New silylated iminophosphorano(amino)phosphines Me3SiN=PPh2N(r)PPh2 (R = Et, nPr, nBu). Crystal and molecular structure of trimethylsilyliminophosphorano(propylamino)-diphenylphosphine Me3SiN=PPh2N(nPr)PPh2. Further oxidative derivatization with S, Se, and azides

Article abstract of DOI:10.1021/ic000878r

Bis(phosphino)amines Ph₂PN(R)PPh₂ (R = Et, ⁿPr, ⁿBu) react with stoichiometric amounts of trimethylsilyl azide to give the trimethylsilyliminophosphorano(amino)phosphines Me₃SiN=PPh₂N(R)PPh₂ (1, R = Et; 2, R = _nPr; 3, R = _nBu) as crystalline compounds. The structure of 2 has been determined by single-crystal X-ray analysis. (Crystal data for 2: monoclinic, P2₁/c, a = 10.235(1) A, b = 16.802(2) A, c = 17.075(2) A, β = 101.05(1)°, V = 2882.9(5) A³, Z = 4.) The structure of 2, which is the first example of an iminophosphoranophosphine with the P^III-N-P^V=N skeleton, was solved by direct methods and refined to R = 0.044. Compound 2 readily reacts with elemental sulfur, selenium, or phosphoryl azide to give fully oxidized phosphinimines Ph₂P(E)N(ⁿPr)Ph₂P= NSiMe₃ (4, E = S; 5, E = Se; 6, E = NP(O)(OPh)₂). Compounds 4-6 are very sensitive to moisture and readily undergo desilylation to give the parent phosphinimines Ph₂P(E)N(ⁿPr)Ph₂P=NH, which can be isolated as moderately stable crystalline solids. The phosphiniminophosphine 2 and the oxidized phosphinimines (4 and 5) react with CpTiCl₃ to give new nitrogen-bound Ti(IV) derivatives Ph₂P(E)N(ⁿPr)Ph₂P=NTi(Cp)Cl₂ (10, E = lone pair; 11, E = S; 12, E = Se). Compounds 1-3 readily react with rhodium(I), palladium(II), and platinum(II) complexes to give five-membered metallacycles via phosphorus(III) and imine nitrogen coordination.

Full text of DOI:10.1021/ic000878r

1802
Inorg. Chem. 2001, 40, 1802-1808
n
New Silylated Iminophosphorano(amino)phosphines Me3SiNdPPh2N(R)PPh2 (R ) Et, Pr,
nBu). Crystal and Molecular Structure of Trimethylsilyliminophosphorano(propylamino)-
diphenylphosphine Me3SiNdPPh2N(nPr)PPh2. Further Oxidative Derivatization with S, Se,
and Azides, Titanium(IV) Transmetalation of the Imine, and Syntheses of Rhodium(I),
Palladium(II), and Platinum(II) Complexes of These Iminophosphorano(amino)phosphines
Maravanji S. Balakrishna,1a S. Teipel,1b A. Alan Pinkerton,1b and Ronald G. Cavell*,1c
Department of Chemistry, University of Alberta, Edmonton, AB, Canada T6G 2G2, and
Department of Chemistry, University of Toledo, Toledo, Ohio, 43606-3390
ReceiVed August 4, 2000
Bis(phosphino)amines Ph2PN(R)PPh2 (R ) Et, nPr, nBu) react with stoichiometric amounts of trimethylsilyl azide
n
to give the trimethylsilyliminophosphorano(amino)phosphines Me3SiNdPPh2N(R)PPh2 (1, R ) Et; 2, R ) Pr;
n
3, R ) Bu) as crystalline compounds. The structure of 2 has been determined by single-crystal X-ray analysis.
(Crystal data for 2: monoclinic, P21/c, a ) 10.235(1) Å, b ) 16.802(2) Å, c ) 17.075(2) Å, â ) 101.05(1)°, V
) 2882.9(5) Å3, Z ) 4.) The structure of 2, which is the first example of an iminophosphoranophosphine with
the PIII-N-PVdN skeleton, was solved by direct methods and refined to R ) 0.044. Compound 2 readily reacts
with elemental sulfur, selenium, or phosphoryl azide to give fully oxidized phosphinimines Ph2P(E)N(nPr)Ph2Pd
NSiMe3 (4, E ) S; 5, E ) Se; 6, E ) NP(O)(OPh)2). Compounds 4-6 are very sensitive to moisture and readily
undergo desilylation to give the parent phosphinimines Ph2P(E)N(nPr)Ph2PdNH, which can be isolated as
moderately stable crystalline solids. The phosphiniminophosphine 2 and the oxidized phosphinimines (4 and 5)
react with CpTiCl3 to give new nitrogen-bound Ti(IV) derivatives Ph2P(E)N(nPr)Ph2PdNTi(Cp)Cl2 (10, E )
lone pair; 11, E ) S; 12, E ) Se). Compounds 1-3 readily react with rhodium(I), palladium(II), and platinum(II)
complexes to give five-membered metallacycles via phosphorus(III) and imine nitrogen coordination.
Introduction
a variety of products. These migration and elimination reactions
provide ready routes to the formation of both early and late
transition metal derivatives wherein element-nitrogen σ-bonds
are developed. We now report the syntheses of the novel
nitrogen-bridged iminophosphoranophosphines Me3SiNdPPh2-
We have described previously the synthesis of a series of
phosphorus-based heterodifunctional ligands that can be obtained
from the partial oxidation of one phosphorus in bis(phosphines)
with azides2-11 or chalcogens.12,13 Of special interest are the
silylated iminophosphoranophosphines, which are obtained from
trimethylsilyl azide oxidation, because the silyl group can be
subsequently replaced,8,10 migrated,14 or eliminated15,16 to form
n
n
N(R)PPh2 (1, R ) Et; 2, R ) Pr; 3, R ) Bu), spectroscopic
characterization of all, and the X-ray structural analysis of 2.
Derivatization of 2 (R ) nPr) with sulfur, selenium, and
phosphoryl azide provides dissymmetric ligands of the type Me3-
SiNdPPh2N(R)P(E)Ph2 (wherein, in the present case, E is S
(4), Se (5), or NP(O)(OPh)2 (6)), which have incurred some
recent interest.17 We have also been able to form the moderately
stable imines HNdPPh2N(R)P(E)Ph2 (7-9) by hydrolytic
desilylation of the parent silylated compounds. The reactions
of 2, 4, or 5 with CpTiCl3 gave nitrogen-bound titanium(IV)
derivatives (10-12) through the elimination of Me3SiCl. Finally
we demonstrate that rhodium(I), palladium(II), and platinum-
(II) chelate complexes (13-23) can be readily prepared with
this suite of ligands. Some related oxidation and coordination
chemistry of the heterofunctional mono(chalcogeno)bis(phos-
phine)amines, obtained from a similar limited oxidation of
(Ph2P)2NH, was briefly described in recent reviews;18,19 how-
ever, most of the developed coordination chemistry of this ligand
(1) (a) University of Alberta (now at Indian Institute of Technology,
Bombay, India). (b) University of Toledo. (c) University of Alberta.
(2) Balakrishna, M. S.; Cavell, R. G. Inorg. Chem. 1994, 33, 3079-3084.
(3) Katti, K. V.; Batchelor, R. J.; Einstein, F. W. B.; Cavell, R. G. Inorg.
Chem. 1990, 29, 808-814.
(4) Katti, K. V.; Cavell, R. G. Phosphorus, Sulfur Silicon Relat. Elem.
1990, 49/50, 467-470.
(5) Katti, K. V.; Cavell, R. G. Organometallics 1991, 10, 539-541.
(6) Katti, K. V.; Santarsiero, B. D.; Pinkerton, A. A.; Cavell, R. G. Inorg.
Chem. 1993, 32, 5919-5925.
(7) Katti, K. V.; Cavell, R. G. Inorg. Chem. 1989, 28, 413-416.
(8) Katti, K. V.; Cavell, R. G. Inorg. Chem. 1989, 28, 413-416.
