Synthesis and reactions of heterodinuclear organoplatinum complexes having an unsymmetrical PN ligand

Article abstract of DOI:10.1021/om030477u

A series of heterodinuclear organoplatinum complexes having an unsymmetrical PN ligand (Et₂NC₂H₄PPh₂-κ²N, P)RPt-ML_n [ML_n = MoCp(CO)₃, R = Me (1), R = Ph (2); ML_n<

Full text of DOI:10.1021/om030477u

4238
Organometallics 2003, 22, 4238-4247
Syn th esis a n d Rea ction s of Heter od in u clea r
Or ga n op la tin u m Com p lexes Ha vin g a n Un sym m etr ica l
P N Liga n d
Susumu Tsutsuminai, Nobuyuki Komine, Masafumi Hirano, and
Sanshiro Komiya*
Department of Applied Chemistry, Faculty of Technology, Tokyo University of Agriculture and
Technology, 2-24-16 Nakacho, Koganei, Tokyo 184-8588, J apan
Received J une 20, 2003
A series of heterodinuclear organoplatinum complexes having an unsymmetrical PN ligand
(Et2NC2H4PPh2-κ2N,P)RPt-MLn [MLn ) MoCp(CO)3, R ) Me (1), R ) Ph (2); MLn ) WCp-
(CO)3, R ) Me (3), R ) Ph (4); MLn ) Co(CO)4, R ) Me (5), R ) Ph (6)] have been synthesized
by metathetical reactions of PtR(NO3)(Et2NC2H4PPh2-κ2N,P), which is prepared in situ from
PtRCl(Et2NC2H4PPh2-κ2N,P) (R ) Me, Ph) and AgNO3, with Na[MLn]. Analogous complexes
with a bidentate nitrogen ligand (tmeda-κ2N,N′)RPt-MoCp(CO)3 [R ) Me (7), Ph (8)] are
also prepared by ligand exchange reaction of (cod)RPt-MoCp(CO)3 with TMEDA (N,N,N′,N′-
tetramethylethylenediamine). These complexes are characterized by NMR and IR spec-
troscopies and elemental analyses, and the molecular structure of 2 is determined by X-ray
structure analysis. Variable-temperature NMR study reveals the reversible partial dissocia-
tion of the Pt-N bond in 2 and 4, where the kinetic parameters are estimated by line shape
q
analysis of 2: ∆G273 ) 57.9 kJ mol-1, ∆Hq) 49.8 kJ mol-1, ∆Sq ) -29.7 J mol-1 K-1
.
Treatment of 1-4 with CO causes partial dissociation of the amino ligand moiety in the PN
ligand from the Pt center to form (Et2NC2H4PPh2-κ1P)(CO)RPt-MCp(CO)3 [M ) Mo, R )
Me (9), Ph (10); M ) W, R ) Me (11), Ph (12)]. Heating of 9 at 70 °C induces CO insertion
to give an equilibrium mixture of (Et2NC2H4PPh2-κ2N,P)(MeCO)Pt-MoCp(CO)3 (14) with 9
in 3:2 ratio. In contrast, the Pt-Co complex 5 with a PN ligand smoothly yields the acetyl
complex (Et2NC2H4PPh2-κ2N,P)(MeCO)Pt-Co(CO)4 (15) on interaction with CO at room
temperature. On the other hand, in the reactions of 1 with Et2NC2H4PPh2 or phosphorus
ligand such as PMe3, PEt3, PPh3, and P(OMe)3, heterolytic cleavage of the Pt-Mo bond takes
place to give ionic complexes [PtMe(PR3)(Et2NC2H4PPh2-κ2N,P)]+[MoCp(CO)3]- [PR3 ) Et2-
NC2H4PPh2 (17), PMe3 (18), PEt3 (19), PPh3 (20), P(OMe)3 (21)].
