Mercurated and palladated iminophosphoranes. Synthesis and reactivity

Article abstract of DOI:10.1021/om0303552

Reaction of the iminophosphorane Ph₃P=NC₆H₄Me-4 (1a) with Hg(OAc)₂ and LiCl gives the mercurated iminophosphorane [Hg{C₆H₃(N=PPh₃)-2-Me-5}Cl] (2). The latter reacts with NaBr to give [Hg{C₆H₃(N=PPh₃)-2-Me-5}Br] (3). 2 reacts with MeC₆H₄NCO-4 or CX₂ (X = O, S) to give [Hg{C₆H₃(N=C=NC₆H₄Me-4′)-2-Me- 5}Cl] (4) or [Hg{C₆H₃{N=C=NC₆H₃(HgCl)-1′-Me -5′}-2-Me-5}Cl] (5), respectively. Iminophosphoranes Ph₃P=NC₆H₄R-4 (1b) react with Pd(OAc)₂ to give the complexes [Pd{κ²-C,N-C₆H₄(PPh₂ =NC₆H₄R-4′)-2}(μ-OAc)]₂ (R = Me (6a), MeO (6b)), in which the palladation takes place at one of the phenyl substituents of the PPh₃ group. Complex 6b reacts with NaBr or ^tBuNC to give [Pd{κ²-C,N-C₆H₄ (PPh₂=NC₆H₄OMe-4′)-2} (μ-Br)]₂ (7) or [Pd{κ²-C,N-C₆ H₄(PPh₂=NC₆H₄OMe-4′)-2}(OAc) (CN^tBu)] (8), respectively. Complexes 6a,b react with NaClO₄ and N,N,N′,N′-tetramethylethylenediamine (tmeda), yielding [Pd{κ²-C,N-C₆H₄(PPh₂ =NC₆H₄R-4′)-2}(tmeda)] ClO₄ (R = Me (9a), MeO (9b)). The compound Ph₃P=NC₆H₄I-2 (1c) adds oxidatively to [Pd₂(dba)₃]?dba (dba = dibenzylideneacetone) in the presence of tmeda, resulting in the formation of complex [Pd{C₆H₄(N=PPh₃)-2}I(tmeda)] (10). The complex 10 reacts (i) with PPh₃ and TlOTf (TfO = CF₃SO₃) to give [Pd{C₆H₄(N=PPh₃)-2}(tmeda)(PPh₃)]TfO (11·TfO), (ii) with XyNC (Xy = C₆H₃Me-2,6) (1:3 molar ratio) to give [Pd{κ²-C,N-C(=NXy)C₆H₄(N=PPh₃) -2}I (CNXy)] (12), and (iii) with XyNC and TlOTf (1:3:1) to give [Pd{κ²-C,N-C(=NXy)C₆H₄(N=PPh₃) -2}(CNXy)₂] TfO (13). An excess of the alkyne MeO₂CC≡CCO₂Me reacts with 10 and AgClO₄ (4:1:1) to give the inserted compound [Pd{κ²-C,N-C(CO₂Me)=C(CO₂Me)C₆ H₄(N=PPh₃)-2}(tmeda)] ClO₄ (14·ClO₄). The crystal structures of 2, 6a·CH₂Cl₂, 9a, 11·TfO, and 14·ClO₄ have been determined by X-ray diffraction studies.

Full text of DOI:10.1021/om0303552

4248
Organometallics 2003, 22, 4248-4259
Mer cu r a ted a n d P a lla d a ted Im in op h osp h or a n es.
Syn th esis a n d Rea ctivity
J ose´ Vicente,*,† J ose´-Antonio Abad,*,† Rafael Clemente, and
J oaqu´ın Lo´pez-Serrano
Grupo de Qu´ımica Organometa´lica, Departamento de Qu´ımica Inorga´nica, Facultad de
Quı´mica, Universidad de Murcia, Apartado 4021, E-30071 Murcia, Spain
M. Carmen Ram´ırez de Arellano*,‡
Departamento de Quı´mica Orga´nica, Facultad de Farmacia, Universidad de Valencia,
46100 Valencia, Spain
Peter G. J ones§
Institut fu¨r Anorganische und Analytische Chemie der Technischen Universita¨t, Postfach 3329,
38023 Braunschweig, Germany
Delia Bautista|
SACE, Universidad de Murcia, Apartado 4021, E-30071 Murcia, Spain
Received May 12, 2003
Reaction of the iminophosphorane Ph3PdNC6H4Me-4 (1a ) with Hg(OAc)2 and LiCl gives
the mercurated iminophosphorane [Hg{C6H3(NdPPh3)-2-Me-5}Cl] (2). The latter reacts with
NaBr to give [Hg{C6H3(NdPPh3)-2-Me-5}Br] (3). 2 reacts with MeC6H4NCO-4 or CX2 (X )
O, S) to give [Hg{C6H3(NdCdNC6H4Me-4′)-2-Me-5}Cl] (4) or [Hg{C6H3{NdCdNC6H3(HgCl)-
1′-Me-5′}-2-Me-5}Cl] (5), respectively. Iminophosphoranes Ph3PdNC6H4R-4 (1b) react with
Pd(OAc)2 to give the complexes [Pd{κ2-C,N-C6H4(PPh2dNC6H4R-4′)-2}(µ-OAc)]2 (R ) Me (6a ),
MeO (6b)), in which the palladation takes place at one of the phenyl substituents of the
t
PPh3 group. Complex 6b reacts with NaBr or BuNC to give [Pd{κ2-C,N-C6H4(PPh2dNC6H4-
OMe-4′)-2}(µ-Br)]2 (7) or [Pd{κ2-C,N-C6H4(PPh2dNC6H4OMe-4′)-2}(OAc)(CNtBu)] (8), re-
spectively. Complexes 6a ,b react with NaClO4 and N,N,N′,N′-tetramethylethylenediamine
(tmeda), yielding [Pd{κ2-C,N-C6H4(PPh2dNC6H4R-4′)-2}(tmeda)]ClO4 (R ) Me (9a ), MeO
(9b)). The compound Ph3PdNC6H4I-2 (1c) adds oxidatively to [Pd2(dba)3]‚dba (dba )
dibenzylideneacetone) in the presence of tmeda, resulting in the formation of complex [Pd-
{C6H4(NdPPh3)-2}I(tmeda)] (10). The complex 10 reacts (i) with PPh3 and TlOTf (TfO )
CF3SO3) to give [Pd{C6H4(NdPPh3)-2}(tmeda)(PPh3)]TfO (11‚TfO), (ii) with XyNC (Xy )
C6H3Me-2,6) (1:3 molar ratio) to give [Pd{κ2-C,N-C(dNXy)C6H4(NdPPh3)-2}I(CNXy)] (12),
and (iii) with XyNC and TlOTf (1:3:1) to give [Pd{κ2-C,N-C(dNXy)C6H4(NdPPh3)-2}(CNXy)2]-
TfO (13). An excess of the alkyne MeO2CCtCCO2Me reacts with 10 and AgClO4 (4:1:1) to
give the inserted compound [Pd{κ2-C,N-C(CO2Me)dC(CO2Me)C6H4(NdPPh3)-2}(tmeda)]ClO4
(14‚ClO4). The crystal structures of 2, 6a ‚CH2Cl2, 9a , 11‚TfO, and 14‚ClO4 have been
determined by X-ray diffraction studies.
In tr od u ction
been prepared through metalation of some of the R
groups. This family consists mainly of a numerous group
of alkyl complexes containing an N,C-chelating ligand
prepared from iminophosphoranes R(Ar)2PdNR′ (R )
alkyl, Ar ) aryl, R′ ) Me3Si, aryl) after the deprotona-
tion of the R-methylene of the R group (class IIa)3,6 and
a few aryl derivatives prepared by metalation or trans-
metalation reactions (class IIb). Thus, lithiation of
Ph3PdNPh with PhLi was long ago reported to give
[LiC6H4(Ph2PdNPh)-2],7 and more recently Stalke re-
ported the lithiation of Ph3PdNSiMe3 with MeLi, af-
fording [LiC6H4(Ph2PdNSiMe3)-2],8 which in reactions
with halides of Zn, Cu(I), In(III), Fe(II), Sn(II), and Pb-
(II) or with Ph3GeCl gives the corresponding aryl
Iminophosphoranes R3PdNR′ are very important
compounds, in view of their numerous applications in
organic chemistry,1 as well as in coordination and
organometallic chemistry. N-bonded complexes are
known for many metals of the periodic table (class I in
Chart 1).2-5 In addition, organometallic complexes have
† E-mail: J .V., jvs@um.es; J .-A.A., jaab@um.es. Web: http://
www.um.es/gqo/.
‡ E-mail: mcra@uv.es.
§ E-mail: p.jones@tu-bs.de.
| E-mail: dbc@um.es.
(1) J ohnson, A. V. Ylides and Imines of Phosphorus; Wiley: New
York, 1993.
10.1021/om0303552 CCC: $25.00 © 2003 American Chemical Society
Publication on Web 09/12/2003

Mercurated and Palladated Iminophosphoranes
Organometallics, Vol. 22, No. 21, 2003 4249
NPh)-2}}(CO)5] (M ) Mn, Re),11 [Pd{κ2-C,N-(C6H3R1-
5){P(C6H4R1-4)2dNC6H4R2-n}(µ-Cl)]2 (R1 ) H, R2 ) Me
(n ) 3, 4), OMe (n ) 4); R1 ) Me, R2 ) OMe (n ) 4)),12
and [Al{κ2-C,N-C6H4{P(Ph)2dNSiMe3}-2}Ph2].13 The
main features of the organo derivatives of iminophos-
phoranes are that the metal is always attached to
substituents at phosphorus and that, in most cases, it
is coordinated to the nitrogen atom. In this paper we
study the palladation and mercuration of iminophos-
phoranes Ph3PdNAr and report the synthesis of the
first organometallics of class III, in which the metal is
bonded to the substituent at nitrogen, as well as some
palladium complexes of class IIb and the first organo-
mercurated iminophosphoranes. From the latter com-
plexes we have prepared the first aryl complexes of any
metal containing a carbodiimide group.
Ch a r t 1
complexes.9 In a few of the above-mentioned organo
complexes, the N is not coordinated (class IIc).10 Finally,
reactions of Ar3PdNR with [M(CH2Ph)(CO)5], Na2-
[PdCl4], or AlPh3 have been reported to give the C,N-
cyclometalated complexes [M{κ2-C,N-C6H4{P(Ph)2d
Exp er im en ta l Section
The IR (solid state) and NMR spectra, elemental analyses,
and melting point determinations were performed as described
earlier.14 Conductivity measurements were made in acetone,
unless otherwise stated. When needed, NMR signals were
assigned with the help of DEPT, COSY, and HETCOR
techniques. The mass spectra were recorded in a Fisons VG-
Autospec apparatus using 3-nitrobenzyl alcohol as a matrix.
“Pd(dba)2” ([Pd2(dba)3]‚dba, dba ) dibenzylideneacetone) was
prepared as described previously.15 The iminophosphoranes
Ph3PdNC6H4Me-4 (1a ) and Ph3PdNC6H4(OMe)-4 (1b) were
prepared following the Kirsanov method1 from the correspond-
ing amine and Ph3PBr2.16 2-Iodoaniline was purchased from
Aldrich. The synthesis of the compounds was carried out
without precautions against light and moisture, unless oth-
erwise stated. The products were filtered in air and dried
under a current of air. The preparative thin-layer chromato-
graphic separations were performed using silica gel 60 ACC
(70-200 µm). In the case of colorless substances fluorescent
silica gel (GF254) was added (approximately 5%).
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Syn th esis of P h 3P dNC6H4I-2 (1c). The reaction was
carried out under nitrogen using freshly distilled benzene. To
a stirred solution of triphenylphosphine (4.58 g, 17.4 mmol)
in benzene (10 mL) was added dropwise a solution of bromine
(2.78 g, 17.4 mmol) in the same solvent (10 mL) using an
addition funnel while keeping the temperature below 10 °C.