(9) Katti, K. V.; Cavell, R. G. Organometallics 1989, 8, 2147-2153.
(10) Li, J.; McDonald, R.; Cavell, R. G. Organometallics 1996, 15, 1033-
1041.
(11) Reed, R. W.; Santarsiero, B.; Cavell, R. G. Inorg. Chem. 1996, 35,
4292-4300.
(12) Balakrishna, M. S.; Klein, R.; Uhlenbrock, S.; Pinkerton, A. A.; Cavell,
R. G. Inorg. Chem. 1993, 32, 5676-5681.
(13) Balakrishna, M. S.; Hiltman, F.; Uhlenbrock, S.; Pinkerton, A. A.;
Cavell, R. G. Unpublished.
(17) (a) Slawin, A. M. Z.; Smith, M. B. New J. Chem. 1999, 23, 777-
783. (b) Slawin, A. M. Z.; Smith, M. B.; Woollins, J. D. Polyhedron
1998, 17, 4465-4473.
(18) Ly, T. Q.; Woollins, J. D. Coord. Chem. ReV. 1998, 176, 451-481.
(19) Bhattacharyya, P.; Woollins, J. D. Polyhedron 1995, 14, 3367-3388.
(14) Katti, K. V.; Cavell, R. G. Inorg. Chem. 1989, 28, 3033-3036.
(15) Katti, K. V.; Cavell, R. G. Comments Inorg. Chem. 1990, 10, 53-73.
(16) Katti, K. V.; Cavell, R. G. Organometallics 1988, 7, 2236-2238.
10.1021/ic000878r CCC: $20.00 © 2001 American Chemical Society
Published on Web 03/06/2001

Iminophosphorano(amino)phosphines
Inorganic Chemistry, Vol. 40, No. 8, 2001 1803
Table 1. 31P NMRa Spectroscopic Data for Iminophosphorano(amino)phosphines and Their Derivatives
compound
no.
δ PIII/P(E)V, ppm
46.2 (d)
46.2 (d)
46.2 (d)
67.5 (d)
64.8 (d)
21.4(dd) (Pb), -10.8(d)(Pc)
41.3 (d)
30.7 (d)
1.5 (dd) (Pb), -10.8 (d) (Pc)
48.9 (d)
68.5 (d)
66.2 (d)
δ PV, ppm
1JPP, Hz
JPSi(Se), Hz
Ph2PN(Et)Ph2PdNSiMe3
Ph2PN(Pr)Ph2PdNSiMe3
Ph2PN(Bu)Ph2PdNSiMe3
Ph2(S)PN(Pr)Ph2PdNSiMe3
Ph2(Se)PN(Pr)Ph2PdNSiMe3
(PhO)2(O)PcNdPbPh2N(Pr)Ph2PadNSiMe3
Ph2(S)PN(Pr)Ph2PdNH
1
2
3
4
5
6
7
8
9
9.2 (d)
9.3 (d)
9.3 (d)
94.7
94.3
94.4
2.4
27.8b
28.1b
28.1b
9.6 (d)
10.7 (d)
9.6 (d)(Pa)
21.5 (d)
23.4 (d)
20.3 (d)(Pa)
55.4 (d)
47.3 (d)
47.4 (d)
7.6
761c
46.5 (JP P ), 9.9 (JP Pb)
b c a
Ph2(Se)PN(Pr)Ph2PdNH
1.1
31.4 (JP P ), 1.3 (JP P )
a b
687c
(PhO)2(O)PcNdPbPh2N(Pr)Ph2PadNH
Ph2PN(Pr)Ph2PdNTi(Cp)Cl2
Ph2(S)PN(Pr)Ph2PdNTi(Cp)Cl2
Ph2(Se)PN(Pr)Ph2PdNTi(Cp)Cl2
b
c
10
11
12
102.4
7.9
5.7
792c
b 2
c 1
a All spectra in CD2Cl2, ppm vs 85% H3PO4; d ) doublet; dd ) doublet of doublets; Et ) ethyl, Pr ) n-propyl, Bu ) n-butyl.
J
.
J
PSe.
PSi
Table 2. Crystal Data for Me3SiNdPPh2N(nPr)PPh2 (2)
system is derived from the deprotonated form of the symmetric
bis(chalcogenophosphine)amine or bis(iminophosphoran)amine
formula
a, Å
b, Å
C30H36N2P2Si
10.235(1)
16.802(2)
17.075(2)
101.05(1)
2882.9(5)
4
mol wt
514.67
(Ph2P(E))2NH (E ) O, S, Se, NR) ligands.19,20
space group
temp, °C
P21/c (No. 14)
-52
0.710 73
1.19
2.1
0.044
c, Å
λ (Mo KR),a Å
Results and Discussion
â, deg
V, Å3
Z
F
calcd, g cm-3
µ (Mo KR), cm-1
The stoichiometric reaction of the bis(diphenylphosphino)-
amines Ph2PN(R)PPh2 (R ) Et, nPr, or nBu) with trimethylsilyl
azide in the absence of solvents at 130-135 °C gave the
respective trimethylsilyliminophosphoranaminophosphines Me3-
Rb
Rw
c
0.054
a Graphite monochromator. b R ) ∑||Fo| - |Fc||/∑|Fo|. c Rw
)
{∑w(|Fo| - |Fc|)2/∑w|Fo| }1/2
.
2
n
n
SiNdPPh2N(R)PPh2 (1, R ) Et; 2, R ) Pr; 3, R ) Bu) as
crystalline products with yields up to 70-85% (eq 1). The
Clearly, the relative reactivity of the bis(diphenylphosphino)-
amines toward trimethylsilyl azide increases with the apparent
basicity at the bridging amine nitrogen, increasing along the
series N(aryl) < N(Me) < N(Et) < N(Pr) < N(Bu). These
substituents control the basicity at the phosphorus center, the
point of attack of the azide. The N-nPr derivative is therefore
ideally suited for preparation of a monooxidized phosphine
imine-phosphophine amine with trimethylsilyl azide through
an ideal combination of reactivity and melting temperature of
the parent bis(phosphino)amine.
N-ethyl derivative was particularly slow to crystallize and gave
the poorest yield; only 60-70% of the starting material was
converted to 1. The desired product in this case can be separated
from starting material by slow recrystallization from acetonitrile
at room temperature. Reaction of Ph2PN(Et)PPh2 with an excess
of trimethylsilyl azide results in more complex reaction path-
ways to give a mixture of products that could not be character-
ized. In contrast, the N-propyl and N-butyl derivatives reacted
smoothly with the azide to give pure products 2 and 3 in good
yield. A previous study of this kind of system suggested that
structures of type (1-3) were very unstable toward polymeri-
zation;21 however, that does not appear to be the case in our
present system. The new iminophosphoranophosphines 1-3 are
moderately air-stable crystalline solids that are soluble in
dichloromethane, toluene, tetrahydrofuran, and warm acetoni-
trile.
It is interesting that the analogous N-methyl and N-phenyl-
aminobis(phosphines) did not react with trimethylsilyl azide
even at their melting point temperatures. Reaction occurs at more
elevated temperatures, but the result under these conditions was
a complex mixture of several products that could not be
characterized. This reluctant reactivity contrasts with the earlier
suggestion21 that facile polymerization was to be expected for
these P-N-PdN systems, but we see that the reactivity of this
system is very greatly influenced by the substituent on the amine
N center. Presumably also the substituents on P and the imine
nitrogen will exert similar differentiation, but we have not
systematically explored this latter aspect of the chemistry.
We note that all of these N-aryl and N-alkyl bis(phosphino)-
amines reacted cleanly with other azides such as (PhO)2P(O)-
N3, p-CN-C6F4N3, and p-CH3-C6H4N3 to give monooxidized
products.2,13
The new iminophosphoranophosphines (1-3) were character-
ized by mass spectrometry, elemental analyses, NMR spectro-
scopic data, and, in the case of 2, a single-crystal X-ray structural
determination. The spectroscopic data are given in Table 1 and
in the Experimental Section. The 31P NMR spectra of com-
2
pounds 1-3 show the expected doublet of doublets with JPP
values of 94.7 (1), 94.3 (2), and 94.4 (3) Hz. The PIII signals
are found at 46.2 ppm (1-3), and the PV signals are at
considerably higher field, 9.2 (1) and 9.3 (2 and 3) ppm. The
PV signals of these silylated compounds also show satellites due
2
to JPSi couplings. The 29Si (INEPT)22 NMR spectra of 1-3
show doublets at -14.1 (1) and -14.0 (2 and 3) ppm due to
coupling with the PV center across two bonds. The 2JPSi values
are 27.8 (1) and 28.1 (2 and 3) Hz.