In tr od u ction
unique reactions such as specific organic group transfer
between different metal centers,4a-c,f,h significant ac-
celeration of â-H elimination,4d accelerated CO insertion
reactions,4e,i and regio- and stereoselective insertion
reactions of thiiranes into Pt-Mn (or -Re) bonds
controlled by an ancillary alkyl ligand.4g Introduction
of an unsymmetrical PN chelating ligand into such
dinuclear complexes is expected to provide a highly
selective reaction environment, because preferential
dissociation of the PN chelating ligand gives a specific
vacant coordination site on a metal center due to facile
dissociation of the nitrogen atom.5 In this paper, we
wish to report the synthesis of novel heterodinuclear
organoplatinum complexes having an unsymmetrical
PN ligand [2-(diphenylphosphino)triethylamine], where
Heterodinuclear complexes attract intrinsic interest
due to their possible cooperative effect of two different
metal centers in catalytic and stoichiometric chemical
reactions.1,2 We previously reported the synthesis of
heterodinuclear organoplatinum or -palladium com-
plexes containing a symmetrical bidentate ligand L2-
RM-M′Ln (L2 ) cod, dppe, tmeda, bpy, phen; R ) alkyl,
aryl; M ) Pt, Pd; M′Ln ) MoCp(CO)3, WCp(CO)3, Mn-
(CO)5, Re(CO)5, FeCp(CO)2, Co(CO)4).3,4 They show
* Corresponding author.
(1) (a) Braunstein, P., Oro, L. A., Raithby P. R., Eds. Metal Clusters
in Chemistry; Wiley-VCH: Weinheim, Germany, 1999. (b) Adams, R.
D., Cotton, F. A., Eds; Catalysis by Di- and Polynuclear Metal Cluster
Complexes; Wiley-VCH: New York, 1998. (c) Chetcuti, M. J . In
Comprehensive Organometallic Chemistry II; Adams, R. D., Ed.;
Pergamon Press: Oxford, U.K., 1995; Vol. 10. (d) Shriver, D. F., Kaesz,
H., Adams, R. D., Eds. The Chemistry of Metal Cluster Complexes;
VCH: New York, 1990.
(2) (a) Braunstein, P.; Morise, X. Organometallics 1998, 17, 540. (b)
Adams, R. D.; Barnard, T. S.; Wu, Z. Li. W.; Yamamoto, J . H. J . Am.
Chem. Soc. 1994, 116, 9103. (c) Braunstein, P.; Knorr, M.; Sta¨hreldt,
J . J . Chem. Soc., Chem. Commun. 1994, 1913.
(4) (a) Komiya, S.; Endo, I. Chem. Lett. 1988, 1709. (b) Fukuoka,
A.; Sadashima, T.; Endo, I.; Ohashi, N.; Kambara, Y.; Sugiura, T.;
Komiya, S. Organometallics 1994, 13, 4033. (c) Fukuoka, A.; Sa-
dashima, T.; Sugiura, T.; Wu, X.; Mizuho, Y.; Komiya, S. J . Organomet.
Chem. 1994, 473, 139. (d) Fukuoka, A.; Sugiura, T.; Yasuda, T.;
Taguchi, T.; Hirano, M.; Komiya, S. Chem. Lett. 1997, 329. (e) Fukuoka,
A.; Fukagawa, S.; Hirano, M.; Komiya, S. Chem. Lett. 1997, 377. (f)
Yasuda, T.; Fukuoka, A.; Hirano, M.; Komiya, S. Chem. Lett. 1998,
29. (g) Komiya, S.; Muroi, S.; Furuya, M.; Hirano, M. J . Am. Chem.
Soc. 2000, 122, 170. (h) Komine, N.; Hoh, H.; Hirano, M.; Komiya, S.
Organometallics 2000, 19, 5251. (i) Fukuoka, A.; Fukagawa, S.; Hirano,
M.; Koga, N.; Komiya, S. Organometallics 2001, 20, 2065.
