.34 g (95.3%) of product.
Mp: 184-185 °C. 1H NMR (500.13 MHz, benzene-d6, 26 °C):
δ ) 7.05 (t, 2 H, JHH ) 7.9 Hz), 6.83 (d, 2 H, JHH ) 7.8 Hz), 6.80
(t, 1 H, JHH ) 7.4 Hz), 5.70 (d, 1 H, JPH ) 12.1 Hz), 1.30 (s, 18
H), 0.35 (s, 3 H), 0.31 (s, 3 H). 13C{1H} NMR (125.76 MHz,
benzene-d6, 26 °C): δ ) 142.0 (d, JPC ) 5.8 Hz), 129.0 (s), 121.7
(s), 118.6 (d, JPC ) 5.8 Hz), 52.9 (s), 31.3 (d, JPC ) 6.2 Hz), 3.5
(s), 3.3 (d, JPC ) 4.5 Hz). 31P{1H} NMR (202.46 MHz, benzene-
d6, 26 °C): δ ) 64.1 (d, JPH ) 12.2 Hz). 29Si NMR (99.35 MHz,
benzene-d6, 26 °C): δ ) 2.6 (s). Anal. Calcd for C16H30N3PSSi:
C, 54.05; H, 8.50; N, 11.82. Found: C, 54.15; H, 8.58; N, 11.80.
[Me2Si(µ-NtBu)2PdSe(NHPh)] (5) (1,3-Di-tert-butyl-2,2-di-
methyl-4-anilino-4-seleno-1,3,2,4-diazasilaphosphetidine). A sus-
pension of gray selenium (0.305 g, 3.86 mmol) in toluene was
treated dropwise at room temperature with a toluene solution of 2
(1.25 g, 3.86 mmol). The mixture was stirred at reflux until it
became clear (18 h) and concentrated in vacuo until a solid
precipitated. This solid was redissolved, and the colorless solution
was stored at -21 °C to afford a white powder (1.44 g, 92.5%).
Mp: 184-186 °C. 1H NMR (500.13 MHz, benzene-d6, 26 °C):
δ ) 7.03 (t, 2 H, JHH ) 7.8 Hz), 6.79 (t, 1 H, JHH ) 7.6 Hz), 6.77
(d, 2 H, JHH ) 7.7 Hz), 5.80 (d, 1 H, JPH ) 14.6), 1.31 (s, 18 H),
0.35 (s, 3 H), 0.29 (s, 3 H). 13C{1H} NMR (125.76 MHz, benzene-
d6, 26 °C): δ ) 141.8 (d, JPC ) 8.5 Hz), 129.0 (s), 122.0 (s), 118.7
aluminum complex bearing two chelating ligands would be
five-coordinate. Given the size of these ligands, this coor-
dination number apparently cannot be attained.
In summary, P-anilino-P-chalcogenodiazasilaphospheti-
dines combine the predictable coordination chemistry of
aminophosphoranes with the steric and electronic advantages
of bis(amino)cyclodiphosph(V)azanes. Because the utility of
aminophosphoranes stems, in part, from their electron-
richness, the cyclic species 3-6 should be even better
ligands, since each phosphorus atom has not one or two but
three (or four) nitrogen substituents. Although these synthetic
and structural studies were limited to group 12 and 13 metals,
they show that the bite angles of these ligands are sufficiently
flexible to accommodate metals ranging in size from 1.18
to 1.48 Å, and one can therefore expect an extensive a
coordination chemistry of P-aminodiazasilaphosphetidines.
Experimental Section
General Procedures. All experiments were performed under an
atmosphere of purified nitrogen or argon, using standard Schlenk
techniques. Solvents were dried and freed of molecular oxygen by
distillation under an atmosphere of nitrogen from sodium or
potassium benzophenone ketyl immediately before use. NMR
spectra were recorded on a Bruker Avance-500 NMR spectrometer.
The 1H, 13C, and 31P NMR spectra are referenced relative to C6D5H
(7.15 ppm), C6D6 (128.0 ppm), and P(OEt)3 (137.0 ppm), respec-
tively. Melting points were obtained on a Mel-Temp apparatus and
are uncorrected. Elemental analyses were performed by E and R
Microanalytical Services, Parsipanny, NJ.