The structure of Ph2PN(nPr)Ph2PdNSiMe3, 2 (Table 2), is
shown with the atom numbering scheme in Figure 1.23 Selected
bond lengths and bond angles are listed in Table 3.
Compound 2 is only the second example13 of a structurally
characterized nitrogen-bridged iminophosphoranophosphine. The
structure consists of a chain of alternating phosphorus and
(22) Blinka, T. A.; Helmer, B. J.; West, R. AdV. Organomet. Chem. 1984,
23, 193-218.
(23) Johnson, C. K. ORTEP; Report ORNL No. 5138; Oak Ridge National
Laboratory: Oak Ridge, TN, 1976.
(20) Witt, M.; Roesky, H. W. Chem. ReV. 1994, 94, 1163-1181.
(21) Scherer, O. J.; Schnabl, G.; Lenhard, T. Z. Anorg. Allg. Chem. 1979,
449, 167-173.

1804 Inorganic Chemistry, Vol. 40, No. 8, 2001
Balakrishna et al.
Scheme 1
Figure 1. Perspective ORTEP23 view of 2 showing the atom numbering
scheme. Hydrogen atoms are omitted for clarity, and the remaining
atoms are shown as 20% ellipsoids.
Table 3. Selected Bond Distances (Å) and Bond Angles (deg) for
Me3SiNdPPh2N(nPr)PPh2 (2)a
Bond Distances (Å)
P(1)-N(1)
P(1)-N(2)
P(1)-C(1)
P(1)-C(7)
P(2)-N(2)
P(2)-C(13)
1.521(3)
1.694(2)
1.821(3)
1.815(3)
1.713(2)
1.835(3)
P(2)-C(19)
1.838(3)
1.669(3)
1.870(3)
1.862(3)
1.854(4)
1.481(4)
observed in PV-N-PIII systems.13,28 The P(1)-N(1) bond length
of 1.521(3) Å is slightly shorter than the typical phospinimide
but is comparable to that observed in Ph2PCH2Ph2PdNSiMe3
(1.529(3) Å).27
Si-N(1)
Si-C(25)
Si-C(26)
Si-C(27)
N(2)-C(28)
Derivatives of 2. Oxidation with S, Se, or Azide. Reaction
of Ph2PN(nPr)Ph2PdNSiMe3 (2) with elemental sulfur or
selenium in toluene under refluxing conditions afforded the
thioyl- (or selenoyl-) phosphino(amino)iminophosphoranes (4
and 5), respectively, in good yield (Scheme 1). Reaction of 2
with phosphoryl azide, N3P(O)(OPh)2, in CH2Cl2 at -40 °C
gave the bis(iminophosphorano)amine, Me3SiNdPPh2N(nPr)-
Ph2PdNP(O)(OPh)2 (6), wherein two different imine function-
alities are developed, in 78% yield. Compounds 4-6 are
monomeric crystalline solids, and relevant data are given in
Table 1.
Bond Angles (deg)
N(1)-P(1)-N(2)
N(1)-P(1)-C(1)
N(1)-P(1)-C(7)
N(2)-P(1)-C(1)
N(2)-P(1)-C(7)
C(1)-P(1)-C(7)
N(2)-P(2)-C(13)
N(2)-P(2)-C(19)
P(1)-N(2)-P(2)
P(1)-N(1)-Si
110.7(1)
111.7(1)
116.1(1)
106.4(1)
104.6(1)
106.6(1)
103.1(1)
105.0(1)
118.2(1)
154.3(2)
101.8(1)
P(1)-N(2)-C(28)
P(2)-N(2)-C(28)
P(1)-C(1)-C(2)
P(1)-C(1)-C(6)
P(1)-C(7)-C(8)
P(2)-C(7)-C(12)
P(2)-C(13)-C(14)
P(2)-C(13)-C(18)
P(2)-C(19)-C(20)
P(2)-C(19)-C(24)
118.0(2)
123.4(2)
117.3(2)
123.6(2)
121.6(2)
119.4(2)
124.8(2)
116.7(2)
117.2(2)
124.0(2)
C(13)-P(2)-C(19)
The 31P NMR spectra of the thioyl- (4) and selenoyl- (5)
derivatives show the expected doublet of doublets with small
2JPP coupling constants because both phosphorus centers are
pentavalent. Derivatives 4 and 5 show very small coupling
constants of 2.4 (4) and 7.6 (5) Hz. The chalcogenyl PV signals
are found at 67.5 (4) and 64.8 (5) ppm, and the iminophospho-
rane P(V) signals appear essentially unchanged, 9.6 (4) and 10.7
(5) ppm, relative to the starting material, 9.3 ppm (2). The
selenoyl derivative (5) also show 1JPSe satellite coupling of 761
Hz, which clearly identifies the P(V) signal arising from the
PdSe center. The mixed bis(iminophosphorane) (6) shows three
sets of signals in the 31P NMR spectrum due to the presence of
three different phosphorus(V) centers. The trimethylsilylimine
P(V) center shows a sharp doublet at 9.6 ppm, which is coupled
a Numbers in parentheses are the standard deviations in the least
significant figure.
nitrogen atoms with notably a trigonal planar geometry around
the bridging nitrogen. The sum of the bond angles at this
bridging nitrogen is 359.6°. The P(1)-N(2)-P(2) bond angle
is 118.2(1)°, within the range of typical P-N-P bond angles
(110-123°) observed in symmetric bis(phosphino)amines24-26
(wherein the trigonal planar geometry around the bridging
nitrogen is retained), and is also comparable with that in the
iminophosphoranophosphine, p-CN-C6F4NdPh2PN(Me)PPh2
(119.44(8)°).13 The bond angle at the imine nitrogen P(1)-
N(1)-Si of 154.3(2)° is slightly larger than that observed in
the analogous P-CH2-P backbone derivative27 Ph2PCH2Ph2Pd
NSiMe3 (150.2(2)°). The P(1)-N(2) bond (1.694(2) Å), which
is formally a bond from an amine nitrogen to a pentavalent
phosphorus, is shorter than the P(2)-N(2) bond (1.713(2) Å),
formally a bond to trivalent phosphorus. This difference is
expected because of the multiple bond character contributed to
the PV-N bond from the greater delocalization of the bridging
nitrogen lone pair toward the pentavalent phosphorus compared
to the trivalent phosphorus center. Similar trends are generally
to the central P(V) center across two bonds (2JP P ) 9.9 Hz).
V
V
The 31P signal due to the latter imino phosphoryl P(V) center
is also a sharp doublet at -10.8 ppm with a r 2JP P value (46.5
Hz) much larger than those shown in the chalcogen derivatives.
The central P(V) signal is therefore a doublet of doublets as
V
V
the result of coupling to both of the other phosphorus centers
(2JPVPV) (9.9 Hz) and J
(46.5 Hz)) in the molecule.
2
PVNPVO
N
N
Conversion of Oxidized Silyl Imides (4-6) to Imides (7-
9). In contrast to the heterodifunctional phosphoraniminophos-
phines (1-3), the mixed derivatives (4-6) were found to be
very moisture-sensitive. Desilylation occurred readily via hy-
drolysis with (wet) undistilled acetonitrile or toluene solvents
to give the corresponding phosphinimines Ph2P(E)N(nPr)Ph2Pd
(24) Chen, H. J.; Barendt, J. F.; Haltiwanger, R. C.; Hill, T. G.; Norman,
A. D. Phosphorus Sulfur Relat. Elem. 1986, 26, 155-162.
(25) Keat, R.; Manojlovic-Muir, L.; Muir, K. W.; Rycroft, D. S. J. Chem.