After the addition was completed, the resulting yellowish
suspension was stirred for a further 30 min, allowing it to
reach room temperature. 2-Iodoaniline (3.87 g, 17.4 mmol) and
dry triethylamine (5 mL) were then added, and the volume of
the reaction mixture was made up to 60 mL with benzene.
The mixture was refluxed under nitrogen for 4 h, the resulting
suspension was filtered through anhydrous magnesium sul-
fate, and the filtrate was evaporated to dryness. The crude
product was redissolved in warm Et2O (100 mL) and cooled to
room temperature. Colorless, well-shaped crystals were col-
lected by filtration, washed with Et2O, and air-dried. Yield:
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1
6.40 mg, 77%. Mp: 124-126 °C. H NMR (300 MHz, CDCl3):
3
4
δ 7.87-7.79 (m, 6 H, PPh3), 7.77 (dt, J H,H ) 8 Hz, J H,H ) 2.5
Hz, J H,P ) 2.5 Hz, 1 H, H3 or H6 C6H4), 7.64-7.40 (m, 9 H,
3
4
PPh3), 6.84 (td, J H,H ) 8 Hz, J H,H ) 2.5 Hz, 1 H, H4 or H5
3
4
C6H4), 6.46 (dt, J H,H ) 8 Hz, J H,H ) 2.5 Hz, J H,P ) 2.5 Hz, 1
(11) Leeson, M. A.; Nicholson, B. K.; Olsen, M. R. J . Organomet.
Chem. 1999, 579, 243.
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1752.
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Rocha, J .; Stalke, D. Organometallics 2000, 19, 3890. Wingerter, S.;
Gornitzka, H.; Bertran, G.; Stalke, D. Eur. J . Inorg. Chem. 1999, 173.
(10) Wingerter, S.; Pfeiffer, M.; Stey, T.; Bolboaca, M.; Kiefer, W.;
Chandrasekhar, V.; Stalke, D. Organometallics 2001, 20, 2730.
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Inorg. Chem. 1997, 36, 5735.
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1065. Heck, R. F. Palladium Reagents in Organic Synthesis; Academic
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4250 Organometallics, Vol. 22, No. 21, 2003
Vicente et al.
H, H3 or H6), 6.35 (td, 3J H,H ) 8 Hz, 4J H,H ) 2.5 Hz, 1H, H5 or
H4). 13C{1H} NMR (50 MHz, CDCl3): δ 151.58 (d, J CP ) 2 Hz,
C, C1 C6H4), 138.77 (d, 1J P,C ) 2 Hz, CH C6H4), 132.72 (d, 2J P,C
) 10 Hz, m-CH PPh3), 131.72 (d, J P,C ) 2.5 Hz, p-CH PPh3),
129.75 (s, quaternary C, probably one of the signals of the
doublet corresponding to i-C-PPh3, whereby the other one may
be obscured by other signals), 128.60 (d, J P,C ) 13 Hz, o-CH
PPh3), 128.16 (s, CH), 119.87 (d, J P,C ) 9.5 Hz, CH), 118.73
(d, J P,C ) 1 Hz, CH), 99.9 (d, J P,C ) 27.5 Hz, quaternary C).
31P{1H} NMR (121 MHz, CDCl3): δ 2.55 (s). Anal. Calcd for
at -78 °C. Then, a large excess of solid CO2 was added. The
mixture was stirred at room temperature for 24 h, allowing it
to reach room temperature. After this time the white precipi-
tate thus formed was filtered off, washed with CH2Cl2, and
dried in vacuo to give 5. Yield: 176 mg, 70%.
Meth od B. An excess of CS2 (160 µL, 2.64 mmol) was added
to a solution of 2 (400 mg, 0.66 mmol) in CH2Cl2 (15 mL), and
the resulting mixture was stirred at room temperature for 24
h. The white precipitate that formed was collected by filtration
and worked up as above. Yield: 114 mg, 50%. Mp: 133-135
°C. IR (Nujol, cm-1): ν 2132, 2100, 2026 (NdCdN), 320 (Hg-
Cl). NMR: not sufficiently soluble. EI MS: m/z 692 (M+ 1.2%),
420 (M+ - HgCl2, 44%) 221 (M+ - 2HgCl, 52%). Anal. Calcd
for C15H12N2Cl2Hg2: C, 26,02; H, 1.75; N, 4.05. Found: C, 26,-
08; H, 1.83; N, 3.95.
C
24H19INP: C, 60.14; H, 4.00; N, 2.92. Found: C, 60.19; H,
3.84; N, 2.96.
Syn th esis of [Hg{C6H3(NdP P h 3)-2-Me-5}Cl] (2). Hg-
(OAc)2 (4.00 gr, 12.55 mmol) and 1a (4.61 gr, 12.55 mmol) were
mixed in THF (100 mL) under nitrogen and the resulting
mixture refluxed for 9 h and then cooled to room temperature,
and a 100% excess of LiCl was added. The suspension was
stirred for a further 12 h at room temperature and filtered.
The resulting solution was evaporated to dryness. The residue
was extracted with CH2Cl2 (5 cm3) and filtered through Celite.
Addition of Et2O (10 mL) precipitated complex 2 as an ivory-
colored solid. Yield: 5.86 gr, 74%. Mp: 186 °C. IR (Nujol, cm-1):
ν 1420 (PdN), 330 (Hg-Cl). 1H NMR (200 MHz, CDCl3): δ
7.66-7.77 (m, 6 H, PPh3), 7.41-7.59 (m, 9 H, PPh3), 6.91 (s, 1
Syn th esis of [P d {K2-C,N-C6H4(P P h 2dNC6H4Me-4′)-2}(µ-
OAc)]2 (6a ). Pd(OAc)2 (610 mg, 2.72 mmol) and 1a (1 g, 2.72
mmol) were mixed in THF (40 mL) under nitrogen. The deep
red solution was stirred for 24 h. The solvent was removed
under reduced pressure, CH2Cl2 was added to the residue, and
the mixture was filtered through Celite. The solution was
concentrated to ca. 5 mL and Et2O (50 mL) added, precipitating
6a as a yellow solid. Yield: 1.11 g, 77%. Dec pt: 200 °C. IR
(Nujol, cm-1): ν 1584, 1556 (CdO), 1186 (PdN). 1H NMR (200
MHz, CDCl3): δ 7.52-6.67 (several m, 18H, aryl), 2.13 (d, 7J P,H
) 2 Hz, 3 H, MeCO2), 1.13 (s, 3 H, Me). 13C{1H} NMR (75 MHz,
CDCl3): δ 179.63 (CdO), 150.83 (d, 2J P,C ) 23 Hz, CPd), 143.13
3
3
H, H6), 6.65 (d, J H,H ) 7.9 Hz, 1 H, H4 or H3), 6.41 (d, J H,H
) 7.9 Hz, 1 H, H3 or H4), 2.17 (s, 3 H, Me). 13C{1H} NMR (50
2
MHz, CDCl3): δ 151.87 (C, C1), 149.2 (d, J P,C ) 4.5 Hz, C2),
4
2
2
1
136.22 (d, J P,C ) 4.7 Hz, C6), 132.47 (d, J P,C ) 9.7 Hz, o-C
(d, J P,C ) 5 Hz, C1 C6H4Me-4), 139.11 (d, J P,C ) 140 Hz, C2
4
1
2
PPh3), 131.89 (d, J P,C ) 2.8 Hz, p-C PPh3), 129.98 (d, J P,C
)
C6H4Pd), 135.54 (d, J P,C ) 15 Hz, C3 C6H4Pd), 132.21 (s, C4
3
99 Hz, i-C PPh3), 129.68 (CH, C4 or C3), 128.68 (d, J P,C ) 12
Hz, m-C PPh3), 127.47(C, C5), 119.82 (d, 3J P,C ) 8.4 Hz, C3 or
C4), 20.51 (Me). 31P{1H} NMR (121 MHz, CDCl3): δ 3.16 (s).
FAB MS: m/z, 603 (M+, 58%), 366 (M+ - HgCl, 100%), 262
(PPh3, 26%). Anal. Calcd for C25H21NClHgP: C, 49.84; H, 3.51;
N, 2.32. Found: C, 49.65; H, 3.48; N, 2.36. Single crystals of
2 were grown by slow diffusion of methanol into solutions of 2
in CH2Cl2.
C6H4Me-4), 131.65-133.10 (m, CH), 130.67 (d, J P,C ) 6 Hz,
CH), 129.93 (d, 2J P,C ) 3 Hz, CH), 129.51 (s, i-C PPh2, the other
component of the doublet may be obscured by other signals),
128.37 (d, J P,C ) 12 Hz, CH), 128.16 (d, J P,C ) 3 Hz, CH),
1
128.11 (d, J P,C ) 84 Hz, C1 i-C PPh2), 128.01 (s, p-CH PPh2),
123.85 (d, 3J P,C ) 14 Hz, C2 C6H4Me-4), 23.03 (s, MeCO2), 20.91
(s, C6H4Me-4). 31P{1H} NMR (121 MHz, CDCl3): δ 53.69 (s).
FAB MS: m/z 1062 ([M+]2, 2%), 531 (M+, 12%), 366 (M+
-
Syn th esis of [Hg{C6H3(NdP P h 3)-2-Me-5}Br ] (3). NaBr
(456 mg, 4.43 mmol) was added to a solution of 2 (445 mg,
0.74 mmol) in acetone (20 mL). The resulting suspension was
stirred for 16 h and then filtered. The filtrate was evaporated
to dryness, and CH2Cl2 (10 mL) was added to the residue. The
solution was concentrated to ca. 3 mL, and n-hexane (20 mL)
was added to give 3 as a pale brown solid. Yield: 371 mg, 78%.
Mp: 193 °C. IR (Nujol, cm-1): ν 1316 (PdN). 1H NMR (200
MHz, CDCl3): δ 7.66-7.77 (m 6 H, PPh3), 7.40-7.57 (m, 9 H,
PPh3), 6.92 (s, 1 H, H6), 6.65 (d, 3J H,H ) 8 Hz, 1 H, H4 or H3),
PdOAc, 100%). Anal. Calcd for C27H24NO2PPd: C, 60.97; H,
4.55; N, 2.63. Found: C, 60.80; H, 4.59; N, 2.65. Single crystals
of 6a ‚CH2Cl2 were grown by slow diffusion of n-hexane into
solutions of 6a in CH2Cl2.
Syn th esis of [P d {K2-C,N-C6H4(P P h 2dNC6H4OMe-4′)-2}-
(µ-OAc)]2 (6b). Pd(OAc)2 (293 mg, 1.30 mmol) and Ph3PdN-
C6H4OMe-4 (1b; 500 mg, 1.30 mmol) were mixed in THF (25
mL) under nitrogen. The deep red solution was stirred for 20
h. The solvent was removed under reduced pressure, CH2Cl2
was added to the residue, and the mixture was filtered through
Celite. The solution was concentrated to ca. 4 mL and Et2O
(50 mL) was added, precipitating 6b as a yellow solid. Yield:
587 mg, 82%. Dec pt: 242 °C. IR (Nujol, cm-1): ν 1585, 1577,
1557 (AcO), 1497, 1175 (PdN). 1H NMR (200 MHz, CDCl3): δ
3
6.42 (d, J H,H ) 8 Hz, 1 H, H3 or H4), 2.16 (s, 3 H, Me). 31P-
{1H} NMR (121 MHz, CDCl3): δ 3.11 (s). FAB MS: m/z, 647
(M+, 76%), 366 (M+ - HgBr, 54%), 262 (PPh3, 18%). Anal.
Calcd for C25H21BrHgNP: C, 46.42; H, 3.27; N, 2.17. Found:
C, 46.21; H, 3.01; N, 2.15.
3
7.52-6.71 (several m, 16H, aryl), 6.49 (d, J H,H ) 8.5 Hz, 2 H,
Syn th esis of [Hg{C6H3(NdCdNC6H4Me-4′)-2-Me-5}Cl]
(4). p-Tolyl isocyanate (200 mg, 1.34 mmol) was added to a
THF (50 mL) solution of 2 (603 mg, 1.00 mmol). The resulting
mixture was stirred for 15 h at room temperature. Then it was
evaporated to dryness. The residue was treated with ethanol,
giving a white precipitate, which was collected by filtration
and air-dried to yield white 4. Yield: 234 mg, 51%. Mp: 155
°C. IR (Nujol, cm-1): ν 2128, 2109 (NdCdN), 329 (Hg-Cl).