Trimethylaluminum was used as 2.0 M heptanes (Aldrich) and
2.4 M hexanes (Acros) solutions. Diethylzinc was purchased from
Acros and diluted to 0.91 M in hexanes. Both [Me2Si(µ-NtBu)2PCl]
(1)27 and p-tolyl azide61 were synthesized by published procedures.
Syntheses. [Me2Si(µ-NtBu)2P(NHPh)] (2) (1,3-Di-tert-butyl-
2,2-dimethyl-4-anilino-1,3,2,4-diazasilaphosphetidine). A cold (0
°C) solution of aniline (7.30 mL, 80.1 mmol) in 25 mL of THF
n
was treated dropwise with BuLi (1.6 M in hexanes, 80.0 mmol),
refluxed for 1 h, and then added dropwise at -78 °C to a solution
of 1 (21.4 g, 80.0 mmol) in 25 mL of toluene. The reaction mixture
was allowed to warm to room temperature and stirred for 18 h.
After all liquids had been removed in vacuo, the remaining solid
was extracted with 50 mL of toluene, and the extract was filtered
through a medium-porosity frit. The clear filtrate was concentrated
in vacuo and stored at -21 °C until the syrupy liquid had solidified.
Yield: 23.4 g (90.3%).
Mp: 45-47 °C. 1H NMR (500.13 MHz, benzene-d6, 26 °C): δ
) 7.12 (t, 2 H, JHH ) 7.9 Hz), 7.00 (dt, 2 H, JHH ) 8.5, 1.2 Hz),
6.76 (tt, 1 H, JHH ) 7.3, 2.1 Hz), 4.35 (s, 1 H), 1.16 (s, 18 H), 0.34
(s, 3 H), 0.33 (s, 3 H). 13C{1H} NMR (125.76 MHz, benzene-d6,
26 °C): δ ) 145.5 (d, JPC ) 11.1 Hz), 129.5 (s), 119.5 (s), 116.9
(d, JPC ) 12.3 Hz), 50.3 (d, JPC ) 10.5), 32.7 (d, JPC ) 6.8 Hz),
8.5 (d, JPC ) 2.5 Hz), 5.3 (s). 31P{1H} NMR (202.46 MHz, benzene-
d6, 26 °C): δ ) 135.8 (s). 29Si NMR (99.35 MHz, benzene-d6, 26
°C): δ ) 9.7 (s). Anal. Calcd for C16H30N3PSi: C, 59.41; H, 9.35;
N, 12.99. Found: C, 59.33; H, 9.64; N, 13.12.
(d, JPC ) 5.9 Hz); 53.3 (s), 31.3 (d, JPC ) 5.9 Hz), 4.1 (d, JPC
)
3.0 Hz), 3.3 (s). 31P{1H} NMR (202.46 MHz, benzene-d6, 26 °C):
δ ) 35.9 (d, JPH ) 14.7 Hz). 29Si NMR (99.35 MHz, benzene-d6,
26 °C): δ ) 4.0 (s). Anal. Calcd for C16H30N3PSeSi: C, 47.75; H,
7.51; N, 10.44. Found: C, 47.69; H, 7.52; N, 10.42.
{[Me2Si(µ-NtBu)2Pd(N-p-tolyl)(NHPh)]‚0.5C6H5Me} (6) (1,3-
Di-tert-butyl-2,2-dimethyl-4-anilino-4-(p-tolylimino)-1,3,2,4-
diazasilaphosphetidine-Hemitoluene). A solution of 2 (6.18 g,
19.1 mmol) in 40 mL of toluene was treated with 2.80 g (21.0
mmol) of p-tolyl azide, dissolved in 10 mL of toluene. The reaction
mixture, which evolved gas, was stirred for 18 h at room
temperature and then refluxed for 2 h, while it became orange-red.
Following two recrystallizations at -21 °C, colorless crystals (6.87
g, 75.8%) were recovered.