Soc., Dalton Trans. 1981, 2192-2198.
(26) Tarassoli, A.; Haltiwanger, R. C.; Norman, A. D. Inorg. Chem. 1982,
21, 2684-2690.
(27) Schmidbaur, H.; Bowmaker, G. A.; Kumberger, O.; Mu¨ller, G.;
Wolfsberger, W. Z. Naturforsch., B 1990, 45b, 476-482.
(28) Ghouse, K. M.; Keat, R.; Mills, H. H.; Roberts, J. M.; Cameron, T.
S.; Howlett, K. D.; Prout, C. K. Phosphorus 1972, 2, 47-48.

Iminophosphorano(amino)phosphines
Inorganic Chemistry, Vol. 40, No. 8, 2001 1805
NH (7, E ) S; 8, E ) Se; 9, E ) NP(O)(OPh)2). These imines
can be isolated as moderately air-stable crystalline solids that
are readily soluble in dichloromethane, acetonitrile, and toluene.
Scheme 2
1
The H NMR spectra of 7-9 clearly indicate that the trimeth-
ylsilyl groups have been removed. The mass spectrometric and
C, H, and N elemental analysis data are also consistent with a
silicon-free product. Further evidence for desilylation also comes
from 31P NMR spectroscopy. The 31P NMR data are given in
Table 1. The 31P NMR spectrum of the desilylated thioyl
derivative (7) exhibits two singlets at 41.3 and 21.5 ppm
assigned to thioylphosphorus(V) and iminephosphorus(V) cen-
ters, respectively; however, no 2JPP coupling was observed. The
phosphinimine center also shifted to higher field (21.5 ppm), a
difference of ca. 12 ppm as a result of desilylation. Similarly,
desilylation shifts the thioyl phosphorus(V) center to ca. 42 ppm,
a difference of -26.2 ppm compared to silyl derivative 4. A
similar difference is observed in the analogous desilylated
selenoyl derivative 8 relative to 5. The 1JPSe coupling in 8 (687
2
Hz) is also decreased by 74 Hz relative to 5, and the JPP
values of the parent silylated compounds. The signals are found
coupling in 8 is a small but observable value of 1.13 Hz. The
31P NMR spectrum of the desilylated bis(imine) 9 exhibits three
sets of signals that are, as expected, similar to the parent
compound 6 with a considerable decrease in the magnitude of
2JP-N-P (from 9.9 to 1.3 Hz) and 2JPdN-P(O) (from 46.5 to 31.4
Hz) as a result of desilylation. In addition two of the P(V) centers
are shifted substantially to higher field; the phosphoryl phos-
phorus resonance is unchanged in keeping with its remote
location from the desilylation site.
Compounds 2, 4, and 5 readily react with CpTiCl3 in
dichloromethane at room temperature with the elimination of
Me3SiCl to provide the Ti(IV)-metalated phosphinimines (10-
12) (eq 2). The oxidized compounds 4 and 5 react more quickly
at 47.3 (11) and 47.4 (12) ppm with the expected doublet of
2
doublets having JPP values of 7.9 (11) and 5.7 (12) Hz. The
chalcogenyl phosphorus(V) signals, however, are found at 68.5
(11) and 66.2 (12) ppm, a low field shift of only about 1.0 ppm
relative to the free ligand. Although the electronic perturbation
arising from the conversion of the imine from a silyl imine to
a titanated imine is substantial, as indicated by the change in
the NMR chemical shift of the PV center, these effects are not
effectively transmitted to the more remote phosphorus center,
which is consistent with there being little interaction between
the Ti and the remote phosphorus center. This also signifies
that electronic effects are not being transmitted through the
backbone.
Rh(I), Pd(II), and Pt(II) Complexes. The heterodifunctional
(trimethylsilyl)(iminophosphoran)aminophosphines, Me3SiNd
n
n
PPh2N(R)-PPh2 (1, R ) Et; 2, R ) Pr; 3, R ) Bu) react
smoothly with [Rh(CO)2Cl]2 in acetonitrile at 25 °C to give
the five-membered metallacycles 13-15 in good yield as
crystalline solids (Scheme 2). NMR data are given in Table 4,
and other data are included in the Experimental Section. The
infrared spectra of complexes 13-15 show νCO absorptions close
to 1977 cm-1, in all cases indicating the mutual cis disposition
of CO and phosphorus(III) centers.2,12 The 31P{1H} NMR spectra
of complexes 13-15 show doublet of doublets for the PIII
centers with a 1JRhP value of about 169 Hz. Thus, the PIII signal
is clearly identified. The PV centers also appear as a doublet of
doublets in the case of 13 (because of a small 2JRhP ) 1.5 Hz)
and simple doublets in the case of 14 and 15 where Rh-PV
coupling is not observed.
than the phosphine Ph2PN(nPr)Ph2PdNSiMe3, 2, indicating that
the oxidation of the free phosphine reduces the delocalization
of the lone pair into the backbone structure and weakens the
N-Si bond and/or increases the basicity at the silylimine center.
This is consistent with the observation that the oxidized
compounds 4 and 5 are more sensitive to moisture than 2. These
compounds, 10-12, are thus very good synthons for formation
of bimetallic complexes with a variety of transition metal
derivatives. In the present cases we do not expect the TiIV center,
being a very hard center with little affinity for soft donors, to
chelate with the phosphine or the chalcogens, and all indications
are that this is so.
Reactions of 1-3 with Cl2M(cod) (M ) Pd or Pt) in CH2Cl2
at 25 °C similarly gives the expected five-membered chelates
16-21 as shown in Scheme 2. The 31P{1H} NMR spectra of
complexes 16-21 again exhibit two doublets due to the PIII
and PV centers, respectively. The 2JPP couplings are in the range
34.8-37.5 Hz. The platinum complexes 19, 20, and 21 exhibit
The 31P NMR spectrum of 10 exhibits two doublets at 48.9
and 55.4 ppm, which are assigned to the phosphorus(III) and
phosphorus(V) centers, respectively, with a 2JPP value of 102.4
Hz. In this and the other titanated derivatives the phosphorus-
(V) center signal shows considerable deshielding upon meta-
lation of the imine with titanium, whereas the chemical shift
arising from the phosphorus(III) or the PV chalcogen centers is
essentially unaffected by this metalation. Thus, for 10 the
chemical shift difference of the PIII center is only 2.7 ppm vs
the free ligand. The 31P NMR spectra of 11 and 12 are quite
similar to that of 10, showing again a large low-field (deshield-
ing) shift at the imine phosphorus, about 37 ppm relative to the
1
very large JPtP couplings of 3900, 3895.4, and 3894 Hz,
respectively, clearly indicative of PIII coordination to Pt and
2
identifying the PIII center. The corresponding JPtP couplings
are 114.7, 92, and 114 Hz, respectively.
Reactions of 2 with K2PdCl4 or K2PtCl4 in a mixture of water
and acetonitrile under reflux conditions give the desilylated
imine complexes 22 and 23 in good yield. Alternatively, the
22 or 23 can be obtained by refluxing 17 or 20 in undistilled
acetonitrile for 6 h. In both cases hydrolysis (forming (Me3-
Si)2O) occurs with the formation of stable imine complexes of

1806 Inorganic Chemistry, Vol. 40, No. 8, 2001
Balakrishna et al.
Table 4. 31P NMRa Spectroscopic Data for Complexes 13-23a
compound
no.