1H NMR (300 MHz, CDCl3): δ 7.24-7.05 (m, 7 H, arom), 2.34
(s, 3 H, Me), 2.31 (s, 3 H, Me). 13C{1H} NMR (50 MHz,
CDCl3): δ 145.63 (s, C), 140.63 (s, C), 138.05 (s, C), 136.91 (s,
CH), 135.97 (s, C), 135.91 (s, C), 134.61 (s, C), 131.08 (s, CH),
130.12 (s, CH, C11), 124.22 (s, CH, C10), 21.02 (s, 2 Me). FAB
MS: m/z, 458 (RHgCl, 65%), 221 (R, 100%). Anal. Calcd for
C6H4Me-4), 3.67 (s, 3 H, OMe), 1.37 (s, 3 H, Me). 13C{1H} NMR
(75 MHz, CDCl3): δ 179.58 (CdO), 155.53 (d, 5J P,C ) 3 Hz, C4
2
C6H4OMe-4), 150.92 (d, J P,C ) 23 Hz, C2 C6H4Pd), 138.84 (d,
1J P,C ) 140 Hz, CPd), 138.70 (d, 2J P,C ) 5 Hz, C1 C6H4OMe-4),
2
135.44 (d, J P,C ) 15 Hz, C3 C6H4Pd), 133.01-127.91 (m,
several CH), 129.9 (d, 1J P,C ) 88 Hz, i-C PPh2), 127.85 (d, 1J P,C
3
) 83 Hz, i-C PPh2), 123.8 (d, J P,C ) 14 Hz, C2 C6H4OMe-4),
112.82 (d, 4J P,C ) 3 Hz, C3 C6H4OMe-4), 55.38 (s, OMe), 22.99
(s, Me). 31P{1H} NMR (121 MHz, CDCl3): δ 55.41 (s). FAB
MS: m/z, 1036 ([M+]2 - AcO, 17%), 547 (M+, 35%), 382 (M+
-
PdOAc, 100%). Anal. Calcd for C27H24NO3PPd: C, 59.19; H,
4.42; N, 2.56. Found: C, 58.80; H, 4.33; N, 2.57.
Syn th esis of [P d {K2-C,N-C6H4(P P h 2dNC6H4OMe-4′)-2}-
(µ-Br )]2 (7). NaBr (75 mg, 0.73 mmol) was added to a THF
suspension of 6b (200 mg, 0.18), and the mixture was stirred
at reflux temperature for 6 h. The resulting orange suspension
was evaporated to dryness, the residue was treated with CH2-
Cl2, and the suspension was filtered through Celite. The
filtrate was concentrated to ca. 2 mL, and Et2O (20 mL) was
C
15H13ClHgN2: C, 39.40; H, 2.87; N, 6.13. Found: C, 39.40;
H, 2.64; N, 5.96.
Syn th esis of [Hg{C6H3{NdCdNC6H3(HgCl)-1′-Me-5′}-2-
Me-5}Cl] (5). Meth od A. A dichloromethane (40 mL) solution
of 2 (441 mg, 0.73 mmol) was cooled in an acetone/CO2 bath

Mercurated and Palladated Iminophosphoranes
Organometallics, Vol. 22, No. 21, 2003 4251
added, precipitating a solid that was collected and dried in
C6H4OMe-4), 133.70-133.38 (m, CH), 130.76 (d, J P,C ) 3 Hz,
CH), 129.65 (d, J P,C ) 18.5 Hz, CH), 129.06 (d, J P,C ) 12 Hz,
vacuo to give pale orange 7. Yield: 93 mg, 50%. Dec pt: 243
°C. IR (Nujol, cm-1): ν 1174 (PdN). 1H NMR (200 MHz,
1
CH), 128.11 (d, J P,C ) 7 Hz, CH), 126.7 (d, J P,C ) 94.5 Hz,
3
3
CDCl3): δ 7.83-6.93 (several m, 16 H, arom), 6,49 (d, J H,H
)
ipso C PPh3), 124.82 (d, J P,C ) 13.5 Hz, C2, C6 C6H4OMe-4),
8.5 Hz, 2 H), 3.65 (s, 3 H, OMe). 31P{1H} NMR (121 MHz,
CDCl3): δ 46.68 (s). FAB MS: m/z 1137 (M+2, 3%), 569 (M+,
3%), 382 (C6H4[PPh2dNC6H4(OMe)-4]-2, 100%). Anal. Calcd
for C25H21BrNOPPd: C, 52.80; H, 3.72; N, 2.46. Found: C,
52.41; H, 3.79; N, 2.58.
4
114.02 (d, J P,C ) 2.5 Hz, C3, C5 C6H4OMe-4), 63.84 (CH2),
58.75 (CH2), 55.31 (Me), 51.10 (Me, tmeda), 49.18 (Me, tmeda).
31P{1H} NMR (121 MHz, CDCl3): δ 42.42 (s). FAB MS: m/z
604 (M+, 100%), 489 (M+ - tmeda, 7%), 382 (M+ - Pd(tmeda),
29%). Anal. Calcd for C31H37ClN3O5PPd: C, 52.85; H, 5.29; N,
5.96. Found: C, 52.62; H, 5.23; N, 5.96.
Syn th esis of [P d {K2-C,N-C6H4(P P h 2dNC6H4OMe-4′)-2}-
(OAc)(CNtBu )] (8). BuNC (62 µL, 0.55 mmol) was added to
t
Syn th esis of [P d {C6H4(NdP P h 3)-2}I(tm ed a )] (10). “Pd-
(dba)2” (401 mg, 0.70 mmol) and tmeda (105 µL, 0.70 mmol)
were mixed in toluene (30 mL) under nitrogen, the mixture
was stirred for 15 min, and then 1c (500 mg, 1.04 mmol) was
added. The resulting suspension was stirred at room temper-
ature for 3 h. After this time the nitrogen atmosphere was no
longer needed. The solvent was evaporated in vacuo, the
greenish residue was treated with CH2Cl2 (20 mL), and the
suspension was filtered through Celite. The orange solution
was then evaporated to dryness and the residue triturated
with Et2O, filtered, washed with Et2O, and air-dried to give
10 as a pale orange solid. Yield: 337 mg, 70%. Dec pt: 160-
a solution of 6b (100 mg, 0.09 mmol) in THF (20 mL) under
nitrogen. The yellow solution turned pale green and was
stirred at room temperature for 24 h. After this time the
protective nitrogen atmosphere was no longer needed. The
solvent was evaporated to dryness, CH2Cl2 (15 mL) was added,
and the mixture was filtered through Celite. The filtrate was
evaporated to dryness, and n-hexane (30 mL) was added to
the residue, precipitating a grayish solid. Yield: 91 mg, 79%.
Mp: 180 °C. IR (Nujol, cm-1): ν 2194 (CtN), 1598, 1576 (OAc),
1196 (NdP). 1H NMR (200 MHz, CDCl3): δ 7.83-6.96 (several
m, 14 H, arom), 6.68 (AB system (δA ) 6.84, δB ) 6.53), 4 H,
C6H4, 2J H,H ) 8 Hz), 3.65 (s, 3 H, OMe), 1.56 (s, 9 H, tBu), 1.47
(s, 3 H, MeCO2). 13C{1H} NMR: the compound decomposes
during the experiment. 31P{1H} NMR (121 MHz, CDCl3): δ
48.48 (s). Anal. Calcd for C32H33N2O3PPd: C, 60.91; H, 5.27;
N, 4,44. Found: C, 60.80; H, 5.51; N, 4.51.
1
169 °C. IR (Nujol, cm-1): ν 1336 (PdN). H NMR (300 MHz,
CDCl3): δ 8.03-7.96 (m, 6 H, PPh3), 7.48-7.36 (m, 9 H, PPh3),
3
4
7.01 (dt, J H,H ) 7 Hz, J H,H ) 2 Hz, J P,H ) 2 Hz, 1 H, H3 or
3
H6 C6H4), 6.41-6.36 (m, 2 H, C6H4), 5.99 (b d, J H,H ) 7 Hz, 1
H, C6H4), 2.78 (s, 3 H, Me), 2.72 (s, 3 H, Me), 2.64-2.49 (m, 4
H, 2CH2), 2.46 (s, 3 H, Me), 2.38 (s, 3 H, Me). 13C{1H} NMR
(75 MHz, CDCl3): δ 138.34 (s, quaternary C), 137.95 (s,
Syn th esis of [P d {K2-C,N-C6H4(P P h 2dNC6H4Me-4′)-2}-
(tm ed a )]ClO4 (9a ). NaClO4 (21 mg, 0.17 mmol), was added
to a suspension of 6a (60 mg, 0.055 mmol) in acetone (30 mL).
An excess of tmeda (N,N,N′,N′-tetramethylethylenediamine,
26 µL, 0.17 mmol), was added to the stirring suspension and
the resulting yellow solution was stirred for a further 4h. The
solvent was evaporated, the residue treated with CH2Cl2 (10
mL) and the solution filtered through Celite. The filtrate was
concentrated to ca. 2 mL. The compound 9a precipitated as a
yellow solid after addition of Et2O (20 mL). Yield: 77 mg, 99%.
Mp: 206 °C. ΛM ) 150 Ω-1 cm2 mol-1. IR (Nujol, cm-1): ν 1189
(PdN), 1081, 621 (ClO4). 1H NMR (200 MHz, CDCl3): δ 7.71-
6.75 (several m, 18 H, arom), 2.78 (s, 6 H, 2Me tmeda), 2.58-
quaternary C), 137.26 (d, J P,C ) 5 Hz, CH), 132.80 (d, J P,C
)
9 Hz, meta CH, PPh3), 131.56 (s, quaternary C), 130.97 (s, para
CH, PPh3), 128.21 (d, J P,C ) 12 Hz, ortho CH, PPh3), 122.619
(s, CH), 118.64 (d, J P,C ) 10 Hz, CH), 116.55 (s, CH), 61.95 (s,
CH2), 58.31 (s, CH2), 50.30 (s, Me), 50.10 (s, Me), 49.61 (s, Me),
48.87 (s, Me). 31P{1H} NMR (121 MHz, CDCl3): δ -5.26 (s).
Anal. Calcd for C30H35IN3PPd: C, 51.33; H, 5.03; N, 5.99.
Found: C, 51.42; H, 5.13; N, 5.93.
Syn th esis of [P d {C6H4(NdP P h 3)-2}(tm ed a )(P P h 3)]TfO
(11‚TfO). TlOTf (60 mg, 0.17 mmol) was added to a solution
of 10 (120 mg, 0.17 mmol) in acetone (10 mL). PPh3 (52 mg,
0.2 mmol) was then added to the suspension. The reaction
mixture was stirred for a further 30 min and was filtered
through Celite. The resulting yellow solution was evaporated
to dryness and the residue triturated with Et2O (15 mL). The
solid was collected by filtration, washed with Et2O, and dried
in vacuo to yield 11‚TfO as a pale yellow solid. Yield: 160 mg,
95%. Mp: 148-150 °C. ΛM ) 144 Ω-1 cm2 mol-1. IR (Nujol,
7
2.55 (m, 4 H, 2CH2), 2.16 (d, J H,P ) 2 Hz, 3 H, Me C6H4Me),
2.08 (s, 6 H, 2Me tmeda). 13C{1H} NMR (50 MHz, CDCl3): δ
2
2
159.13 (d, J P,C ) 19 Hz, C-Pd), 143.14 (d, J P,C ) 5 Hz, C1
C6H4Me-4), 143.10 (d, 1J P,C ) 126 Hz, C2), 133.65-124.88 (m,
CH), 132.32 (d, J P,C ) 3 Hz, C4 C6H4Me-4), 126.70 (d, J P,C
5
1
)
3
94 Hz, i-C PPh3), 124.83 (d, J P,C ) 14 Hz, C2 and C6 C6H4-
Me-4), 63.88 (CH2), 58.83 (CH2), 51.18 (Me, tmeda), 49.25 (Me,
tmeda), 20.66 (Me). 31P{1H} NMR (121 MHz, CDCl3): δ 41.72
(s). FAB MS: m/z 588 (M+, 100%), 437 (M+ - tmeda, 7%), 366
(M+ - Pd(tmeda), 35%). Anal. Calcd for C31H37ClN3O4PPd: C,
54.08; H, 5.42; N, 6.10. Found: C, 53.77; H, 5.17; N, 6.52.