Mp: 134-135 °C. 1H NMR (500.13 MHz, benzene-d6, 26 °C):
δ ) 7.51 (s, 1 H), 7.31 (d, 2 H, JHH ) 7.7 Hz), 7.24 (t, 2 H, JHH
) 7.4 Hz), 7.14 (d, 2 H, JHH ) 7.0 Hz), 6.95 (d, 2 H, JHH ) 7.9
Hz), 6.85 (t, 1 H, JHH ) 7.2 Hz), 2.13 (s, 3 H), 1.17 (s, 18 H), 0.47
(s, 3 H), 0.46 (s, 3 H). 13C{1H} NMR (125.76 MHz, benzene-d6,
[Me2Si(µ-NtBu)2PdO(NHPh)] (3) (1,3-Di-tert-butyl-2,2-di-
methyl-4-anilino-4-oxo-1,3,2,4-diazasilaphosphetidine). At 0 °C,
a solution of 2 (0.490 g, 1.52 mmol) in 15 mL of toluene was treated
with cumene hydroperoxide (0.29 mL, 1.5 mmol), and the mixture
(61) Smith, P. A.; Brown, B. B. J. Am. Chem. Soc. 1951, 73, 2438-2441.
Inorganic Chemistry, Vol. 41, No. 5, 2002 1251

Haagenson et al.
26 °C): δ ) 148.2 (d, JPC ) 1.6 Hz), 143.3 (d, JPC ) 2.9 Hz),
129.4 (s), 128.8 (s), 128.5 (s), 122.4 (d, JPC ) 14.0 Hz), 121.1 (d,
JPC ) 11.1 Hz), 119.2 (s), 52.0 (s), 31.9 (d, JPC ) 5.5 Hz), 20.7
(s), 3.5 (d, JPC ) 2.9 Hz), 3.4 (d, JPC ) 2.8 Hz). 31P{1H} NMR
(202.46 MHz, benzene-d6, 26 °C): δ ) 12.0 (s). 29Si NMR (99.35
MHz, benzene-d6, 26 °C): δ ) -3.1 (s). Anal. Calcd for C26.5H41N4-
PSi: C, 67.05; H, 8.71; N, 11.80. Found: C, 67.12; H, 8.84; N,
11.85.
3.0 (s), -6.6 (s). 31P{1H} NMR (202.46 MHz, benzene-d6, 26 °C):
δ ) 19.7 (s). 29Si NMR (99.35 MHz, benzene-d6, 26 °C): δ ) 3.9
(s). Anal. Calcd for C18H35N3AlPSeSi2: C, 47.15; H, 7.69; N, 9.16.
Found: C, 47.25; H, 7.73; N, 9.14.
{[Me2Si(µ-NtBu)2Pd(N-p-tolyl)(NPh)-KN2]AlMe2} (10) ((1,3-
Di-tert-butyl-2,2-dimethyl-4-anilino-4-(p-tolylimino)-1,3,2,4-
diazasilaphosphetidinyl-KN2)dimethylaluminum). The addition
of 0.46 mL of AlMe3 to 6 (0.453 g, 1.01 mmol), dissolved in 10
mL of cold (0 °C) toluene, caused a rapid gas evolution. After the
clear, colorless solution had been stirred at room temperature for
18 h, it was concentrated in vacuo and stored at -21 °C. Yield:
0.457 g, 92.9%, of colorless crystals.
{[Me2Si(µ-NtBu)2PdS(NPh)-KN-KS]Tl} (7) ((1,3-Di-tert-butyl-
2,2-dimethyl-4-anilino-4-thio-1,3,2,4-diazasilaphosphetidinyl-
KN-KS)thallium(I)). A cold solution of 4 (0.356 g, 1.00 mmol) in
n
10 mL of toluene was treated dropwise with 0.40 mL of BuLi.