δ PIII, ppm
δ PV, ppm
2JPP, Hz
1JMP, Hz
2JMP, Hz
[(CO)Rh(Cl){PPh2N(Et)Ph2P)NSiMe3}-κP,κNimine
[(CO)Rh(Cl){PPh2N(Pr)Ph2P)NSiMe3}-κP,κNimine
]
]
13
14
15
16
17
18
19
20
21
22
23
91.7 (dd)
92.2 (dd)
92.4 (dd)
69.7 (d)
70.3 (d)
70.0 (d)
41.8 (d)
42.3 (d)
42.5 (d)
90.2 (d)
61.1 (d)
37.1 (dd)
36.4 (d)
36.6 (d)
44.1 (d)
43.5 (d)
44.5 (d)
45.8 (d)
45.1 (d)
45.2 (d)
67.3 (d)
66.1 (d)
47.0
47.0
47.1
37.5
37.6
36.9
34.8
34.7
34.8
47.1
38.0
169
169
169
1.5
[(CO)Rh(Cl){PPh2N(Bu)Ph2P)NSiMe3}-κP,κNimine
]
[Cl2Pd{PPh2N(Et)Ph2P)NSiMe3}-κP,κNimine
[Cl2Pd{PPh2N(Pr)Ph2P)NSiMe3}-κP,κNimine
]
]
[Cl2Pd{PPh2N(Bu)Ph2P)NSiMe3}-κP,κNimine
]
[Cl2Pt{PPh2N(Et)Ph2P)NSiMe3}-κP,κNimine
[Cl2Pt{PPh2N(Pr)Ph2P)NSiMe3}-κP,κNimine
]
]
3900
3895
3894
115
114
114
[Cl2Pt{PPh2N(Bu)Ph2P)NSiMe3}-κP,κNimine
]
[Cl2Pd{PPh2N(Pr)Ph2P)NH}-κP,κNimine
[Cl2Pt{PPh2N(Et)Ph2P)NH}-κP,κNimine
]
]
4092
92
a All spectra in CDCl2 or CD2Cl2; ppm vs 85% H3PO4; d ) doublet; dd ) doublet of doublets.
procedures or with small modifications thereof. N3SiMe3 and N3P(O)-
(OPh)2 were purchased from Aldrich.
the metals. This behavior parallels that observed for the reaction
of Ph2PCH2PPh2dNSiMe3 with these same metal salts under
similar conditions.3 The major difference is that the methylene-
bridged system seems to be more reactive. The presence of N-H
bonds in complexes 22 and 23 is clearly indicated by infrared
absorptions for νNH at 3336 and 3340 cm-1, respectively. Further
evidence is provided by the substantive changes in the 31P{1H}
NMR spectra of the complexes: the palladium complex 22
appears as a doublet of doublets arising from PIII (90.2 ppm)
and PV (67.3 ppm) centers. Both centers are considerably
deshielded relative to the (trimethylsilyl)imine analogue 23. The
low-field shifts of 44 and 58 ppm for PIII and PV centers,
respectively, are parallel to similar large shifts in the free ligands
as the result of desilylation.
1H, 31P, and 29Si NMR spectra were obtained on a Bruker WH 400
instrument (operating at 400.13, 161.97, and 79.50 MHz, respectively)
using SiMe4, 85% H3PO4, and SiMe4, respectively, as the external
standards. An INEPT22 sequence was employed to enhance signals in
the 29Si NMR spectra. CD2Cl2 was used both as solvent and as an
internal lock. Positive shifts lie downfield of the standard in all cases.
Infrared spectra were recorded on a Nicolet 20SX FTIR spectrometer
in CH2Cl2 solution. Mass spectra were recorded on a Kratos MS9
instrument. Microanalysis were performed by the Microanalytical
Laboratory in the Department of Chemistry at the University of Alberta.
Melting points are uncorrected.
Synthesis of Ph2PN(R)Ph2PdNSiMe3 (1, R ) Et; 2, R ) nPr; 3,
n
R ) Bu). A mixture of Ph2PN(R)PPh2 (10 mmol) and Me3SiN3 (11
mmol) placed in a 100 mL round-bottomed flask fitted with a condenser
was heated with stirring in an oil bath maintained at 125-130 °C for
8 h. The resultant clear melt was subjected to vacuum to remove excess
azide and any other volatile material, then cooled and dissolved in CH3-
CN (25 mL). The solution was allowed to stand overnight at room
temperature whereupon a colorless crystalline solid precipitated in good
yield.
Summary
A stable multifunctional NdPVN-PIII system can be readily
obtained by oxidation of one phosphorus of a bis(phosphino)-
amine with azidotrimethylsilane. The propylamino derivative
has been structurally characterized and shows a planar central
nitrogen. In contrast to a previous literature suggestion that such
PdN-P-N systems were unstable toward polymerization, we
find these materials to be quite stable. A variety of chelate
complexes of Rh, Pd, and Pt have been prepared from the
iminophosphoranaminophosphine. The silylated imino (amino)
phosphines readily yield metalated iminophosphoranamino-
phosphines as demonstrated by synthesis of the TiIV derivative,
the first example of a metalated derivative of this particular
system. The iminophosphoranaminophosphines readily undergo
further oxidation with chalcogens and azides to give the doubly
oxidized derivatives that have different functionalities on the
phosphorus, thus creating asymmetric ligands of the form
(R′)NdPPh2N(R)P(E)Ph2. In this way asymmetric bis(imines)
as well as the hard-soft iminothio or iminoselenoyl ligands,
all of which have great potential use as chelate ligands, can be
prepared. On hydrolysis, those silylated imines in which the
other phosphorus center was oxidized afforded the free imines
as unexpectedly stable materials. In all cases the imine (N-H)
ligand could be further stabilized by complexation, for example,
to Pt or Pd centers.
1. Yield: 73%. Mp: 118-119 °C. Anal. Calcd for C29H34N2P2Si:
C, 69.60; H, 6.80; N, 5.60. Found: C, 69.67; H, 6.79; N, 5.28. MS EI
1
(m/z): 500 (M+). H NMR (CD2Cl2): δ phenyl rings, 7.90, 7.40 (m,
20H); δ CH2, 3.58 (m, 2H); δ CH3, 0.50 (t, 3H), δ Me3Si, 0.0 (s, 9H).
2
31P{1H} NMR (CD2Cl2): δ PIII, 46.2 (d); δ PV, 9.2 (d), JPP ) 94.7
2
Hz. 29Si NMR (CD2Cl2): δ -14.1 (d, JSiP ) 27.8 Hz).
2. Yield: 86%. Mp: 122-124 °C. Anal. Calcd for C30H36N2P2Si:
C, 70.04; H, 7.00; N, 5.45. Found: C, 70.01; H, 7.07; N, 5.42. MS EI
1
(m/z): 514 (M+). H NMR (CD2Cl2): δ phenyl rings, 7.85, 7.45 (m,
20H); δ CH2, 3.30 (m, 2H), 0.85 (m, 2H); δ CH3, 0.40 (t, 3H); δ Me3-
Si, 0.00 (s, 9H). 31P{1H} NMR (CD2Cl2): δ PIII, 46.2 (d), δ PV, 9.3
2
2
(d), JPP ) 94.3 Hz. 29Si NMR (CD2Cl2): δ -14.0 (d, JSiP ) 28.1
Hz).
3. Yield: 79%. Mp: 104-106 °C. Anal. Calcd for C31H38N2P2Si:
C, 70.45; H, 7.19; N, 5.30. Found: C, 70.43; H, 7.24; N, 5.26. MS EI
1
(m/z): 528 (M+). H NMR (CD2Cl2): δ phenyl rings, 7.82, 7.40 (m,
20H); δ (CH2), 3.35 (m, 2H), 0.80 (m, 4H); δ (CH3), 0.50 (t, 3H); δ
Me3Si, 0.0 (s, 9H). 31P{1H} NMR (CD2Cl2): δ PIII, 46.2 (d); δ PV, 9.3
2
2
(d), JPP ) 94.4 Hz. 29Si NMR (CD2Cl2): δ -14.0 (d, JSiP ) 28.1
Hz).
Preparation of SdPPh2N(nPr)Ph2PdNSiMe3 (4) and SedPPh2N-
(nPr)Ph2PdNSiMe3 (5). A mixture of Ph2PN(nPr)Ph2PdNSiMe3 (0.5
g, 0.97 mmol) and sulfur (0.031 g, 0.97 mmol) in toluene (20 mL)
was heated under reflux conditions for 12 h. The solution was then
cooled to 25 °C and concentrated to 8 mL under vacuum, and 5 mL of
n-hexane was added. Keeping this solution at 0 °C gave analytically
pure crystalline product in 78% yield. The selenium analogue Sed
PPh2N(nPr)Ph2PdNSiMe3 (5) was prepared similarly and obtained as
a pinkish-white crystalline product in 76% yield.