(3) Abbreviations used in this article: cod ) 1,5-cyclooctadiene
(C8H12), dppe ) 1,2-bis(diphenylphosphino)ethane (Ph2PC2H4PPh2),
tmeda ) N,N,N′,N′-tetramethylethylenediamine (Me2NC2H4NMe2).
Free ligands are expressed by capital letters.
10.1021/om030477u CCC: $25.00 © 2003 American Chemical Society
Publication on Web 09/16/2003

Heterodinuclear Organoplatinum Complexes
Organometallics, Vol. 22, No. 21, 2003 4239
Sch em e 1
in THF at -30 °C gave novel heterodinuclear organo-
platinum complexes having an unsymmetrical PN ligand,
(Et2NC2H4PPh2-κ2N,P)RPt-MLn [MLn ) MoCp(CO)3, R
) Me (1), R ) Ph (2); MLn ) WCp(CO)3, R ) Me (3), R
) Ph (4); MLn ) Co(CO)4, R ) Me (5), R ) Ph (6)]
(Scheme 1).
Single crystals of complex 2 suitable for X-ray struc-
ture analysis were obtained by recrystallization from
toluene/hexane. The crystallographic data and selected
bond distances and angles are summarized in Tables 1
and 2, respectively, and an ORTEP drawing is depicted
in Figure 1.
reversible dissociation of the nitrogen atom is observed
by VT NMR. Facile insertion of carbon monoxide into
the Pt-C bond is demonstrated for these heterodi-
nuclear complexes with a hemilabile PN ligand.
The geometry around Pt in 2 is square planar, and
the Mo has a three-leg piano-stool type structure. These
structural features around both metals are consistent
with the electronic configurations of d8 Pt(II) and d6 Mo-
(0), since d8 complexes normally take a square-planer
geometry, and it is known that Mo(0) anionic complex
[MoCp(CO)3]- has a three-leg piano-stool type structure,
but Mo(II) complexes6 such as MoCl(CO)2(Ph2PN(Me)-
CH(Me)(Ph))6b and MoClCp(CO)36c usually have a four-
leg piano-stool type structure. The IR data also support
this electronic configurations (vide infra). The Pt-Mo
bond distance is 2.8989(9) Å, which is in a typical range
of Pt-Mo single bonds reported for dinuclear and cluster
complexes such as (cod)PhPt-MoCp(CO)3 [2.8320(12)
Å],4b Cp2Mo2Pt(µ-PPh2)(CO)5 [2.860(2), 2.872(2) Å],7 and
[CpMo(CO)2(µ-dppm)Pt(dppm)]+ [2.912(4) Å].8
Among three carbonyl ligands of Mo, two of them
(C(25)-O(1) and C(26)-O(2)) coordinate to the Pt center
from both above and below the Pt coordination plane.
The Mo(1)-C(25)-O(1) [162.6(9)°] and Mo(1)-C(26)-
O(2) [167.1(7)°] linkages are slightly bent, and Pt(1),
C(25), Mo(1), and C(26) are located in the same plane.
These facts imply that these two CO ligands have weak
interactions with Pt. This semibridging carbonyl group9
was also observed in some heterodinuclear complexes
such as (tmeda)Cu-MoCp(CO)39b and (Ph3P)2Rh-MoCp-
(CO)3.9c
Resu lts a n d Discu ssion
Syn th esis a n d Ch a r a cter iza tion of Heter od i-
n u clea r Or ga n op la tin u m Com p lexes Ha vin g a n
Un sym m etr ica l P N Liga n d . Heterodinuclear orga-
noplatinum complexes having an unsymmetrical PN
ligand were prepared by the metathetical reaction of
PtRCl(Et2NC2H4PPh2-κ2N,P) (R ) Me, Ph) with various
carbonylmetallates. Starting complexes PtRCl(Et2NC2H4-
PPh2-κ2N,P) were prepared by the ligand exchange
reaction of PtRCl(cod) with 2-(diphenylphosphino)tri-
ethylamine. The 31P{1H} NMR spectrum of PtMeCl(Et2-
NC2H4PPh2-κ2N,P) shows a singlet at δ 27.4 with a large
1J Pt-P value of 4862 Hz, suggesting that the phosphorus
atom is located in a position trans to the Cl ligand,
which has a smaller trans influence than the Me ligand.