Mp: 170-171 °C. 1H NMR (500.13 MHz, benzene-d6, 26 °C):
δ ) 7.23-7.17 (m, 4 H), 7.12 (d, 2 H, JHH ) 8.2 Hz), 6.96 (d, 2
H, JHH ) 8.3 Hz), 6.85 (tt, 1 H, JHH ) 6.9, 1.5 Hz), 2.15 (s, 3 H),
1.04 (s, 18 H), 0.41 (s, 3 H), 0.40 (s, 3 H), 0.01 (s, 6 H). 13C{1H}
NMR (125.76 MHz, benzene-d6, 26 °C): δ ) 145.8 (s), 143.0 (s),
129.9 (s), 129.3 (s), 129.2 (s), 120.5 (s), 120.4 (s), 120.3 (s), 52.7
(s), 31.7 (d, JPC ) 5.5 Hz), 20.7 (s), 3.0 (dd, JPC ) 4.8, 2.9 Hz),
-8.5 (s). 31P{1H} NMR (202.46 MHz, benzene-d6, 26 °C): δ )
6.3 (s). 29Si NMR (99.35 MHz, benzene-d6, 26 °C): δ ) -1.1 (s).
Anal. Calcd for C25H42N4AlPSi: C, 61.95; H, 8.73; N, 11.56.
Found: C, 61.57; H, 8.94; N, 11.63.
{[Me2Si(µ-NtBu)2PdS(NPh)-KN-KS]2Zn} (11) (Bis(1,3-di-
tert-butyl-2,2-dimethyl-4-anilino-4-thio-1,3,2,4-diazasilaphos-
phetidinyl-KN-KS)zinc). To a sample of 4 (0.352 g, 0.990 mmol),
dissolved in 20 mL of cold (0 °C) toluene, was added dropwise
0.55 mL of the diethylzinc solution. The ice bath was removed,
and the clear, colorless reaction mixture was stirred for 18 h at
room temperature. It was then concentrated in vacuo and kept at
rom temperature until 0.311 g of colorless plates had formed.
Yield: 81%.
Mp: 302-304 °C. 1H NMR (500.13 MHz, benzene-d6, 26 °C):
δ ) 7.54 (d, 2 H, JHH ) 8.5 Hz), 7.26 (t, 2 H, JHH ) 7.4 Hz), 6.92
(t, 1 H, JHH ) 7.3 Hz), 1.33 (s, 18 H), 0.34 (s, 3 H); 0.25 (s, 3 H).
13C{1H} NMR (125.76 MHz, benzene-d6, 26 °C): δ ) 149.0 (d,
JPC ) 10.6 Hz), 129.0 (s), 122.0 (d, JPC ) 15.6 Hz), 120.3 (s),
53.0 (s), 31.7 (d, JPC ) 5.7 Hz), 3.3 (d, JPC ) 3.9 Hz), 2.9 (s).
31P{1H} NMR (202.46 MHz, benzene-d6, 26 °C): δ ) 48.2 (s).
29Si NMR (99.35 MHz, benzene-d6, 26 °C): δ ) 1.3 (s). Anal.
Calcd for C32H58N6P2S2Si2Zn: C, 49.63; H, 7.55; N, 10.85.
Found: C, 49.67; H, 7.73; N, 10.98.
After gas evolution had ceased, the reaction mixture was refluxed
for 1 h and then added dropwise to a cold (0 °C) suspension of
TlCl (0.240 g, 1.00 mmol) in 10 mL of THF. The mixture was
stirred at room temperature for 18 h, taken to dryness in vacuo,
and finally extracted with 10 mL of toluene. The extract was filtered
through a medium-porosity frit, and the clear filtrate was concen-
trated in vacuo to ca. 5 mL and stored at -21 °C. Several fractions
of thin, colorless plates afforded 0.391 g of product. Yield: 70%.
1
Mp: 201-203 °C (dec). H NMR (500.13 MHz, benzene-d6,
26 °C): δ ) 7.32 (t, 2 H, JHH ) 7.5 Hz), 7.15 (d, 2 H, J ) 7.4
Hz), 6.92 (td, 1 H, JHH ) 7.2 Hz, 0.8 Hz), 1.34 (s, 18 H), 0.41 (s,
3 H), 0.39 (s, 3 H). 13C{1H} NMR (125.76 MHz, benzene-d6, 26
°C): δ ) 149.3 (d, JPC ) 8.6 Hz), 128.0 (s); 121.9 (d, JPC ) 16.3
Hz), 119.6 (s), 52.7 (s), 31.8 (d, JPC ) 5.3 Hz); 4.1 (s), 3.6 (d, JPC
) 3.8 Hz). 31P{1H} NMR (202.46 MHz, benzene-d6, 26 °C): δ )
38.3 (s). 29Si NMR (99.4 MHz, benzene-d6, 26 °C): δ ) -1.4 (s).