Experimental Section
All experiments were performed under an atmosphere of dry argon
using Schlenk techniques. Solvents were dried and distilled prior to
use. Ph2PN(R)PPh2 (R ) Et, Pr, or Bu29), [Pd(cod)Cl2],30 [Pt(cod)-
n
n
32
Cl2],31 and [Rh(CO)2Cl]2 were prepared according to published
4. Mp: 109-111 °C. Anal. Calcd for C30H36N2P2SSi: C, 65.93; H,
6.59; N, 5.13. Found: C, 65.98; H, 6.73; N, 5.14. MS EI (m/z): 546
(29) Ewart, G.; Lane, A. P.; McKechnie, J.; Payne, D. S. J. Chem. Soc.
1964, 1543-1547.
(30) Drew, D.; Doyle, J. R. Inorg. Synth. 1972, 13, 52.
(31) Drew, D.; Doyle, J. R. Inorg. Synth. 1972, 13, 48.
(32) McCleverty, J. A.; Wilkinson, G. Inorg. Synth. 1966, 8, 211-214.

Iminophosphorano(amino)phosphines
Inorganic Chemistry, Vol. 40, No. 8, 2001 1807
1
(M+). H NMR (CD2Cl2): δ phenyl rings, 7.95, 7.60, 7.37 (m, 20H);
11. Mp: 172 °C (dec). Anal. Calcd for C32H32Cl2N2P2STi: C, 58.45;
H, 4.87; N, 4.26. Found: C, 58.02; H, 4.47; N, 4.13. MS EI (m/z):
567 (M+). 1H NMR (CD2Cl2): δ phenyl rings, 8.05, 7.50 (m, 20H); δ
(C5H5), 6.20 (s, 5H); δ (CH2), 3.42 (m, 2H), 1.35 (m, 2H); δ (CH3),
0.20 (t, 3H). 31P{1H} NMR (CD2Cl2): δ P(S), 68.5 (d); δ P(N), 47.3
δ CH2, 3.40 (m, 2H); 1.10 (m, 2H); δ CH3, 0.30 (t, 3H); δ Me3Si,
-0.35 (s, 9H). 31P{1H} NMR (CD2Cl2): δ P(S), 67.5 (d); δ P(NSiMe3),
2
9.6 (d), JPP ) 2.4 Hz.
5. Mp: 143 °C. Anal. Calcd for C30H36N2P2SeSi: C, 60.70; H, 6.07;
N, 4.72. Found: C, 60.82; H, 6.00; N, 4.67. MS EI (m/z): 593 (M+).
1H NMR (CD2Cl2): δ phenyl rings, 7.90, 7.60, 7.50, 7.32 (m, 20H); δ
CH2, 3.35 (m, 2H), 1.05 (m, 2H); δ CH3, 0.22 (t, 3H); δ Me3Si, -0.20
(s, 9H). 31P{1H} NMR (CD2Cl2): δ P(Se), 64.8 (d); δ P(NSiMe3), 10.7
2
(d), JPP ) 7.9 Hz.
12. Mp: 148 °C (melts with dec). Anal. Calcd for C32H32Cl2N2P2-
SeTi: C, 54.55; H, 4.54; N, 3.97. Found: C, 53.98; H, 4.46; N, 3.88.
1H NMR (CD2Cl2): δ phenyl rings, 8.0, 7.50 (m, 20H); δ (C5H5), 6.60
2
21
(d), JPP ) 7.6 Hz,
J
) 761 Hz.
(s, 5H); δ (CH2), 3.40 (m, 2H), 1.35 (m, 2H); δ (CH3), 0.24 (t, 3H).
PSe
2
Conversion of EdPPh2N(nPr)Ph2PNSiMe3 to the Imines Ed
PPh2N(nPr)-Ph2PdNH (7, E ) S; 8, E ) Se). Recrystallization of 4
or 5 (0.18) in a mixture of undistilled (lab grade) toluene and hexane
(1:1) or in acetonitrile at 0 °C led to the formation of pure 7 or 8,
respectively, as crystalline products in quantitative yield.
31P{1H} NMR (CD2Cl2): δ P(Se), 66.2 (d); δ P(N), 47.4 (d), JPP
5.7 Hz, JPSe ) 792 Hz.
)
1
Preparation of Complexes [(CO)Rh(Cl){PPh2N(R)Ph2PdNSiMe3}-
κP,κNimine] (13-15). In general a solution of 1 (0.3 mmol) in dry CH3-
CN (10 mL) was added to a solution of [Rh(CO)2Cl]2 (0.15 mmol)
also in CH3CN (8 mL). The reaction mixture was stirred at room
temperature for 2 h and cooled to 0 °C to give yellow crystalline
products in good yield.
7. Mp: 134-136 °C. Anal. Calcd for C27H28N2P2S: C, 68.35; H,
5.91; N, 5.91. Found: C, 68.10; H, 5.78; N, 5.97. MS EI (m/z): 474
(M+). 1H NMR (CD2Cl2): δ phenyl rings, 8.00, 7.45 (m, 20H); δ CH2,
2.72 (m, 2H), 1.45 (m, 2H); δ CH3, 0.80 (t, 3H). 31P{1H} NMR (CD2-
13. Yellow crystals, yield: 86%. Mp: 220 °C (dec). Anal. Calcd
for C30H34ClN2OP2RhSi: C, 54.00; H, 5.10; N, 4.20. Found: C, 53.84;
H, 5.09; N, 4.16. IR (CH2Cl2): νCO cm-1. 1H NMR (CD2Cl2): δ phenyl
rings, 7.95, 7.70, 7.50 (m, 20H); δCH , 2.95 (m, 2H); δCH , 0.90 (t, 3H);
2
Cl2): δ P(S), 41.3 (s); δ P(NH), 21.5 (s). No JPP was observed.
8. Mp: 149-151 °C. Anal. Calcd for C27H28N2P2Se: C, 62.18; H,
5.37; N, 5.37. Found: C, 62.09; H, 5.37; N, 5.40. MS EI (m/z): 521
(M+). 1H NMR (CD2Cl2): δ phenyl rings, 8.05, 7.40 (m, 20H); δ CH2,
2.75 (m, 2H), 1.50 (m, 2H); δ CH3, 0.80 (t, 3H). 31P{1H} NMR (CD2-
Cl2): δ P(Se), 30.7 (d); δ P(NH), 23.4 (d), 2JPP ) 1.13 Hz, 1JPSe ) 687
Hz.
2
3
δ
(CH ) Si, -0.10 (s, 9H). 29Si NMR (INEPT, 79.5 MHz, in CD2Cl2, ppm
3
3
versus Me4Si): δ 7.24(d), 2JPSi ) 9.63 Hz. 31P{1H} NMR (CD2Cl2): δ
P(III), 91.7 (dd); δ P(V), 37.1 (d), 2JPP ) 47 Hz, 1JRhP ) 169 Hz, 2JPP
) 1.5 Hz.
Preparation of (PhO)2P(O)dNPPh2N(nPr)Ph2PdNSiMe3 (6) and
the Imine (9). A solution of N3P(O)(OPh)2 (0.27 g, 0.97 mmol) in
CH2Cl2 (10 mL) was added dropwise to a solution of 2 (0.5 g, 0.97
mmol), also dissolved in CH2Cl2 (10 mL), at -40 °C. After the addition
was complete the mixture was slowly warmed to room temperature
and stirred for 3 h. The solution was then concentrated to 8 mL, 3-4
mL of n-hexane was added, and the solution was cooled to 0 °C
whereupon 8 precipitated as a white crystalline solid. Recrystallization
of 8 in LR grade (undistilled) CH3CN and n-hexane (1:1) (manipulation
under air) yielded the desilylated compound (PhO)2P(O)NPPh2N(nPr)-
Ph2PdNH (9).