1
In the H NMR of PtMeCl(Et2NC2H4PPh2-κ2N,P), the
methylene protons of the NCH2CH3 moiety appear as
two doublets of quartets at δ 3.14 and 3.40, indicating
that these methylene protons are diastereotopic. The
fact is an indication of rigid coordination of both
nitrogen and phosphorus atoms to the Pt center. The
Pt-Me resonance is observed at δ 0.58 as a doublet with
2
a
195Pt satellite (3J P-H ) 4.2 Hz, J Pt-H ) 76.0 Hz).
These spectroscopic data are comparable to that of a
similar complex, PtMeI(Me2NC2H4PPh2-κ2N,P), re-
ported by Schubert et al.5g Thus the starting complex
PtMeCl(Et2NC2H4PPh2-κ2N,P) has a square-planar ge-
ometry, as depicted in eq 1. Analogous spectroscopic
data are also obtained for PtPhCl(Et2NC2H4PPh2-
κ2N,P). Metathetical reactions of PtR(NO3)(Et2NC2H4-
IR spectra of Pt-Mo or Pt-W complexes (1-4) show
strong ν(CO) bands at ca. 1750-1900 cm-1, which are
similar to those for the known M(0) complexes [MoCp-
(CO)3]- and [WCp(CO)3]- rather than M(II) complexes
MoMeCp(CO)3 and WMeCp(CO)3.4b,10a,b Complexes 5
and 6 also show similar ν(CO) bands (1867-2026 cm-1
)
for the Co(-I) complex [Co(CO)4]-.4c,i,10b These data also
suggest that the oxidation states of the platinum and
connecting metals in 1-6 are likely to be Pt(II) and M(0)
(M ) Mo, W) or Co(-I), although the formal oxidation
states are Pt(I) and M(I) (M ) Mo, W) or Pt(I) and Co-
(0).
The 31P{1H} NMR spectra of these complexes show a
1
singlet with 195Pt satellites having a large J Pt-P value
PPh2-κ2N,P), prepared in situ from PtRCl(Et2NC2H4-
PPh2-κ2N,P) and AgNO3, with excess amounts of Na[MLn]
(ca. 4000-4600 Hz), suggesting that the phosphorus
atom of the PN ligand is located in a trans position to
(5) (a) Braunstein, P.; Naud, F. Angew. Chem., Int. Ed. 2001, 40,
680. (b) Anderson, G. K.; Lumetta, G. J . Organometallics 1985, 4, 1542.
(c) Dekker, G. P. C. M.; Buijs, A.; Elsevier, C. J .; Vrieze, K.; Smeets,
W. J . J .; Spek, A. L.; Wang, Y. F.; Stam, C. H. Organometallics 1992,
11, 1937. (d) Mauthner, K.; Slugovc, C.; Mereiter, K.; Schmid, R.;
Kirchner, K. Organometallics 1997, 16, 1956. (e) Hayashi, T.; Kumada,
M. Acc. Chem. Res. 1982, 15, 395. (f) Yoshida, H.; Shirakawa, E.;
Kurahashi, T.; Nakao, Y.; Hiyama, T. Organometallics 2000, 19, 5671.
(g) Pfeiffer, J .; Kickelbick, G.; Schubert, U. Organometallics 2000, 19,
62. (h) Mu¨ller, C.; Lachicotte, R. J .; J ones, W. D. Organometallics 2002,
21, 1975.
(6) (a) Poli, R. Organometallics 1990, 9, 1892. (b) Rxisner, G. M.;
Berkal, I. J . Chem. Soc., Chem. Commun. 1978, 691. (c) Bueno, C.;
Churchll, M. R. Inorg. Chem. 1981, 20, 2197.