Single crystals of 9a were grown by slow diffusion of n-hexane
into solutions of 9a in CH2Cl2.
1
cm-1): ν 1272, 1030 (triflate). H NMR (300 MHz, CDCl3): δ
7.63-7.51 (m, 9 H, PPh3), 7.45-7.34 (m, 15 H, PPh3), 7.19-
7.12 (m, 6 H, PPh3), 7.08-7.03 (m, 1 H, H3 or H6 C6H4), 6.44
3
4
(td, J H,H ) 7.5 Hz, J H,H ) 1 Hz, 1 H, H4 or H5 C6H4), 6.31
3
4
(td, J H,H ) 7.5 Hz, J H,H ) 1 Hz, 1 H, H4 or H5 C6H4), 5.96
(dd, 3J H,H ) 7.5 Hz, 4J H,H ) 1, 1 H, H3 or H6 C6H4), 3.35-3.28
(m, 1 H, CH2), 3.08-2.99 (m, 1 H, CH2), 2.73 (s, 3 H, Me), 2.70-
2.64 (m, 1 H, CH2), 2.53-2.48 (m, 1 H, CH2), 2.17 (s, 3 H, Me),
2.00 (s, 3 H, Me), 1.94 (s, 3 H, Me). 13C{1H} NMR (75 MHz,
CDCl3): δ 153.4 (s, C2), 144.20 (d, J C,P ) 9.5 Hz, CPd), 135.30
(t, 4J ) 5.3 Hz, CH6), 134.50 (d, J C,P ) 11.7 Hz, ortho CH’s
Syn th esis of [P d {K2-C,N-C6H4(P P h 2dNC6H4OMe-4′)-2}-
(tm ed a )]ClO4 (9b). NaClO4 (50 mg, 0.41 mmol), was added
to a suspension of 6b (150 mg, 0.14 mmol) in acetone (30 mL).
An excess of tmeda (62 µL, 0.41 mmol), was added to the
stirred suspension, and the resulting orange solution was
stirred for a further 4 h. The solvent was removed, the residue
was treated with CH2Cl2 (10 mL), and the solution was filtered
through Celite. The filtrate was concentrated to ca. 2 mL, and
Et2O (20 mL) was added, precipitating 9b as a pink solid.
Yield: 177 mg, 92%. Mp: 196 °C. ΛM ) 151 Ω-1 cm2 mol-1. IR
2
PPh3), 132.43 (d, J C,P ) 9.5 Hz, ortho CH’s PPh3), 131.85 (s,
para CH’s PPh3), 130.85 (d, 1J C,P ) 97.0 Hz, i C’s PPh3), 130.55
1
(s, para CH’s PPh3), 130.54 (d, J C,P ) 47.3 Hz, i C’s PPh3),
3
128.58 (d, J C,P ) 11.6 Hz, meta CH’s PPh3), 128.29 (d, J C,P
)
)
3
1
(Nujol, cm-1): ν 1178 (PdN), 1089, 622 (ClO4). H NMR (200
9.9 Hz, meta CH’s PPh3), 124.66 (s, CH4), 121.53 (d, J C,P
10.9 Hz, CH3), 117.37 (s, CH5), 61.20 (s, CH2), 60.90 (s, CH2),
51.20 (s, Me), 50.80 (s, Me), 47.90 (s, Me), 47.00 (s, Me). 31P-
{1H} NMR (121 MHz, CDCl3): δ 27.55 (s, Pd-PPh3), 2.55 (s,
NdPPh3). Anal. Calcd for C49H50F3N3O3P2PdS: C, 59.67; H,
5.11; N, 4.26; S, 3.25. Found: C, 59.39; H, 5.23; N, 4.15; S,
3.12. Single crystals of 11‚TfO were grown by slow diffusion
of Et2O into solutions of 11‚TfO in CDCl3.
MHz, CDCl3): δ 7.70-7.30 (several m, 12 H, arom), 7.11 (m,
3
1 H, arom), 6.89 (d, J H,H ) 9 Hz 2 H, C6H4OMe-4), 6.82 (m, 1
3
H, arom), 6.57 (d, J H,H ) 9 Hz, 2 H, C6H4OMe-4), 3.68 (s, 3
H, OMe), 2.77 (s, 6 H, 2Me), 2.74-2.54 (m, 4 H, 2CH2), 2.11
(s, 6 H, 2Me). 13C{1H} NMR (50 MHz, CDCl3): δ 159.03 (d,
5
2J P,C ) 19 Hz, C-Pd), 155.54 (d, J P,C ) 3 Hz, C4 C6H4OMe-
4), 142.96 (d, 1J P,C ) 124.4 Hz, C2), 138.74 (d, 2J P,C ) 5 Hz, C1

4252 Organometallics, Vol. 22, No. 21, 2003
Vicente et al.
Syn th esis of [P d {K2-C,N-C(dNXy)C6H4(NdP P h 3)-2}I(C-
NXy)] (12). To a solution of 10 (100 mg, 0.14 mmol) in CH2-
Cl2 (15 mL) was added XyNC (Xy ) 2,6-dimethylphenyl; 57
mg, 0.44 mmol), and the mixture was stirred for 10 min. Then
the solution was filtered through Celite and the solvent
removed in vacuo. The orange crude product was stirred in
Et2O (10 mL), and the solid obtained was filtered, washed with
Et2O, and air-dried to yield 12 as a yellow solid. Yield: 110
mg, 91%. Mp: 188-190 °C. IR (Nujol, cm-1): ν 2156 (CtN),
1666 (CdN). 1H NMR (400 MHz, CDCl3): δ 8.10-8.00 (m,
was recrystallized from CH2Cl2/Et2O. Yield: 105 mg, 92% for
the crude sample; 85 mg, 74% after recrystallization. Dec pt:
138-140 °C. ΛM ) 171 Ω-1 cm2 mol-1. IR (KBr pellet, cm-1):
1
ν 1694 (CdO), 1094, 624 (ClO4). H NMR (300 MHz, CDCl3):
3
δ 7.79 (d, J H,H ) 7.5 Hz, 1 H, C6H4), 7.73-7.70 (m, 9 H ortho
and para H’s PPh3), 7.60-7.57 (m, 6 H meta H’s PPh3), 7.1-
7.05 (m, 1 H, C6H4), 7.00-6.98 (m, 2 H, C6H4), 5.31 (s, 2 H,
CH2Cl2), 3.69 (s, 3 H, CO2Me), 3.39 (s, 3 H, CO2Me), 2.8-2.6
(m, 2 H, CH2, tmeda), 2.68 (s, 3 H, Me tmeda), 2.59 (s, 3 H,
Me tmeda), 2.55 (s, 3 H, Me, tmeda), 2.4-2.3 (m, 2 H, CH2
tmeda), 1.69 (s, 3 H, Me, tmeda). 13C{1H} NMR (50 MHz,
CDCl3): δ 172.18 (CO), 162.89 (CO), 149.24 (d, J P,C ) 5 Hz,
quaternary C), 142.11 (d, J P,C ) 6 Hz, quaternary C), 141.12
(d, J P,C ) 5.5 Hz, quaternary C), 134.48 (d, 2J P,C ) 10 Hz, ortho
3
4
6 H, ortho or meta H’s PPh3), 7.78 (dt, J H,H ) 7.5 Hz, J H,H
)
1.5 Hz, J P,H ) 1.5 Hz, 1 H, H3 or H6 C6H4), 7.64-7.59 (m,
3 H, para H’s PPh3), 7.56-7.51 (m, 6 H, ortho or meta H’s
3
3
PPh3), 7.03 (t, J H,H ) 7.5 Hz, 1 H4, Xy), 6.88 (d, J H,H ) 7.5
Hz, 2 H, Xy), 6.76-6.69 (m, 3 H, Xy and H4 or H5 C6H4), 6.65
4
CH, PPh3), 134.01 (d, J P,C ) 2.5 Hz, para CH, PPh3), 132.01
3
3
(t, J H,H ) 7.5 Hz, 1 H, H4 or H5), 6.40 (t, J H,H ) 7.5 Hz, 1
(d, J P,C ) 1.5 Hz, quaternary C), 130.09 (d, J P,C ) 3 Hz, CH),
3
H4, Xy), 6.16 (d, J H,H ) 7.5 Hz, 1H, H3 or H6 C6H4), 2.38 (s,
129.27 (d, 3J P,C ) 12 Hz, meta CH, PPh3), 126.06 (d, J P,C ) 3.5
6 H, 2 Me), 2.11 (s, 6 H, 2Me). 13C{1H} NMR (100 MHz,
CDCl3): δ 180.55 (quaternary C), 154.79 (d, J P,C ) 2.5 Hz,
quaternary C), 151.24 (quaternary C), 142.93 (quaternary C),
142.76 (quaternary C), 134.22 (d, J P,C ) 9.6 Hz, ortho or meta
Hz, CH), 125.13 (d, J P,C ) 100 Hz, ipso C PPh3), 124.33 (d,
1
J P,C ) 3.5 Hz, CH), 63.74 (s, CH2), 58.77 (CH2), 53.02 (Me),
51.65 (Me), 51.60 (Me), 49.14 (Me), 48.34 (Me), 47.38 (Me). 31P-
{1H} NMR (121 MHz, CDCl3): δ 35.3 (s). Anal. Calcd for
4
CH’s PPh3), 134.02 (quaternary C), 132.97 (d, J P,C ) 2 Hz, p
C37H43Cl3N3O8PPd: C, 49.30; H, 4.81; N, 4.66. Found: C,
CH’s PPh3), 130.00 (CH, Xy), 128.70 (d, J P,C ) 9.7 Hz, ortho
49.03; H, 4.73; N, 4.82. Single crystals of 14‚ClO4‚CDCl3 were
grown by slow diffusion of Et2O into solutions of 14‚ClO4 in
CDCl3.
or meta CH’s PPh3), 128.21 (CH, Xy), 127.43 (CH, Xy), 127.22
2
(quaternary C), 127.14 (CH, Xy), 126.40 (d, J P,C ) 100 Hz,
ipso C’s PPh3), 125.43 (CH, C3 or C6 C6H4), 122.99 (CH, Xy),
120.38 (CH, C4 or C5 C6H4), 119.86 (d, J P,C ) 7.5 Hz, CH, C3
or C6 C6H4), 19.29 (s, Me), 18.59 (s, Me). 31P{1H} NMR (121
MHz, CDCl3): δ 26.45 (s). Anal. Calcd for C42H37IN3PPd: C,
59.48; H, 4.40; N, 4.95. Found: C, 59.31; H, 4.44; N, 5.07.