14. Yellow crystals, yield: 89%. Mp: 206 °C (dec). Anal. Calcd
for C31H36ClN2OP2RhSi: C, 54.66; H, 5.29; N, 4.11. Found: C, 54.66;
H, 5.15; N, 4.12. IR (CH2Cl2): νCO cm-1. 1H NMR (CD2Cl2): δ phenyl
rings, 7.97, 7.70, 7.50 (m, 20H); δ(CH ) , 2.70 (m, 2H), 1.40 (m, 2H);
2
2
δ
CH , 0.40 (t, 3H); δCH ) Si, -0.15 (s, 9H). 29Si NMR (INEPT, CD2Cl2,
3
3 3
79.5 MHz, ppm versus Me4Si): δ 5.4 (d), JPSi ) 9.2 Hz. 31P{1H}
2
2
NMR (CD2Cl2): δ P(III), 92.2 (dd); δ P(V), 36.4 (d), JPP ) 47 Hz,
1JRhP ) 169 Hz.
15. Bright yellow crystals, yield: 94%. Mp: 154 °C (dec). Anal.
Calcd for C32H38ClN2OP2RhSi: C, 55.29; H, 5.47; N, 4.02. Found: C,
1
55.18; H, 5.27; N, 4.10. IR (CH2Cl2): νCO cm-1. H NMR (CD2Cl2):
6. Yield: 78%. Mp: 114 °C. Anal. Calcd for C42H46N3O3P3Si: C,
66.23; H, 6.04; N, 5.51. Found: C, 66.3; H, 6.00; N, 5.33. MS EI
(m/z): 761 (M+). 1H NMR (CD2Cl2): δ phenyl rings, 8.20, 7.93, 7.70
(m, 30H); δ CH2, 3.70 (m, 2H), 1.25 (m, 2H); δ CH3, 0.50 (t, 3H); δ
Me3Si, 0.0 (s, 9H). 31P{1H} NMR (CD2Cl2): δ P{NP(O)(OPh)2}, 21.4
δ phenyl rings, 7.90, 7.68, 7.56 (m, 20H); δ(CH ) , 2.78 (m, 2H), 1.35
2
3
(m, 2H), 0.75 (m, 2H); δCH , 0.50 (t, 3H); δ(CH ) Si, 0.22 (s, 9H). 29Si
3
3 3
NMR (CD2Cl2, INEPT, 79.5 MHz, ppm versus Me4Si): δ 5.4 (d), 2JPSi
) 8.7 Hz. 31P{1H} NMR (CD2Cl2): δ P(III), 92.4 (dd); δ P(V), 36.6
2
1
(d), JPP ) 47.1 Hz, JRhP ) 169 Hz.
2
(dd); δ P(NSiMe3), 9.6 (d); δ P(O), -10.8 (d), JP-N-P ) 9.9 Hz,
Preparation of Complexes [Cl2M{PPh2N(R)Ph2PdNSiMe3}-
κP,κNimine] (16, M ) Pd, R ) Et; 17, M ) Pd, R ) Pr; 18, M ) Pd,
R ) Bu; 19, M ) Pt, R ) Et; 20, M ) Pt, R ) Pr; 21, M ) Pt, R
) Bu). A solution of 1-3 (0.3 mmol) in dry CH2Cl2 (10 mL) was
added dropwise to a solution of (cod)MCl2 (0.3 mmol) in CH2Cl2 (10
mL). The reaction mixture was stirred at room temperature for 3 h.
The solution was then concentrated to 8 mL, and 3 mL of n-hexane
was added. Cooling this solution to 0 °C gave analytically pure samples.
16. Yellow crystals, yield: 86%. Mp: 180 °C (dec). Anal. Calcd
for C29H34Cl2N2P2PdSi: C, 51.36; H, 5.02; N, 4.13. Found: C, 51.28;
H, 5.12; N, 3.96. 1H NMR (CD2Cl2): δ phenyl rings, 8.05, 7.80, 7.65,
7.50 (m, 20H); δCH , 2.95 (m, 2H); δCH , 0.95 (t, 3H), -0.15 (s, 9H).
2JP(O)-NdP ) 46.5 Hz.
9. Mp: 120-122 °C. Anal. Calcd for C39H38N3O3P3: C, 67.92; H,
5.51; N, 6.09. Found: C, 67.86; H, 5.53; N, 6.01. MS EI (m/z): 689
1
(M+). H NMR (CD2Cl2): δ phenyl rings, 8.25, 7.90, 7.55, 7.40 (m,
30H); δ CH2, 2.0 (m, 2H), 1.38 (m, 2H); δ CH3, 0.30 (t, 3H). 31P{1H}
NMR (CD2Cl2): δ P{NP(O)(OPh)2}, 1.5 (dd); δ P(NH), 20.3 (d); δ
2
2
P(O), -10.5 (d), JP-N-P ) 1.3 Hz, JP(O)-NdP ) 31.4 Hz.
Preparation of Ph2PN(nPr)Ph2PdNTi(Cp)Cl2 (10). A solution of
3 (0.2 g, 0.39 mmol) in CH2Cl2 (8 mL) was added dropwise to a solution
of CpTiCl3 (0.085 g, 0.39 mmol) in the same solvent (10 mL) at room
temperature, and the mixture was stirred for 3 h. The clear-yellow
solution was concentrated to 8 mL, 4 mL of n-hexane was added, and
the solution was then cooled to 0 °C to give 10 as a yellow
microcrystalline solid.
2
3
2
29Si NMR (CD2Cl2): δ 11.3 (d), JPSi ) 8.6 Hz. 31P{1H} NMR (CD2-
2
Cl2): δ P(III), 69.7(dd); δ P(V), 44.1 (d), JPP ) 37.5 Hz.
17. Yellow crystals, yield: 91%. Mp: 164 °C (dec). Anal. Calcd
Yield: 81%. Mp: 108 °C (dec). Anal. Calcd for C32H32Cl2N2P2Ti:
C, 61.45; H, 5.12; N, 4.48. Found: C, 61.20; H, 5.15; N, 4.38. MS
FAB (m/z): 625 (M+). 1H NMR (CD2Cl2): δ phenyl rings, 8.00, 7.60,
7.40 (m, 20H); δ (C5H5), 6.22 (s, 5H); δ CH2, 3.50 (m, 2H), 0.90 (m,
2H); δ CH3 0.40 (t, 3H). 31P{1H} NMR (CD2Cl2): δ PIII, 48.9 (d); δ
for C30H36Cl2N2P2PdSi: C, 52.06; H, 5.20; N, 4.05. Found: C, 51.92;
H, 5.16; N, 4.02. H NMR (CD2Cl2): δ phenyl rings, 7.75 (m, 20H);
1
δ
(CH ) , 2.70 (m, 2H), 1.45 (m, 2H); δCH , 0.40 (t, 3H); δ(CH ) Si, 0.0 (s,
2
2
3
3 3
9H). 29Si NMR (CD2Cl2): δ 9.4 (d), JPSi ) 7.7 Hz. 31P{1H} NMR
2
2
(CD2Cl2): δ P(III), 70.3(dd); δ P(V), 43.5 (d), JPP ) 37.6 Hz.
2
PV, 55.4 (d), JPP ) 102.4 Hz.
18. Yellow crystals, yield: 89%. Mp: 196 °C (dec). Anal. Calcd
for C31H38Cl2N2P2PdSi: C, 52.72; H, 5.39; N, 3.96. Found: C, 52.56;
H, 5.38; N, 3.78. 1H NMR (CD2Cl2): δ phenyl rings, 7.90, 7.75, 7.60,
Preparation of EdPPh2N(nPr)Ph2PdNTi(Cp)Cl2 (11, E ) S; 12,
E ) Se). To a solution of 4 or 5 (ca. 30 mmol) (prepared in situ as
described above) in toluene (20 mL) was added, dropwise, a solution
of CpTiCl3 (ca. 30 mmol) also in toluene (10 mL) at room temperature.
The mixture was stirred for 3 h before it was concentrated to 15 mL
under vacuum. A total of 5 mL of diethyl ether was added, and a stream
of argon was passed over the solution overnight whereupon yellow
microcrystals of 11 or 12, respectively, were obtained in 70-72% yield.