Anal. Calcd for C16H29N3PSSiTl: C, 34.38; H, 5.23; N, 7.52.
Found: C, 34.49; H, 5.40; N, 7.74.
{Me2Si(µ-NtBu)2PdS(NPh)-KN-KS]AlMe2} (8) ((1,3-Di-tert-
butyl-2,2-dimethyl-4-anilino-4-thio-1,3,2,4-diazasilaphosphetidi-
nyl-KN-KS)dimethylaluminum). To a cold (0 °C) solution of 4
(0.704 g, 1.98 mmol) in 20 mL of hexanes was added dropwise
1.00 mL of AlMe3 in heptanes. The colorless solution was allowed
to slowly warm to room temperature and kept at that temperature
for 18 h. It was concentrated in vacuo and stored at -21 °C to
afford 0.722 g of colorless needles. Yield: 89%.
Mp: 164-166 °C. 1H NMR (500.13 MHz, benzene-d6, 26 °C):
δ ) 7.25 (d, 2 H, JHH ) 7.6 Hz), 7.13 (t, 2 H, JHH ) 7.5 Hz), 6.85
(t, 1 H, JHH ) 7.4 Hz), 1.18 (s, 18 H), 0.29 (s, 3 H), 0.20 (s, 3 H),
-0.02 (s, 6 H). 13C{1H} NMR (125.76 MHz, benzene-d6, 26 °C):
{[Me2Si(µ-NtBu)2PdSe(NPh)-KN-KSe]2Zn} (12) (Bis(1,3-di-
tert-butyl-2,2-dimethyl-4-anilino-4-seleno-1,3,2,4-diazasilaphos-
phetidinyl-KN-KSe)zinc). To a sample of 5 (0.402 g, 1.00 mmol),
dissolved in 10 mL of cold (0 °C) toluene, was added dropwise
0.55 mL of the diethylzinc solution. The clear, colorless reaction
mixture, which evolved ethane, was allowed to warm to room
temperature and stirred for an additional 18 h. It was then
concentrated in vacuo and stored at -21 °C until 0.398 g of
colorless crystals had formed. Yield: 92%.
Mp: 306-308 °C. 1H NMR (500.13 MHz, benzene-d6, 26 °C):
δ ) 7.60 (d, 2 H, JHH ) 8.0 Hz); 7.24 (t, 2 H, JHH ) 7.5 Hz); 6.91
(t, 1 H, JHH ) 7.3 Hz); 1.34 (s, 18 H); 0.32 (s, 3 H); 0.25 (s, 3H).
13C{1H} NMR (125.76 MHz, benzene-d6, 26 °C): δ ) 149.8 (d,
JPC ) 13.6 Hz), 129.0 (s), 122.2 (d, JPC ) 16.0 Hz), 120.5 (s),
53.3 (s), 31.6 (d, JPC ) 5.4 Hz), 3.9 (d, JPC ) 2.8 Hz), 2.8 (s).
31P{1H} NMR (202.46 MHz, benzene-d6, 26 °C): δ ) 32.3 (s).
29Si NMR (99.4 MHz, benzene-d6, 26 °C): δ ) 2.2 (s). Anal. Calcd
for C32H58N6P2Se2Si2Zn: C, 44.27; H, 6.73; N, 9.68. Found: C,
44.38; H, 6.81; N, 9.62.
δ ) 145.9 (d, JPC ) 8.8 Hz), 129.4 (s), 121.6 (s), 120.3 (d, JPC
)
14.4 Hz), 53.3 (s), 31.4 (d, JPC ) 6.0 Hz), 3.1 (s), 3.1 (s), -7.0 (s).
31P{1H} NMR (202.5 MHz, benzene-d6, 26 °C): δ ) 35.8 (s). 29Si
NMR (99.35 MHz, benzene-d6, 26 °C): δ ) 3.1 (s). Anal. Calcd
for C18H35N3AlPSSi: 52.53; H, 8.57; N, 10.21. Found: C, 52.13;
H, 8.92; N, 10.28.