Syn t h esis of [P d {K2-C,N-C(dNXy)C6H 4(NdP P h 3)-2}-
(CNXy)2]TfO (13). XyNC (53 mg, 0.41 mmol) and TlOTf (51
mg, 0.14 mmol) were added to a solution of 10 (100 mg, 0.14
mmol) in acetone (5 mL). The resulting suspension was stirred
for 5 min and then filtered through Celite. The yellow solution
was evaporated to dryness, the residue was treated with Et2O
(10 mL), and the solid was filtered, washed with Et2O, and
dried in an air stream, giving 13 as a yellow solid. Yield: 120
Cr ysta l Str u ctu r e Deter m in a tion s. Crystal data and
numerical details of data collection and structure refinement
are given in Table 1. For the compounds 11‚TfO and 14‚ClO4‚
CDCl3, data were collected on a Bruker SMART 1000 CCD
diffractometer and those for the compounds 2, 6a ‚CH2Cl2, and
9a on a Siemens P4 diffractometer. Special features of refine-
ment: 9a , the perchlorate anion is disordered over two sites,
which were refined with 50% occupancy; 11‚TfO, the poor
crystal quality is reflected in the lack of precision; 14‚ClO4‚
CDCl3, the solvent molecule is disordered over two positions
with a common carbon site. The structures were refined
anisotropically using the program SHELXL-97 (G. M. Sheld-
rick, University of Go¨ttingen, Go¨ttingen, Germany). Hydrogen
atoms were included using rigid methyl groups or a riding
model.
mg, 90% with respect to isonitrile. Dec pt: 173-5 °C. ΛM
)
140 Ω-1 cm2 mol-1. IR (Nujol, cm-1): ν 2180 (CtN), 2168 (Ct
1
N), 1634 (CdN). H NMR (300 MHz, CDCl3, 40 °C): δ 8.02-
3
7.95 (m, 6 H, ortho or meta H’s PPh3), 7.88 (d, J H,H ) 7.5 Hz,
Resu lts a n d Discu ssion
1 H, H3 or H6 C6H4), 7.72-7.69 (m, 3 H, para H’s PPh3), 7.60-
3
7.59 (m, 6 H, ortho or meta H’s PPh3), 7.17 (t, J H,H ) 7.5 Hz,
Objectives a n d Meth od s. One of the main objectives
of our research has been the synthesis of ortho-func-
tionalized arylpalladium(II) complexes, because we have
found that they undergo insertion of unsaturated re-
agents, e.g. isocyanides, alkynes, and CO, to give
interesting complexes or organic compounds.17-20 At the
beginning of this work we were interested in preparing
palladated complexes containing the ortho iminic aryl
group of type III (Chart 1) (i) because we assumed they
would be more reactive toward the above-mentioned
unsaturated reagents than those containing a chelating
ligand of type IIb, (ii) because no organometallic com-
pound of any metal with such group was known, and
(iii) because of the interesting chemistry that the
iminophosphorane group could offer if the N atom were
not coordinated to Pd(II). Four different synthetic routes
2 H, 2 × H4 coord XyNC), 6.98 (d, 3J H,H ) 7.5 Hz, 4 H, 2 × H3
and H5 coord XyNC), 6.81-6.72 (m, 4 H, H3 and H5 insert
3
XyNC and H4 and H5 C6H4), 6.49 (t, J H,H ) 7.5 Hz, 1 H, H4
3
insert XyNC), 6.26 (d, J H,H ) 7.5 Hz, 1 H, H3 or H6 C6H4),
1
2.38 (s, 6 H, 2Me), 1.97 (b s, 12 H, 4Me). H NMR (300 MHz,
CDCl3, -60 °C): δ 8.09-8.02 (m, 6 H, ortho or meta H’s PPh3),
3
7.88 (d, J H,H ) 7.5 Hz, 1 H, H3 or H6 C6H4), 7.83-7.78 (m, 3
H, para H’s PPh3), 7.68-7.65 (m, 6 H, ortho or meta H’s PPh3),
3
7.24-7.17 (m, 2 H, 2 × H4 coord XyNC), 7.03 (d, J H,H ) 7.5
Hz, 2 H, H3 and H5 coord XyNC), 6.97 (d, 3J H,H ) 7.5 Hz, 2 H,
H3 and H5 coord. XyNC), 6.91-6.84 (m, 3 H, H3 and H5 insert
3
XyNC and H4 or H5 C6H4), 6.80 (t, J H,H ) 7.5 Hz, 1 H, H4 or
3
H5 C6H4), 6.55 (t, J H,H ) 7.5 Hz, 1 H, H4 insert XyNC), 6.27
3
(d, J H,H ) 7.5 Hz, 1 H, H3 or H6 C6H4), 2.47 (s, 6 H, 2Me),
2.11 (s, 6 H, 2Me), 1.63 (s, 6 H, 2Me). 31P{1H} NMR (121 MHz,
CDCl3): δ 28.6 (s). Anal. Calcd for C52H46F3N4O3PPdS: C,
62.37; H, 4.63; N, 5.59; S, 3.20. Found: C, 62.07; H, 4.67; N,
5.71; S, 2.90.
Syn th esis of [P d{K2-C,N-C(CO2Me)dC(CO2Me)C6H4(Nd
P P h 3)-2}(tm ed a )]ClO4‚CH2Cl2 (14‚ClO4). MeO2CCtCCO2-
Me (70 µL, 0.57 mmol) and AgClO4 (30 mg, 0.145 mmol) were
added to a stirred suspension of 10 (100 mg, 0.14 mmol) in
acetone (15 mL). The mixture was stirred for 30 min and then
filtered through Celite. The resulting solution was evaporated
to dryness, Et2O (10 mL) was added to the residue, and the
solid obtained was filtered, washed with Et2O, and air-dried
to give 14‚ClO4 as a pale yellow powder. The crude sample
(17) Vicente, J .; Abad, J . A.; Frankland, A. D.; Lopez-Serrano, J .;
Ramirez de Arellano, M. C.; J ones, P. G. Organometallics 2002, 21,
272.
(18) Vicente, J .; Abad, J . A.; Mart´ınez-Viviente, E.; J ones, P. G.
Organometallics 2002, 21, 4454.
(19) Vicente, J .; Saura-Llamas, I.; Turp´ın, J .; Ram´ırez de Arellano,
M. C.; J ones, P. G. Organometallics 1999, 18, 2683. Vicente, J .; Abad,
J . A.; Fo¨rtsch, W.; J ones, P. G.; Fischer, A. K. Organometallics 2001,
20, 2704.
(20) Vicente, J .; Abad, J . A.; Shaw, K. F.; Gil-Rubio, J .; Ram´ırez de
Arellano, M. C.; J ones, P. G. Organometallics 1997, 16, 4557.

Mercurated and Palladated Iminophosphoranes
Organometallics, Vol. 22, No. 21, 2003 4253
Ta ble 1. Cr ysta l Da ta for Com p ou n d s 2, 6a ‚CH2Cl2, 9a , 11‚TfO, a n d 14‚ClO4
2
6a ‚CH2Cl2
9a
11‚TfO
14‚ClO4‚CDCl3
formula
cryst color, habit
cryst size (mm)
cryst syst
space group
a (Å)
C25H21ClHgNP
colorless, block
0.56 × 0.26 × 0.24
triclinic
P1h
8.978(2)
10.714(3)
12.053(3)
86.500(18)
72.212(14)
85.46(2)
1099.6(5)
2
C55H50Cl2N2O4P2Pd2
yellow, block
0.50 × 0.34 × 0.18
triclinic
P1h
10.802(2)
11.848(2)
21.500(4)
97.91(3)
91.32(3)
111.29(3)
2531.7(9)
2
C31H37ClN3O4PPd
yellow, prism
0.28 × 0.23 × 0.14
monoclinic
P21/n
11.1979(8)
9.0604(6)
30.930(2)
90
97.071(6)
90
3114.2(4)
4
C49H50F3N3O3P2PdS
pale yellow, plate
0.31 × 0.20 × 0.05
monoclinic
P21/n
10.966(7)
30.880(18)
13.527(8)
90
C37H42Cl4N3O8PPd
pale yellow, prism
0.40 × 0.15 × 0.10
monoclinic
P21/n
13.6861(8)
14.6217(11)
21.1817(12)
90
104.121(3)
90
4110.7(5)
4
b (Å)
c (Å)
R (deg)
â (deg)
100.00(4)
90
4511(5)
γ (deg)
V (Å3)
Z
4
Fcalcd (Mg m-3
Mr
)
1.819
602.44
0.710 73
173
1.507
1.468
688.46
0.710 73
298
1.452
986.32
0.710 73
133
1.512
935.91
0.710 73
133
1148.61
0.710 73
173
λ (Å)
T (K)
F(000)
580
7.204
1164
0.93
1416
0.773
3.0-25.0
ψ scans
5888
2032
0.59
1.3-26.4
face indexed
40 136
1912
0.80
1.6-30.0
face indexed
81 456
µ(Mo KR) (mm-1
θ range (deg)
abs cor
)
3.0-25.0
3.2-25.0
ψ scans
ψ scans
no. of rflns coll
4163
10 204
no. of indep rflns
Rint
3844
0.0246
8849
0.023
5469
0.0278
9245
0.294
12 038
0.046
transmissn
no. of data/restraints/
params
0.0874-0.2767
3844/27/263
0.756-0.912
8849/32/608
0.8127-0.8995
5469/178/412
0.867-0.978
9245/147/559
0.785-0.927
12 038/339/521
R1 (I > 2σ(I))
0.0273
0.0674
1.4
0.0271
0.073
0.6
0.0374
0.0771
0.28
0.107
0.250
1.7
0.032
0.085
0.9
wR2 (all rflns)
max ∆F (e Å-3
S(F2)
)
1.03
1.03
1.034
1.12
1.03
Sch em e 1
were envisaged. (i) Iminophosphoranes could be mer-
curated, followed by transmetalation to palladium. This
was the first attempted method, in view of our wide
experience in the synthesis of organomercurials and
their use to prepare organo complexes of different
metals, including Pd(II),20-23 and because mercuration
of the related benzylidenanilines occurs at the ortho
iminic aryl group.24 (ii) Iminophosphoranes could be
palladated using reaction conditions different from those
previously reported that led to complexes of type IIb.12
(iii) A Kirsanov reaction could be used, starting from
some o-aminoaryl complexes that we had previously
reported.17 (iv) An iminophosphorane could be synthe-
sized containing an o-iodo substituent at the iminic aryl
group followed by an oxidative addition reaction using
a Pd(0) complex.
Mer cu r a tion of Im in op h osp h or a n es. Syn th esis
of Ar yl Com p lexes Con ta in in g a Ca r bod iim id e
Gr ou p . The reaction of the iminophosphorane 1a with
(21) Vicente, J .; Arcas, A.; Bautista, D.; J ones, P. G. Organometallics
1997, 16, 2127.
(22) Vicente, J .; Abad, J . A.; Rink, B.; Herna´ndez, F.-S.; Ram´ırez
de Arellano, M. C. Organometallics 1997, 16, 5269.
(23) Vicente, J .; Arcas, A.; Borrachero, M. V.; Hursthouse, M. B. J .
Chem. Soc., Dalton Trans. 1987, 1655. Vicente, J .; Chicote, M. T.;
Martin, J .; Artigao, M.; Solans, X.; Font-Altaba, M.; Aguilo´, M. J . Chem.
Soc., Dalton Trans. 1988, 141. Vicente, J .; Arcas, A.; Borrachero, M.
V.; Mol´ıns, E.; Miravitlles, C. J . Organomet. Chem. 1989, 359, 127.
Vicente, J .; Abad, J . A.; Stiakaki, M. A.; J ones, P. G. J . Chem. Soc.,
Chem. Commun. 1991, 137. Vicente, J .; Abad, J . A.; J ones, P. G.
Organometallics 1992, 11, 3512. Vicente, J .; Abad, J . A.; Gil-Rubio,
J .; J ones, P. G.; Bembenek, E. Organometallics 1993, 12, 4151. Vicente,
J .; Abad, J . A.; Gil-Rubio, J .; J ones, P. G. Inorg. Chim. Acta 1994, 222,
1. Vicente, J .; Abad, J . A.; Ferna´ndez-de-Bobadilla, R.; J ones, P. G.;
Ram´ırez de Arellano, M. C. Organometallics 1996, 15, 24. Vicente, J .;
Arcas, A.; Blasco, M. A.; Lozano, J .; Ram´ırez de Arellano, M. C.
Organometallics 1998, 17, 5374. Vicente, J .; Arcas, A.; Ferna´ndez-
Herna´ndez, J .; Bautista, D. Organometallics 2001, 20, 2767.
(24) Ding, K. L.; Wu, Y. J .; Hu, H. W.; Shen, L. F.; Wang, X.
Organometallics 1992, 11, 3849.
Hg(OAc)2 in refluxing THF followed by the addition of
LiCl resulted in the formation of the mercurated species
[Hg{C6H3(NdPPh3)-2-Me-5}Cl] (2) (Scheme 1), in which
the metalation had taken place at the imine aryl group,
giving the first example of a class III metalated imino-
phosphorane (Chart 1) and also the first organomercu-
rated iminophosphorane. The metathetical reaction of
2 with NaBr gave the complex [Hg{C6H3(NdPPh3)-2-
Me-5}Br] (3).