7.45 (m, 20H); δ(CH ) , 2.75 (m, 2H), 1.40 (m, 2H), 0.90 (m, 2H); δ(CH )
,
2 3
3
0.50 (t, 3H); δ(CH ) Si, -0.15 (s, 9H). 29Si NMR (CD2Cl2): δ 9.7 (d),
3
3
2JPSi ) 7.8 Hz. 31P{1H} NMR (CD2Cl2): δ P(III), 70.0 (dd); δ P(V),
2
44.5 (d), JPP ) 36.9 Hz.
19. Yellow crystals, yield: 88%. Mp: 222 °C (dec). Anal. Calcd
for C29H34Cl2N2P2PtSi: C, 45.43; H, 4.43; N, 3.65. Found: C, 45.278;

1808 Inorganic Chemistry, Vol. 40, No. 8, 2001
Balakrishna et al.
H, 4.43; N, 3.50. 1H NMR (CD2Cl2): δ phenyl rings, 8.00, 7.80, 7.65,
7.50 (m, 20H); δ CH2, 3.05 (m, 2H); δ (CH3), 1.00 (t, 3H); δ (CH3)3-
crystallized from CH3CN, was mounted on a Pyrex filament with epoxy
resin. Unit cell dimensions were determined from 25 well-centered
reflections (9° < θ < 15°). Intensity data (6193 total reflections
2
Si, 0.0 (s, 9H). 29Si NMR (CD2Cl2): δ 12.6 (d), JPSi ) 9.7 Hz. 31P-
2
2
{1H} NMR (CD2Cl2): δ P(III), 41.8 (dd); δ P(V), 45.8 (d), JPP
34.8 Hz, JPtP ) 3890 Hz, JPtP ) 115 Hz.
)
measured, 5853 unique, 3531 reflections with Fo > 3.00σ(Fo)2 were
1
2
collected with an Enraf-Nonius CAD4 diffractometer at the University
of Toledo using graphite-monochromated Mo KR (λ ) 0.710 73 Å)
radiation by the (ω-2θ) scan technique (2θmax ) 52.0°). Parameters
are given in Table 2. Direct methods were used for structure solution.33
Hydrogen atoms were calculated on idealized positions and included
in the refinement as riding atoms with fixed isotropic thermal
parameters. The final cycle of refinement minimizing the function
20. Yellow crystals, yield: 92%. Mp: 162 °C (dec). Anal. Calcd
for C30H36Cl2N2P2PtSi: C, 46.15; H, 4.61; N, 3.58. Found: C, 46.03;
1
H, 4.79; N, 3.51. H NMR (CD2Cl2): δ phenyl rings, 7.75 (m, 20H);
δ (CH2)2, 2.80 (m, 2H), 1.45 (m, 2H); δ (CH3), 0.40 (t, 3H); δ (CH3)3-
1
Si, -0.05 (s, 9H). 29Si NMR (CD2Cl2): δ 10.8 (d), JPSi ) 8.6 Hz.
2
31P{1H} NMR (CD2Cl2): δ P(III), 42.3 (dd); δ P(V), 45.1 (d), JPP
34.7 Hz, JPtP ) 3895 Hz, JPtP ) 114 Hz.
)
1
2
2
∑w(|Fo| - |Fc|)2 (weight w is defined as 4Fo /σ2(Fo)2) led to the final
21. Yellow crystals, yield: 86%. Mp: 256 °C (dec). Anal. Calcd
for C31H38Cl2N2P2PtSi‚0.5CH2Cl2: C, 45.20; H, 4.66; N, 3.34. Found:
agreement factors shown in Table 2. Scattering factors for neutral atoms
and the corrections for anomalous dispersions were taken from
International Tables for X-Ray Crystallography, 1974.34 All computa-
tions were carried out using the Mo1EN program set.35 The ORTEP23
view of 2 is illustrated in Figure 1 showing the atom numbering scheme.
Selected bond lengths and angles are given in Table 4. The full details
are provided as Supporting Information.
1
C, 45.51; H, 4.67; N, 3.26. H NMR (CD2Cl2): δ phenyl rings, 8.00,
7.78, 7.63, 7.50 (m, 20H); δ (CH2)3, 2.88 (m, 2H), 1.43 (m, 2H); δ
0.85 (m, 2H); δ CH3, -0.05 (s, 9H). 29Si NMR (CD2Cl2): δ 10.7 (d),
2JPSi ) 8.5 Hz. 31P{1H} NMR (CD2Cl2): δ P(III), 42.5 (dd); δ P(V),
2
1
2
45.2 (d), JPP ) 34.8 Hz, JPtP ) 3894 Hz, JPtP ) 114 Hz.
Preparation of Complexes [Cl2M{PPh2N(R)Ph2PdNH}-κP,κNimine
(22, M ) Pd; 23, M ) Pt). A solution of 2 (3 mmol) in CH3CN (10
mL) was added dropwise to a solution of K2MCl4 (M ) Pd or Pt) (3
mmol) in distilled water (5 mL) at room temperature. After addition
was complete, the mixture was refluxed for 3 h and then cooled to
room temperature to give a yellow crystalline product. The product
was further purified by crystallization from a mixture of CH2Cl2 and
n-hexane (1:2) at 0 °C.
]
Acknowledgment. We thank the Natural Sciences and
Engineering Research Council of Canada, Ligands, Inc., Cal-
gary, Alberta and the University of Alberta for financial support
for work at the University of Alberta. A.A.P. also thanks the
College of Arts and Sciences, University of Toledo, for support
of the diffractometer laboratory.
Supporting Information Available: X-ray crystallographic files
in CIF format for the structure determination of Me3SiNdPPh2N(nPr)-
PPh2, 2. This material is available free of charge via the Internet at
http://pubs.acs.org.
22. Orange yellow crystals, yield: 88%. Mp: 236 °C (dec). Anal.
Calcd for C27H28Cl2N2P2Pd: C, 52.30; H, 4.52; N, 4.52. Found: C,
1
52.26; H, 4.62; N, 4.34. H NMR (CD2Cl2): δ (phenyl rings), 7.95,
7.75, 7.64, 7.55 (m, 20H); δ (CH2)2, 2.75 (m, 2H), 0.75 (m, 2H); δ
CH3, 0.30 (t, 3H). 31P{1H} NMR (CD2Cl2): δ P(III), 90.2 (dd); δ P(V),
IC000878R
2
67.3 (d), JPP ) 47.1 Hz.
23. Orange yellow crystals, yield: 84%. Mp: 259 °C (dec). Anal.
Calcd for C27H28Cl2N2P2Pt: C, 53.04; H, 4.74; N, 4.42. Found: C,
52.76; H, 4.59; N, 4.37. 1H NMR (CD2Cl2): δ phenyl rings, 7.95, 7.40,
7.20 (m, 20H); δ (CH2)3, 2.85 (m, 2H), 1.40 (m, 2H), 0.95 (m, 2H); δ
CH3, 0.25 (t, 3H). 31P{1H} NMR (CD2Cl2): δ P(III), 61.1 (dd); δ P(V),
(33) Main, P.; Fiske, S. J.; Hull, S. E.; Lessinger, L.; Germain, G.; DeClerq,
J. P.; Woolfson, M. M. MULTAN 80; University of York: England,
1980.
(34) International Tables for X-Ray Crystallography; Kynoch Press:
Birmingham, 1974; Vol. IV, Table 2.3.1 (present distributor D. Reidel,
Dordrecht, The Netherlands).
(35) Fair, C. K. MolEN, An InteractiVe, Intelligent System for Crystal
Structure Analysis, User Manual; Enraf-Nonius: Delft, The Nether-
lands, 1990.
2
1
2
66.1 (d), JPP ) 38 Hz, JPtP ) 4092 Hz, JPtP ) 92 Hz.
Crystal Structure Determination of Me3SiNdPPh2N(nPr)PPh2,
2. A colorless crystal of 2 (0.36 mm × 0.17 mm × 0.25 mm),