(7) Blum, T.; Braunstein, P. Organometallics 1989, 8, 2504.
(8) Braunstein, P.; Bellefon, C. M.; Lanfranchi, M.; Tiripicchio, A.
Organometallics 1984, 3, 1772.
(9) (a) Crabtree, R. H.; Lavin, M. Inorg. Chem. 1986, 25, 805. (b)
Doyle, G.; Eriksen, A. Organometallics 1985, 4, 2201. (c) Carlton, L.;
Lindsell, W. E.; McCullough, K. J .; Preston, P. N. J . Chem. Soc., Dalton
Trans. 1984, 1693. (d) Sargent, A. L.; Hall, M. B. J . Am. Chem. Soc.
1989, 111, 1563.

4240 Organometallics, Vol. 22, No. 21, 2003
Ta ble 1. Cr ysta l Da ta for 2 a n d 21
Tsutsuminai et al.
2‚C7H8
21
empirical formula
fw
C
39H42MoNO4PPt
C30H41MoNO6P2Pt
864.63
894.77
cryst dimens (mm)
cryst syst
lattice params
a (Å)
0.36 × 0.27 × 0.27
0.60 × 0.56 × 0.28
triclinic
triclinic
12.329(3)
12.895(10)
b (Å)
13.802(2)
12.975(6)
c (Å)
11.781(4)
11.403(4)
R (deg)
97.88(2)
111.88(2)
80.27(2)
1827.4(9)
99.80(3)
95.46(5)
115.16(5)
1671(1)
â (deg)
γ (deg)
V (Å3)
space group
Z value
D
P1h (No. 2)
P1h (No. 2)
2
2
calc (g cm-3
)
1.626
1.718
F000
884.00
42.31
Mo Ka (λ ) 0.71069 Å)
graphite monochromated
852.00
46.74
Mo Ka (λ ) 0.71069 Å)
graphite monochromated
µ(Mo Ka) (cm-1
)
radiation
tempareture (°C)
scan type
2θmax (deg)
-33.0
20.0
ω-2θ
55.0
ω-2θ
55.0
8712
8364 (Rint ) 0.022)
direct methods
6228
334
0.048; 0.066
1.08
no. of reflns measd
no. of unique reflns
structure solution
no. of observations (I > 3.00σ(I))
no. of variables
8007
7666 (Rint ) 0.023)
direct methods
6660
370
0.029; 0.046
1.51
residuals: Ra; Rw
GOF
b
a
b
2
1/2
R ) ∑||Fo| - |Fc||/∑|Fo|. Rw ) [∑w(|Fo| - |Fc|)2/∑wFo
] .
spectra, the methylene protons of the NCH2CH3 moiety
for 5 and 6 are diastereotopic, suggesting rigid coordi-
nation of the nitrogen atom to the Pt center. In contrast,
the methylene protons of 1-4 appeared as a quartet or
a broad singlet, suggesting involvement of some dy-
namic processes (vide infra). Methylene signals of the
PCH2CH2N unit of 2 appear as a broad doublet and
singlet at δ 2.7 and 2.8 due to coupling with a neighbor-
ing P nucleus at 258 K. The peak of the lower field in
the doublet accidentally overlaps with the singlet, giving
two apparently broad singlets in a 1:3 ratio.
F igu r e 1. ORTEP drawing of (Et2NC2H4PPh2-κ2N,P)-
PhPt-MoCp(CO)3 (2). All hydrogen atoms and solvent are
omitted for clarity. Ellipsoids represent 50% probability.
Heterodinuclear organoplatinum complexes with a
bidentate nitrogen ligand, (tmeda-κ2N,N′)RPt-MoCp-
(CO)3 [R ) Me (7), Ph (8)], have also been synthesized
by the ligand exchange reaction of (cod)RPt-MoCp(CO)3
with TMEDA (eq 2). 1H NMR of 7 and 8 show two sharp
methyl resonances for TMEDA with Pt satellites, indi-
cating square-planar geometry at Pt with rigid coordi-
nation of TMEDA.