4254 Organometallics, Vol. 22, No. 21, 2003
Vicente et al.
Sch em e 2
Zimmer reported that the room-temperature reactions
of HgX2 (X ) Cl, Br, I) with 1a and similar iminophos-
phoranes lead to the adducts [HgX2{N(dPPh3)Ar}]; the
crystal structure of one such compound shows it to be
the dimer [HgCl(µ-Cl){N(dPPh3)Ph}]2.4 When these
room-temperature reactions were carried out with imi-
nophosphoranes substituted at the meta position or with
the electron-withdrawing p-NO2 group, no reaction took
place, and if elevated temperatures (80 °C) and extended
reaction times were used, OPPh3 and [Ph3PNHAr]X
were isolated. Therefore, our use of the appropriate Ar
group and of Hg(OAc)2 instead of mercury halides and
the heating of the reaction mixture seem to be the
factors responsible for the different reaction products
obtained from mercury salts and iminophosphoranes.
The formation of 2 contrasts with that observed in
all the other metalation reactions of iminophosphoranes,
which take place at one of the aryl groups bonded to
the phosphorus atom (see Introduction). However, the
result is not unexpected, since mercuration occurs
through electrophilic aromatic substitution and the
imine nitrogen activates its aryl ring toward such
substitution.25 In addition, Wu et al. have reported that
mercuration of a large number of benzylidenanilines
also occurs at the ortho position of the N-phenyl ring24
and corrected a previous suggestion that such mercu-
ration occurred at the C-aryl group.26 Wu suggested a
four-step mechanism for the mercuration of benzyli-
denanilines that could also operate in the case of 1a :
(i) formation of the adduct A (Scheme 2) such as those
reported by Zimmer (see above, X ) OAc);4 (ii) formation
of the π-complex B with an N-phenyl ring, as proposed
for some γ-(arylpropyl)mercury compounds;27 (iii) con-
version of the π-complex into the Wheland or σ-complex
intermediate C; (iv) loss of HOAc and formation of an
acetato complex that would react with LiCl to give 2.
The presence of the iminophosphorane group at the
ortho position of these aryl mercurials encouraged us
to exploit its well-known reactivity. Thus, the compound
2 reacts with p-tolyl isothiocyanate, resulting in its
transformation into the mercurated carbodiimide [Hg-
{C6H3(NdCdNC6H4Me-4′)-2-Me-5}Cl] (4) (Scheme 1).
The reaction of 2 with CO2 or CS2 permits the isolation
of the dimetalated carbodiimide [Hg{C6H3{NdCdNC6H3-
(HgCl)-1′-Me-5′}-2-Me-5}Cl] (5). 4 and 5 are the first
aryl complexes of any metal containing a carbodiimide
group.
Pt(II),21,31 Rh(III),32 Sn(IV),33 and Tl(III).34 However,
attempted analogous reactions of 2 and 3 with Me4N-
[AuCl4], (Me4N)2[Pd2Cl6], [PdCl2(PPh3)2], [Pd(PPh3)3],
(30) Vicente, J .; Chicote, M. T. Inorg. Chim. Acta 1981, 54, L259.
Vicente, J .; Chicote, M. T.; Bermu´dez, M. D. Inorg. Chim. Acta 1982,
63, 35. Vicente, J .; Chicote, M. T.; Arcas, A.; Artigao, M. Inorg. Chim.
Acta 1982, 65, L251. Vicente, J .; Chicote, M. T.; Arcas, A.; Artigao,
M.; J ime´nez, R. J . Organomet. Chem. 1983, 247, 123. Vicente, J .;
Chicote, M. T.; Bermu´dez, M. D.; Solans, X.; Font-Altaba, M. J . Chem.
Soc., Dalton Trans. 1984, 557. Vicente, J .; Chicote, M. T.; Bermu´dez,
M. D. J . Organomet. Chem. 1984, 268, 191. Vicente, J .; Chicote, M.
T.; Bermu´dez, M. D.; Garc´ıa-Garc´ıa, M. J . Organomet. Chem. 1985,
295, 125. Vicente, J .; Chicote, M. T.; Bermu´dez, M. D.; Sa´nchez-
Santano, M. J .; J ones, P. G.; Fittschen, C.; Sheldrick, G. M. J .
Organomet. Chem. 1986, 310, 401. Vicente, J .; Chicote, M. T.; Bermu´-
dez, M. D.; Sa´nchez-Santano, M. J .; J ones, P. G. J . Organomet. Chem.
1988, 354, 381. Vicente, J .; Bermu´dez, M. D.; Chicote, M. T.; Sa´nchez-
Santano, M. J . J . Organomet. Chem. 1990, 381, 285. Vicente, J .;
Bermu´dez, M. D.; Sa´nchez-Santano, M. J .; Paya´, J . Inorg. Chim. Acta
1990, 174, 53. Vicente, J .; Bermu´dez, M. D.; Carrio´n, F. J .; Mart´ınez-
Nicola´s, G. J . Organomet. Chem. 1994, 480, 103. Vicente, J .; Bermu´dez,
M. D.; Carrio´n, F. J .; J ones, P. G. J . Organomet. Chem. 1996, 508, 53.
Vicente, J .; Bermu´dez, M. D.; Carrio´n, F. J .; J ones, P. G. Chem. Ber.
1996, 129, 1301. Vicente, J .; Bermu´dez, M. D.; Carrio´n, F. J .; J ones,
P. G. Chem. Ber. 1996, 129, 1395.
(31) Vicente, J .; Chicote, M. T.; Martin, J .; J ones, P. G.; Fittschen,
C.; Sheldrick, G. M. J . Chem. Soc., Dalton Trans. 1986, 2215. Vicente,
J .; Abad, J . A.; Teruel, F.; Garc´ıa, J . J . Organomet. Chem. 1988, 345,
233.
(32) Vicente, J .; Martin, J .; Chicote, M. T.; Solans, X.; Miravitlles,
C. J . Chem. Soc., Chem. Commun. 1985, 1004. Vicente, J .; Martin, J .;
Solans, X.; Font-Altaba, M. Organometallics 1989, 8, 357. Vicente, J .;
Abad, J . A.; Lahoz, F. J .; Plou, F. J . J . Chem. Soc., Dalton Trans. 1990,
1459.
Attem p ts to Tr a n sm eta la te th e Tr ip h en ylp h os-
p h or a n eim in oa r yl Gr ou p . We have reported the
synthetic utility of organomercurials in the synthesis
of organo derivatives of Au(I),28,29 Au(III),29,30 Pd(II),20-23
(25) Olah, G. A.; Yu, S. H.; Parker, D. G. J . Org. Chem. 1976, 41,
1983. Damude, L. C.; Dean, P. A. W. J . Chem. Soc., Chem. Commun.
1978, 1083. Damude, L. C.; Dean, P. A. W. J . Organomet. Chem. 1979,
181, 1. Fung, C. W.; Khorramdel-Vahed, M.; Ranson, R. J .; Roberts,
R. M. G. J . Chem. Soc., Perkin Trans. 2 1980, 267. Larock, R. C.
Organomercury Compounds in Organic Synthesis. Reactivity and
Structure; Springer-Verlag: Berlin, 1985.
(26) Singh, H. B.; McWhinnie, W. R. J . Chem. Soc., Dalton Trans.
1985, 821.
(27) Kiefer, E. F.; Waters, W. L.; Calson, D. A. J . Am. Chem. Soc.
1968, 90, 5127.
(28) Vicente, J .; Arcas, A.; Chicote, M. T. J . Organomet. Chem. 1983,
252, 257. Vicente, J .; Arcas, A.; J ones, P. G.; Lautner, J . J . Chem. Soc.,
Dalton Trans. 1990, 451. Vicente, J .; Chicote, M. T.; Gonza´lez-Herrero,
P.; Gru¨nwald, C.; J ones, P. G. Organometallics 1997, 16, 3381.
(29) Vicente, J .; Bermu´dez, M. D.; Chicote, M. T.; Sa´nchez-Santano,
M. J . J . Organomet. Chem. 1989, 371, 129.

Mercurated and Palladated Iminophosphoranes
Organometallics, Vol. 22, No. 21, 2003 4255
Sch em e 3
and [PtCl2(bpy)] have proved unsuccessful. Because
diarylmercurials are generally better transmetalating
agents, we also attempted to prepare [Hg{C6H3(Nd
PPh3)-2-Me-5}2]. However, 2 does not symmetrize with
ammonia35 and gives mixtures when reacted with Me4-
NCl22 or PPh3.36
P a lla d a tion of Im in op h osp h or a n es. The only pa-
per on the palladation of iminophosphoranes reported
the synthesis of the complexes [Pd{κ2-C,N-(C6H3R1-5)-
{P(C6H4R1-4)2dNC6H4R2-n}(µ-Cl)]2 (R1 ) H, R2 ) Me
(n ) 3, 4), OMe (n ) 4); R1 ) Me, R2 ) OMe (n ) 4)) by
addition of the ligand to a methanol solution of Na2-
[PdCl4].5 We decided to try a similar reaction, but using
Pd(OAc)2 and THF, to compare the results with those
obtained in the mercuration and to see if the change of
the reaction conditions could lead to a triphenylphos-
phoraneiminoaryl complex. However, not unexpectedly,
the room-temperature reaction of the iminophosphorane
1a or 1b with Pd(OAc)2 results in the formation of the
cyclopalladated complex [Pd{κ2-C,N-C6H4(PPh2dNC6H4R-
4′)-2}(µ-OAc)]2 (R ) Me (6a ), MeO (6b)) (Scheme 3),
similar to those previously reported in which the pal-
ladation has taken place at the ortho position of one of
the phenyl rings bonded to the phosphorus atom,
permitting the formation of a five-membered ring
through the coordination of the nitrogen atom; in
addition, the acetato ligand acts as bridge forming a
dimer, as confirmed by the X-ray diffraction study for
6a ‚CH2Cl2 (see below).
Although formation of an adduct is, as in mercuration
reactions, the proposed first step in palladation reac-
tions involving N-donor aryl ligands (intermediate A in
Scheme 2),37 the formation of the five-membered-ring
σ-complex intermediate D seems to be preferred to the
postulated formation of a π-complex with the N-phenyl
ring in mercuration reactions. In fact, it is quite general
that formation of a five-membered ring including a
double bond (endo isomer), as in complexes 6a ,b, is
preferred to other alternatives in cyclopalladation reac-
tions.38
Complex 6b reacted with NaBr to give the bromo
derivative [Pd{κ2-C,N-C6H4(PPh2dNC6H4OMe-4′)-2}(µ-
intractable mixture. When a mixture of 6a or 6b was
refluxed with PhCtCPh in CHCl3 or toluene, most
starting materials were recovered. Although 6a reacted
t
Br)]2 (7) and with an excess of the isonitrile BuNC to
give the complex [Pd{κ2-C,N-C6H4(PPh2dNC6H4OMe-
4′)-2}(OAc)(CNtBu)] (8). However, the reactions of 6a
1
with MeO2CCtCCO2Me, and H NMR and IR spectra
t
with BuNC (1:3) or XyNC (Xy ) 2,6-dimethylphenyl;
were in agreement with the formation of a monoinserted
complex (such as 14‚ClO4; see below), the product of the
reaction could not be isolated analytically pure. Com-
plexes 6a ,b reacted with NaClO4 and tmeda (N,N,N′,N′-
tetramethylethylenediamine), affording the cationic
1:3) and of 6b with XyNC (1:2 and 1:3 molar ratios) gave
intractable mixtures. CO did not react with complex 6a
but with 6b gave Pd metal, unreacted 6b, and an
(33) Brianso´, J . L.; Sola´ns, X.; Vicente, J . J . Chem. Soc., Dalton
Trans. 1983, 169. Vicente, J .; Chicote, M. T.; Carren˜o, R. M.; Ramirez
de Arellano, M. C. J . Organomet. Chem. 1989, 368, 263. Vicente, J .;
Chicote, M. T.; Ramirez de Arellano, M. C.; Pelizzi, G.; Vitali, F. J .