{[Me2Si(µ-NtBu)2PdSe(NPh)-KN-KSe]AlMe2} (9) ((1,3-Di-tert-
butyl-2,2-dimethyl-4-anilino-4-seleno-1,3,2,4-diazasilaphosphe-
tidinyl-KN-KS)dimethylaluminum). To a cooled (0 °C) toluene
solution of AlMe3 (1.00 mmol) was added a toluene solution of 5
(0.400 g, 0.993 mmol). The reaction mixture, which remained
colorless and clear, was stirred at room temperature until all gas
evolution had ceased (ca. 18 h). It was concentrated in vacuo and
stored at -21 °C to produce 0.385 g of colorless needles. Yield:
84%.
Mp: 164-166 °C. 1H NMR (500.13 MHz, benzene-d6, 26 °C):
δ ) 7.31 (d, 2 H, JHH ) 8.5 Hz), 7.13 (t, 2 H, JHH ) 7.6 Hz), 6.85
(t, 1 H, JHH ) 7.4 Hz), 1.19 (s, 18 H), 0.25 (s, 3 H), 0.18 (s, 3 H);
0.06 (s, 6 H). 13C {1H} NMR (125.76 MHz, benzene-d6, 26 °C):
δ ) 146.7 (d, JPC ) 10.8 Hz), 129.4 (s), 121.8 (s), 120.5 (d, JPC
14.4 Hz), 53.6 (s), 31.3 (d, JPC ) 5.9 Hz), 3.6 (d, JPC ) 3.1 Hz),
)
{[Me2Si(µ-NtBu)2Pd(N-p-tolyl)(NPh)-KN2]2Zn} (13) (Bis(1,3-
di-tert-butyl-2,2-dimethyl-4-anilino-4-(p-tolylimino)-1,3,2,4-di-
1252 Inorganic Chemistry, Vol. 41, No. 5, 2002

Diazasilaphosphetidines and Their Metal Compounds
azasilaphosphetidinyl-KN2)zinc). In a manner strictly identical with
that used for the syntheses of 7 and 8, a sample of 6 (0.428 g,
0.999 mmol) and 0.55 mL of the diethylzinc stock solution were
allowed to react. Several fractions of a white powder yielded 0.395
g of product. Overall yield: 86%.
Mp: 320-322 °C. 1H NMR (500.13 MHz, benzene-d6, 26 °C):
δ ) 7.43 (d, 2 H, JHH ) 8.0 Hz), 7.34 (d, 2 H, JHH ) 8.2 Hz), 7.24
(t, 2 H, JHH ) 7.7 Hz), 7.03 (d, 2 H, JHH ) 8.2 Hz), 6.88 (t, 1H,
JHH ) 7.3 Hz), 2.22 (s, 3 H), 1.22 (s, 18 H), 0.53 (s, 3 H), 0.52 (s,
3 H). 13C{1H} NMR (125.76 MHz, benzene-d6, 26 °C): δ ) 149.2
(s), 146.4 (s), 129.4 (s), 128.8 (s), 127.6 (s), 122.5 (d, JPC ) 14.4
Hz), 122.3 (d, JPC ) 14.1 Hz), 119.0 (s), 52.2 (d, JPC ) 2.6 Hz),
32.2 (d, JPC ) 5.2 Hz), 20.8 (s), 3.5 (m). 31P{1H} NMR (202.46
MHz, benzene-d6, 26 °C): δ ) 13.2 (s). 29Si NMR (99.4 MHz,
benzene-d6, 26 °C): δ ) -3.5 (s). Anal. Calcd for C46H72N8Si2P2-
Zn: C, 60.01; H, 7.88; N, 12.17. Found: C, 60.14; H, 7.96; N,
12.28.
Acknowledgment. We thank the Chevron Phillips Chemi-
cal Co. for financial support.
Supporting Information Available: Six X-ray crystallographic
files for structures 3, 4, 6-8, and 11 in CIF format. This material
is available free of charge via the Internet at http://pubs.acs.org.
IC010973F
Inorganic Chemistry, Vol. 41, No. 5, 2002 1253