Ta ble 2. Selected Bon d Len gth s a n d An gles for 2
Bond Lengths (Å)
Pt(1)-Mo(1)
Pt(1)-P(1)
Mo(1)-C(25)
Mo(1)-C(27)
C(26)-O(2)
2.8989(9)
2.253(2)
1.979(8)
1.92(1)
Pt(1)-C(1)
Pt(1)-N(1)
Mo(1)-C(26)
C(25)-O(1)
C(27)-O(3)
2.001(9)
2.330(6)
1.975(10)
1.16(1)
1.17(1)
1.18(2)
Dyn a m ic Beh a vior of th e P N Ch ela te Liga n d .
Variable-temperature (VT) H NMR of 2 and 4 show
Bond Angles (deg)
1
Mo(1)-Pt(1)-C(1)
C(1)-Pt(1)-P(1)
Mo(1)-C(25)-O(1)
Mo(1)-C(27)-O(3)
Pt(1)-Mo(1)-C(26)
83.7(3) Mo(1)-Pt(1)-N(1)
90.2(3) N(1)-Pt(1)-P(1)
162.6(9) Mo(1)-C(26)-O(2)
103.2(2)
82.8(2)
167.1(7)
54.0(3)
dynamic behavior for the diastereotopic methylene
protons of the coordinating diethylamino moiety, while
other signals remain sharp. The methylene protons of
the ethyl group in 2 or 4 appear as a broad singlet or
quartet at room temperature. However, on lowering the
temperature as shown in Figure 2, the signal initially
broadens and then gradually splits into two peaks. At
175(1)
Pt(1)-Mo(1)-C(25)
58.2(2) Pt(1)-Mo(1)-C(27) 102.8(3)
MLn rather than Me, with a strong trans influence in
solution.4 The trans influence of Co is smaller than that
of Mo and W (see Experimental Section). In the 1H NMR

Heterodinuclear Organoplatinum Complexes
Organometallics, Vol. 22, No. 21, 2003 4241
F igu r e 3. Variable-temperature 1H NMR spectra of the
methyl and methylene regions in coordinating TMEDA of
8 in CD2Cl2.
COCD3, whereas in C6D5CD3 it does not coordinate or
very weakly coordinates to Pt. Despite this difference,
the observed ∆G273q values are very close to each other,
showing their good compensation effect of ∆Hq and ∆Sq
in this reaction.
On the other hand, the methylene resonance of 1
started to broaden at 233 K, but did not reach the
coalescence point even lowering to 180 K. The difference
of the dissociation rates in 1 and 2 may be attributable
to the difference of the trans effect of Me and Ph ligands;
the rate of Pt-N bond rupture trans to Me in 1 is much
faster than that trans to Ph in 2.
F igu r e 2. Variable-temperature 1H NMR spectra of the
diastereotopic methylene protons in the NEt2 moiety of 2
in CD3COCD3. (right) Observed spectra. (left) Simulated
spectra. × indicates impurity.
258 K, two doublets of quartets with equal intensity
appear due to couplings between the diastereotopic
geminal protons, which further couple to the methyl
protons.