Chem. Soc., Dalton Trans. 1990, 279. Vicente, J .; Chicote, M. T.;
Ram´ırez de Arellano, M. C.; J ones, P. G. J . Organomet. Chem. 1990,
394, 77. Vicente, J .; Chicote, M. T.; Ram´ırez de Arellano, M. C.; J ones,
P. G. J . Chem. Soc., Dalton Trans. 1992, 1839.
(34) Vicente, J .; Abad, J . A.; Gutierrez-J ugo, J . F.; J ones, P. G. J .
Chem. Soc., Dalton Trans. 1989, 2241.
(35) Nesmeyanov, A. N. Selected Works in Organic Chemistry;
Pergamon Press: Oxford, U.K., 1963; p 385. Lutsenko, I. F.; Khomutov,
R. M. Dokl. Akad. Nauk SSSR 1953, 88, 837.
(36) Seyferth, D.; Towe, R. H. Inorg. Chem. 1962, 1, 185.
(37) Gomez, M.; Granell, J .; Martinez, M. Organometallics 1997, 16,
2539. Ryabov, A. D. Chem. Rev. 1990, 90, 403.
(38) Navarro-Ranninger, C.; Lopez-Solera, I.; Alvarez-Valdes, A.;
Rodriguez-Ramos, J . H.; Masaguer, J . R.; Garcia-Ruano, J . L. Orga-
nometallics 1993, 12, 4104. Crispini, A.; Ghedini, M. J . Chem. Soc.,
Dalton Trans. 1997, 75.
complexes
[Pd{κ2-C,N-C6H4(PPh2dNC6H4R-4′)-2}-
(tmeda)]ClO4 (R ) Me (9a ), MeO (9b)) (Scheme 3).
Syn th esis of Tr ip h en ylp h osp h or a n eim in oa r yl
P a lla d iu m (II) Com p lexes. After the above fruitless
attempts to prepare triphenylphosphoraneiminoaryl
palladium(II) complexes, we attempted reactions based
on the Kirsanov reaction, i.e., ArNH2 + PPh3Br2
f
ArNdPPh3 + 2BrH. The first attempt consisted of the
synthesis, through oxidative addition reactions, of some
o-aminoaryl complexes (ArNH2 ) [Pd(C6H4Y-5-NH2-2)X-
(L2)], Y ) H, X ) I, L2 ) bpy (2,2′-bipyridine); Y ) NO2,
X ) Br, L2 ) tmeda) that we had previously prepared.17
However, 31P NMR spectra of the mixture resulting from
the reactions of these complexes with PPh3Br2 in

4256 Organometallics, Vol. 22, No. 21, 2003
Vicente et al.
Sch em e 4
Sch em e 5
be followed by coordination of the imine nitrogen,
forming a chelate and displacing the tmeda ligand to
give the intermediate [Pd{κ2-C,N-C(dNXy)C6H4(Nd
PPh3)-2}I]2. This would be the slower step of the process.
The dinuclear intermediate would rapidly react with
unreacted XyNC to give 12, even when using an 1:1
t
molar ratio. Complex 10 reacted with BuNC in a 1:1
or 1:3 molar ratio or using an excess of isocyanide giving
complex mixtures. The cis geometry of the carbon donor
ligands in 12 is in accord with the high transpho-
bia18,21,39 between such ligands. The reaction of 10 with
TlOTf and 2 equiv of XyNC gave the cationic complex
[Pd{κ2-C,N-C(dNXy)C6H4(NdPPh3)-2}(CNXy)2]TfO (13).
Reactions of 10 with CO led to complex mixtures. The
same reaction followed by addition of TlOTf gave a
product whose 31P NMR and IR spectra are compatible
with monoinsertion of CO and coordination of the
nitrogen atom to give a five-membered ring, in addition
to some minor impurities that could not be removed.
Insertion reactions of alkynes into the Pd-C bond are
also of current interest.20,40 Complex 10 reacts with
MeO2CCtCCO2Me (dmad) and AgClO4 to give the
alkenyl derivative [Pd{κ2-C,N-C(CO2Me)dC(CO2Me)-
C6H4(NdPPh3)-2}(tmeda)]ClO4 (14‚ClO4), the result of
insertion of the alkyne into the Pd-C bond and coor-
dination of the nitrogen atom, creating a six-membered
chelate ring (Scheme 5), as confirmed by X-ray diffrac-
tion studies. Several attempts to prepare similar com-
plexes were unfruitful. Thus, using PhCtCPh, 3-hex-
yne, or PhCtCCO2Me instead of dmad gave intractable
mixtures of products. When in the reaction of 10, TlOTf
was used instead of AgClO4, the NMR spectra of the
product 14‚OTf showed the presence of the pure mono-
inserted complex but a low (by 1.5%) elemental analysis
of carbon was found.
refluxing benzene show a complex mixture that we could
not separate. Finally, we succeeded by reacting Ph3Pd
NC6H4I-2 (1c), prepared by the Kirsanov method1 from
2-iodoaniline and Ph3PBr2,16 with a mixture of “Pd-
(dba)2” ([Pd2(dba)3]‚dba, dba ) dibenzylideneacetone)
and tmeda to give [Pd{C6H4(NdPPh3)-2}I(tmeda)] (10)
(Scheme 4). Reaction of 10 with PPh3 and TlOTf (TfO
) CF3SO3) resulted in the formation of the cationic [Pd-
{C6H4(NdPPh3)-2}(tmeda)(PPh3)]TfO (11‚TfO). When in
this reaction AgClO4 was used instead of TlOTf, the
NMR spectra of the product 11‚ClO4 were similar to
those of 11‚TfO but it did not give the correct analysis.
As mentioned above, we planned to study the reac-
tions of some of these new complexes with unsaturated
molecules. Thus, complex 10 reacted with XyNC (Xy )
2,6-dimethylphenyl; 1:3.1 molar ratio; Scheme 4) to give
[Pd{κ2-C,N-C(dNXy)C6H4(NdPPh3)-2}I(CNXy)] (12). Sur-
prisingly, when the reaction was carried out in a 1:1
molar ratio, 12 and the starting material 10 were
isolated. We have reported that when similar complexes
containing the ortho substituent C(O)Me or CN were
reacted with XyNC, the first isolable compound was the
product of the insertion of the isocyanide.18 It is then
reasonable to assume that formation of the inserted
complex [Pd{C(dNXy)C6H4(NdPPh3)-2}I(tmeda)] would
Complex 10 reacts with 4-MeC6H4NCO to give the
corresponding carbodiimide complex. However, it was
obtained impure in low yield.
(39) Vicente, J .; Abad, J . A.; Frankland, A. D.; Ram´ırez de Arellano,
M. C. Chem. Eur. J . 1999, 5, 3066.

Mercurated and Palladated Iminophosphoranes
Organometallics, Vol. 22, No. 21, 2003 4257
F igu r e 1. (a) Thermal ellipsoid plot (50% probability) of 2 with the labeling scheme. Selected bond lengths (Å) and angles
(deg): Hg-C(1) ) 2.042(5), Hg-Cl ) 2.3184(14), P-N ) 1.576(4), N-C(2) ) 1.393(6); C(1)-Hg-Cl ) 173.02(13), C(2)-
N-P ) 127.1(3). (b) Ladders parallel to the b axis formed through Hg‚‚‚Cli contacts ((i) 1 - x, 1 - y, -z, Hg‚‚‚Cli ) 3.4125-
(17) Å) and C(34)-H(34)‚‚‚Clii hydrogen bonds ((ii) -x + 1, -y, -z, C(34)‚‚‚Clii ) 3.663(6) Å, H(34)‚‚‚Clii ) 2.77 Å, C(34)-
H(34)‚‚‚Clii ) 156.8°).
Sp ectr oscop ic Da ta . The spectroscopic data of the
reported compounds are in accordance with the pro-
posed structures. The insolubility of 5 has prevented us
from studying it by NMR, but its EI MS spectrum shows
a signal of low intensity (1.2%) corresponding to the
molecular ion.
The dimeric complexes 6a ,b show in their 13C NMR
spectra that the two phenyl rings of the PPh2 group are
inequivalent, since their respective ipso carbons reso-
nate at different frequencies. This is in accordance with
the X-ray structural determination of 6a ‚CH2Cl2 (see
below).
additional signals at 22.03 and 12.08 ppm and a very
weak signal at 29.9 ppm.
1
A recent H, 19F, 31P, and 35Cl PGSE diffusion study
on the complexes 11‚TfO, 11‚ClO4, 14‚TfO, and 14‚ClO4
shows that the diffusion coefficients of cation and anion
in acetone are quite different. The cation seems to move
independently and move much slower than the anion.
However, in chloroform, the diffusion coefficients for
cation and anion in the triflates are almost identical,
indicating complete ion pairing, while in the perchlor-
ates they are slightly different, suggesting that the ion
pairing is not as strong.41
1
The compound 13 is fluxional. Its H NMR spectrum
The tmeda complexes 10, 11‚TfO, and 14‚ClO4 show
1
four Me signals in their H and 13C NMR spectra. This
shows a signal at 2.38 ppm corresponding to the two
methyls of a Xy group and another signal at 1.97 ppm
integrated to 12 H, corresponding to two Xy groups.
When the temperature is lowered to -60 °C, the
expected three signals (at 2.47, 2.11, and 1.63 ppm) were
observed. The signal at about 2.4 ppm should be
assigned to the inserted isonitrile if a fast exchange of
the coordinated cis isocyanides at room temperature is
assumed. We have reported a similar behavior in the
complex [Pd{{κ2-C,N-C(dNXy)C6H4NH2-2}(CNXy)2]TfO.17
X-r a y Str u ctu r e Deter m in a tion s. The crystal and
molecular structures of the compounds 2, 6a ‚CH2Cl2,
9a, 11‚TfO, and 14‚ClO4‚CDCl3 have been determined
by X-ray diffraction studies (Table 1). The mercurial 2
(Figure 1a) shows a distorted linear structure (C(1)-
Hg-Cl ) 173.03(13) Å). The P-N distance (1.576(4) Å)
corresponds to a double bond,42 and it is similar to that
observed in related iminophosphoranes.43 In the crystal
the mercury atom forms dimers through Hg‚‚‚Cl con-
tacts shorter than the sum of the van der Waals radii
(Figure 1b). Similar interactions have been reported.44
suggests, in the cases of 10 and 11‚TfO, that the aryl
ring has restricted rotation around the C-Pd bond and,
in the case of 14‚ClO4, that the six-membered chelate
ring is not planar, as is observed in the solid state
according to the X-ray diffraction studies of 14‚ClO4‚
CDCl3 (see below). Because the complex 11‚TfO slowly
decomposes in solution, the 13C NMR spectrum shows
minor peaks due to impurities. To distinguish the
signals belonging to 11‚TfO, a long-range C-H correla-
tion (HMBC) was done. C2 and CPd assignments (153.4
and 144.20 ppm, respectively) were tentative and were
based upon experimental data from organic aryl imi-
nophosphoranes (chemical shifts for C1 in 1 and 2 are
151.58 and 151.87 ppm, respectively). After the 13C
NMR spectra were acquired and HMBC experiments
(3.5 h) carried out, the 31P NMR spectrum showed two
(40) Albert, J .; Granell, J .; Sales, J .; Solans, X. J . Organomet. Chem.
1989, 379, 177. Pfeffer, M. Recl. Trav. Chim. Pays-Bas 1990, 109, 567.
Dupont, J .; Pfeffer, M.; Theurel, L.; Rotteveel, M. A.; Decian, A.;
Fischer, J . New J . Chem. 1991, 15, 551. Maassarani, F.; Pfeffer, M.;
Borgne, G. L. Organometallics 1990, 9, 3003. Sutter, J . P.; Pfeffer, M.;
Decian, A.; Fischer, J . Organometallics 1992, 11, 386. Ryabov, A. D.;
Vaneldik, R.; Leborgne, G.; Pfeffer, M. Organometallics 1993, 12, 1386.
Beydoun, N.; Pfeffer, M.; Decian, A.; Fischer, J . Organometallics 1991,
10, 3693. Lopez, C.; Solans, X.; Tramuns, D. J . Organomet. Chem. 1994,
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Organometallics 1999, 18, 2683. Yagyu, T.; Osakada, K.; Brookhart,
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G. H.; Peng, S. M.; Liu, S. T. Organometallics 2001, 20, 5557. Gul, N.;
Nelson, J . H.; Willis, A. C.; Rae, A. D. Organometallics 2002, 21, 2041.