In contrast, the methylene protons of the ethyl group
in Pt-Co complexes 5 and 6 appear as two well-
separated doublets of quartets (5: δ 2.93 and 3.23, 6: δ
3.01 and 3.28 in C6D5CD3) at ambient temperature,
indicating no such dynamic behavior. However, on
raising the temperature to 373 K in C6D5CD3, these
signals gradually broadened but did not reach complete
1
On the other hand, Cp resonanes in H NMR spectra
of 2 or 4 show no notable change in this temperature
range. This dynamic behavior is conveniently inter-
preted by the facile and reversible Pt-N bond rupture,
making the two diastereotopic methylene protons mag-
netically equivalent (eq 3). Such hemilabile behavior
had been reported for some mononuclear platinum or
palladium complexes with PN11 or bidentate nitrogen
ligands.12 From the line shape analysis of these VT
NMR spectra of 2, dissociation rate constants of the
amino group at various temperatures were estimated
in both acetone and toluene, giving kinetic parameters
coalescence. Kinetic parameters are also estimated from
q
these limited data as follows: ∆G273 ) 74.2 kJ mol-1
,
∆Hq ) 78.5 kJ mol-1, ∆Sq ) 15.4 J mol-1 K-1 for 5 and
∆G273 ) 76.8 kJ mol-1, ∆Hq ) 84.5 kJ mol-1, ∆Sq
28.3 J mol-1 K-1 for 6.
)
q
The large ∆Gq values for Pt-Co complexes compared
to Pt-Mo complexes imply that the Pt-N bond rupture
for Pt-Co complexes is more difficult than that for Pt-
Mo complexes. This may be due to a decrease in electron
density at Pt, making coordination of the nitrogen donor
to Pt stronger, since the Mo anion is a better donor than
Co. Although the difference of the estimated ∆Gq values
for 5 and 6 is small, it is an indication of trans effect of
the Me and Ph ligands.
as follows: ∆G273q ) 57.9 kJ mol-1, ∆Hq ) 49.8 kJ mol-1
,
∆Sq ) -29.7 J mol-1 K-1 in CD3COCD3 and ∆G273
)
q
56.4 kJ mol-1, ∆Hq ) 63.0 kJ mol-1, ∆Sq ) 24.2 J mol-1
K-1 in C6D5CD3. It is interesting to note that the ∆Sq
value obtained in CD3COCD3 is negative, but positive
in C6D5CD3, despite the dissociative nature of the
reaction. The fact suggests that the coordination of CD3-
COCD3 to the Pt center is involved in stabilizing the
resulting unstable three-coordinate species in CD3-
In the case of Pt-Mo analogues having a symmetrical
bidentate phosphine ligand, (dppe-κ2P,P′)MePt-MoCp-
(CO)3,4c such a dynamic process was not observed and
the DPPE ligand rigidly binds to the Pt center in a
bidentate fashion even at 70 °C. On the other hand, the
Pt-Mo complex with TMEDA (8) in CD2Cl2 shows
(10) (a) Piper, T. S.; Wilkinson, G. J . Inorg. Nucl. Chem. 1956, 3,
104. (b) Burlitch, J . M.; Theyson, T. W. J . Chem. Soc., Dalton Trans.
1974, 828.
(11) (a) la Torre, F. G.; J alo´n, F. A.; Lo´pez-Agenjo, A.; Manzano, B.
R.; Rodr´ıguez, A.; Strum, T.; Weissensteiner, W.; Mart´ınez-Ripoll, M.
Organometallics 1988, 7, 4634. (b) Amatore, C.; Fuxa, A.; J utand, A.
Chem. Eur. J . 2000, 6, 1474.
(12) (a) Romeo, R.; Scolaro, L. M.; Nastasi, N.; Arena, G. Inorg.
Chem. 1996, 35, 5087. (b) Delis, J . G. P.; Aubel, P. G.; Vrieze, K.; van
Leeuwen, P. W. N. M.; Veldman, N.; Spek, A. L.; van Neer, F. J . R.
Organometallics 1997, 16, 2948. (c) Gogoll, A.; O¨ rnebro, J .; Grennberg,
H.; Ba¨ckvall, J . E. J . Am. Chem. Soc. 1994, 116, 3631.
1
dynamic behavior in its VT H NMR spectra (Figure 3),
though TMEDA is not unsymmetrical.
The proton NMR resonances of the methylene protons
of TMEDA are observed as two inequivalent multiplets
at δ 2.74 and 2.98 at ambient temperature, due to
different trans ligands of Me and Mo. At temperature
below 263 K, the resonances begin to broaden and

4242 Organometallics, Vol. 22, No. 21, 2003
Tsutsuminai et al.