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Serrano, J . Organometallics 2002, 21, 5841.
(42) Allen, F. H.; Kennard, O.; Watson, D. G.; Brammer, L.; Orpen,
A. G.; Taylor, R. J . Chem. Soc., Perkin Trans. 1 1987, S1.
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Dehnicke, K.; Beck, J .; Hiller, W.; Strahle, J .; Maurer, A.; Feuske, D.
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Acta Crystallogr., Sect. C 1994, 50, 255.
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R.; Gabbai, F. P. Organometallics 2001, 20, 3169.

4258 Organometallics, Vol. 22, No. 21, 2003
Vicente et al.
F igu r e 3. Thermal ellipsoid representation (50% prob-
ability) of 9a with the labeling scheme. Selected bond
lengths (Å) and angles (deg): Pd-C(11) ) 2.019(3), Pd-
N(1) ) 2.055(2), Pd-N(3) ) 2.117(3), Pd-N(2) ) 2.201(3),
P-N(1) ) 1.607(3); C(11)-Pd-N(1) ) 82.78(12), C(11)-
Pd-N(3) ) 97.38(13), N(1)-Pd-N(2) ) 95.34(10), N(3)-
Pd-N(2) ) 84.17(11).
F igu r e 2. Ellipsoid representation of 6a with 50% prob-
ability ellipsoids and the labeling scheme. The solvent has
been omitted for clarity. Selected bond lengths (Å) and
angles (deg): Pd(1)-C(1) ) 1.959(3), Pd(1)-O(3) ) 2.041-
(2), Pd(1)-N(1) ) 2.050(2), Pd(1)-O(2) ) 2.1153(19), Pd-
(1)-Pd(2) ) 3.0113(8), Pd(2)-C(13) ) 1.964(3), Pd(2)-N(2)
) 2.051(2), Pd(2)-O(1) ) 2.0601(19), Pd(2)-O(4) ) 2.143-
(2), P(1)-N(1) ) 1.605(2), P(2)-N(2) ) 1.610(2); C(1)-Pd-
(1)-O(3) ) 90.34(10), C(1)-Pd(1)-N(1) ) 86.74(10), O(3)-
Pd(1)-N(1) ) 174.39(8), C(1)-Pd(1)-O(2) ) 173.95(9),
C(13)-Pd(2)-N(2) ) 85.79(10), C(13)-Pd(2)-O(1) ) 91.80-
(10), N(2)-Pd(2)-O(1) ) 173.23(8), C(13)-Pd(2)-O(4) )
177.48(9).
A C-H‚‚‚Cl-Hg hydrogen bond, within the strong
angularly dependent C-H‚‚‚Cl interaction range, con-
nects the mercury dimers, forming a ladder (Figure
1b).45 It has been shown that metal-bound chlorine is a
good hydrogen bond acceptor.46
The palladated complex 6a ‚CH2Cl2 shows a dimeric
structure with two bridging acetato ligands (Figure 2).
Each palladium has a square-planar geometry, but the
molecule is not planar. The iminophosphorane has been
metalated at one of the ortho carbons of one of the Ph
groups, and the iminic nitrogen coordinates to the
palladium, forming a five-membered chelate ring. The
P-N distances (P(1)-N(1) ) 1.607(2) Å; P(2)-N(2) )
1.611(2) Å) are somewhat longer than that found in 2,
and they are quite similar to the P-N distances found
in an ortho-manganated iminophosphorane (1.603(3),
1.597(4), 1.594(4) Å).11 Therefore, the P-N lengthening
could be due to the N coordination. The different Pd-O
distances found (Pd(1)-O(1) ) 2.0429(19) Å (trans to
N); Pd(1)-O(3) ) 2.1148(18) Å (trans to C); Pd(2)-O(2)
) 2.1433(19) Å (trans to C); Pd(2)-O(4) ) 2.0599(18) Å
(trans to N)) reflect the greater trans influence exerted
by the carbon donor ligand with respect to the iminic
nitrogen. The bridging acetates hold both Pd atoms at
a distance of 3.0113(8) Å. Similar complexes show equal
or even shorter distances.47 The molecular packing
involves two C-H‚‚‚O contacts. One of them (C(11)-
H(11)‚‚‚O(2) (-x + 2, -y + 1, -z + 1)) links the
molecules into dimers.
F igu r e 4. Ellipsoid representation of 11‚TfO with 50%
probability ellipsoids and the labeling scheme. The anion
has been omitted for clarity. Selected bond lengths (Å) and
angles (deg): Pd-C(11) ) 1.997(7), Pd-N(2) ) 2.177(7),
Pd-N(1) ) 2.239(6), Pd-P(1) ) 2.252(3), P(2)-N(3) )
1.570(7), N(3)-C(12) ) 1.373(10); C(11)-Pd-N(2) ) 92.2-
(3), N(2)-Pd-N(1) ) 82.1(3), C(11)-Pd-P(1) ) 84.4(2),
N(1)-Pd-P(1) ) 101.2(2), C(12)-N(3)-P(2) ) 127.8(5).
distance (1.611(4) Å) is virtually identical with that
shown by the complex 6a ‚CH2Cl2. The different Pd-
N(2) (2.204(4) Å) and Pd-N(3) (2.116(3) Å) distances
indicate again the greater trans influence of the carbon
donor ligand.
The structure of 11‚TfO confirms the palladation at
the N-aryl substituent (Figure 4). In agreement with
(47) See for example: Selbin, J .; Abboud, K.; Watkins, S. F.;
Gutierrez, M. A.; Fronczek, F. R. J . Organomet. Chem. 1983, 241, 259.
Ukhin, L. Y.; Dolgopolova, N. A.; Kuz’mina, L. G.; Struchkov, Y. T. J .
Organomet. Chem. 1981, 210, 263. O’Keefe, B. J .; Steel, P. J . Orga-
nometallics 1998, 17, 3621. Cardenas, D. J .; Echavarren, A. M.;
Ramirez de Arellano, M. C. Organometallics 1999, 18, 3337. Teijido,
B.; Fernandez, A.; Lopez-Torres, M.; Castro-J uiz, S.; Suarez, A.;
Ortigueira, J . M.; Vila, J . M.; Fernandez, J . J . J . Organomet. Chem.
2000, 598, 71. Churchill, M. R.; Wasserman, H. J .; Young, G. J . Inorg.
Chem. 1980, 19, 762. Fuchita, Y.; Takahashi, K.; Kanehisa, N.;
Shinkimoto, K.; Kai, Y.; Kasai, N. Polyhedron 1996, 15, 2777. Navarro-
Ranninger, C.; Zamora, F.; Martinez-Cruz, L. A.; Isea, R.; Masaguer,
J . R. J . Organomet. Chem. 1996, 518, 29. Zhao, G.; Yang, Q.-C.; Mak,
T. C. W. Organometallics 1999, 18, 3623. Dupont, J .; Gruber, A. S.;
Fonseca, G. S.; Monteiro, A. L.; Ebeling, G.; Burrow, R. A. Organo-
metallics 2001, 20, 171. Navarro-Ranninger, C.; Zamora, F.; Lopez-
Solera, I.; Monge, A.; Masaguer, J . R. J . Organomet. Chem. 1996, 506,
149.
The structure of 9a (Figure 3) reveals a distorted-
square-planar coordination around the palladium atom.
The dihedral angle between the planes defined by Pd-
N(2)-N(3) and Pd-C(11)-N(1) is 12.8°. The P-N(1)
(45) Aakero¨y, C. B.; Evans, T. A.; Seddon, K. R.; Pa´linko´, I. New J .
Chem. 1999, 145.
(46) Aullo´n, G.; Bellamy, D.; Brammer, L.; Bruton, E. A.; Orpen, A.
G. Chem. Commun. 1998, 653.

Mercurated and Palladated Iminophosphoranes
Organometallics, Vol. 22, No. 21, 2003 4259
in the complexes 6a ‚CH2Cl2 and 9a . The C(7)-C(8) bond
distance (1.341(2) Å) corresponds to a CdC double bond.
The N-Pd bond distances of the tmeda ligands (Pd-
N(2) ) 2.1114(16) Å; Pd-N(3) ) 2.1692(16) Å) are in
accordance with the smaller trans influence of the iminic
nitrogen ligand as compared to the alkenyl ligand. When
the Pd-N(3) distance is compared with the Pd-N(2)
length in the cationic complex 9a , the scale of trans
influence C-aryl > C-alkenyl > N-donor ligand can be
established. The molecular packing involves four short
C-H‚‚‚O contacts, three of which link the molecules into
layers parallel to the xy plane.
Con clu sion s
We have studied transmetalation, metalation, and
oxidative addition reactions to prepare iminophospho-
ranes metalated in the substituent at N. Mercuration
leads to the desired complexes, which are the first
organomercurated iminophosphoranes. From one of
them we have prepared the first aryl complexes of any
metal containing a carbodiimide group. Palladation of
iminophosphoranes occurs at one aryl group attached
at P. However, the desired palladium complexes can be
prepared through oxidative addition reactions. These
complexes insert an isocyanide or an alkyne to give
iminoacyl or vinyl derivatives. The products of the
oxidative addition reactions, their derivatives, and their
related mercuric compounds are the first iminophos-
phoranes metalated at the substituent at N of any
metal.
F igu r e 5. Ellipsoid representation of 14‚ClO4 with 50%
probability ellipsoids and the labeling scheme. The anion
has been omitted for clarity. Selected bond lengths (Å) and
angles (deg): Pd-C(8) ) 2.0068(18), Pd-N(1) ) 2.0519-
(15), Pd-N(2) ) 2.1114(16), Pd-N(3) ) 2.1692(16), P-N(1)
) 1.6317(16), C(7)-C(8) ) 1.341(2); C(8)-Pd-N(1) )
85.24(7), C(8)-Pd-N(2) ) 97.08(7), N(1)-Pd-N(3) )
93.36(6), N(2)-Pd-N(3) ) 84.04(6), C(11)-N(1)-P ) 115.18-
(12), C(11)-N(1)-Pd ) 109.83(11), P-N(1)-Pd ) 124.64-
(8), C(8)-C(7)-C(12) ) 123.54(17), C(8)-C(7)-C(21) )
119.56(17), C(12)-C(7)-C(21) ) 116.89(16), C(7)-C(8)-
C(23) ) 118.69(16), C(7)-C(8)-Pd ) 122.45(14), C(23)-
C(8)-Pd ) 118.70(12).
the above conclusion on the influence of coordination
on the P-N distance, the P(2)-N(3) length (1.570(7) Å)
is very similar to that of the mercurial 2 and shorter
than those in the complexes 6a ‚CH2Cl2 and 9a . The
greater trans influence of the aryl as compared to the
PPh3 ligand is shown by the longer Pd-N(1) distance
(2.239(6) Å) as compared to Pd-N(2) (2.177(7) Å). The
molecular packing involves four very short C-H‚‚‚O
contacts that link the molecules into thick layers paral-
lel to the xz plane.
The complex 14‚ClO4‚CDCl3 exhibits a square-planar
coordination around the palladium, which confirms the
insertion of the alkyne into the Pd-C bond, giving a
six-membered chelate ring (Figure 5). The iminic P-N(1)
distance is 1.6317(16) Å, somewhat longer than those
Ack n ow led gm en t. We thank the Ministerio de
Ciencia y Tecnolog´ıa, FEDER (Grant No. BQU2001-
0133) and the Fonds der Chemischen Industrie for
financial support and Fundacio´n Se´neca (Comunidad
Auto´noma de la Regio´n de Murcia, Murcia, Spain) for
the award of a grant to J .L.-S.
Su p p or tin g In for m a tion Ava ila ble: Listings of all re-
fined and calculated atomic coordinates, anisotropic thermal
parameters, and bond lengths and angles for 2, 6a ‚CH2Cl2,
9a , 11‚TfO, and 14‚ClO4‚CDCl3. This material is available free
of charge via the Internet at http://pubs.acs.org.
OM0303552