Sch em e 2
decoalesce at 213 K. On further lowering the tempera-
ture, two sets of signals gradually appeared at 183 K,
each set consisting of a triplet and a doublet, probably
due to selective couplings between geminal and vicinal
protons, although one doublet signal at higher field is
obscured by overlapping with large methyl signals of
TMEDA. One of the couplings between two vicinal
protons may be negligible due to a coincidental H-C-
C-H dihedral angle of 90° by the restricted ligand
conformation. It is also notable that the dynamic process
is independent of addition of free TMEDA. This obser-
vation indicates that this dynamic process does not
involve dissociation of the nitrogen atom from the Pt
center, but an intramolecular process. Therefore for the
present dynamic behavior, a mechanism involving a
facile equatorial/axial hydrogen site exchange process
due to interconversion between the λ and δ conformers
is proposed (eq 4).13
195Pt satellites, the 2J Pt-H coupling constant value being
61 Hz for 9, which is smaller than that for 1 (74 Hz).
The difference reflects a stronger trans influence of the
CO ligand than the nitrogen ligand. In the 13C{1H}
NMR spectroscopy of 9, one of the carbonyl carbons
appeared as a singlet at δ 189.2 (1J Pt-C ) 1031 Hz) with
1
195Pt satellites. The J Pt-C value is comparable to the
coupling constant of 906 Hz in PtPhCl(CO)(PMePh2),
where CO is located cis to the phosphorus atom and
trans to the Ph group.14 The IR spectrum of 9 shows a
strong ν(CO) band at 2039 cm-1. The molar electric
conductivity of 9 in THF was very low, suggesting that
9 is not an ionic complex but a neutral one. From these
results, the N atom is not coordinated to Pt as shown
in eq 5, and CO is located at the site cis to P and trans
to the methyl group. However, the symmetrical biden-
tate phosphine analogue (dppe-κ2P,P′)MePt-MoCp-
4c
(CO)3 did not react at all with CO under the same
reaction conditions. On the other hand, the reaction of
the Pt-Mo dinuclear complex 7 having a TMEDA ligand
with CO (1 atm) in CD3COCD3 did not cause a partial
displacement of the NMe2 group by CO, but resulted in
formation of the cationic complex [PtMe(CO)(tmeda-
κ2N,N′)]+[MoCp(CO)3]- (13) with a small amount of
uncharacterized “Pt-Me” species [δ 0.96, 2J Pt-H ) 62.8
Hz]. The “Pt-Me” species is tentatively assigned as
[PtMe(CO)3]+[MoCp(CO)3]-, since complete liberation of
TMEDA was followed. However, addition of 2 equiv of
TMEDA completely suppressed the formation of the
“Pt-Me” species and formation of only 13 was observed.
In the 1H NMR of 13, the chemical shift of the Cp
resonance was identical to anionic complex Na[MoCp-
(CO)3]. Two methyl resonances for TMEDA are observed
at δ 2.94 and 3.24 with 195Pt satellites (3J Pt-H ) 39.4
and 22.8 Hz, respectively), and the Pt-Me signal appears
As described earlier, the facile intramolecular dis-
sociation process of the N atom in the PN ligand of 2 is
1
frozen out in the H NMR at 258 K. However, further
lowering of the temperature to 213 K caused another
line broadening of both methylene signals of the ethyl
and PC2H4N units. The dynamic behavior may also be
originated from the fast conformation change of the
methylene chain, although observation of the complete
rigid structure is not successful under the observed
temperature.
R ea ct ion of H et er od in u clea r Com p lexes w it h
CO. When 1-4 were treated with CO (1 atm) in acetone
or benzene, the coordinating nitrogen atom of the PN
ligand was readily displaced by CO to give (Et2NC2H4-
PPh2-κ1P)(CO)RPt-MCp(CO)3 (9-12) (eq 5).
2
at δ 0.90 with a J Pt-H of 69.1 Hz. These observations
indicate that the resulting cationic complex has a
square-planar geometry, as depicted in eq 6. Preferen-
tial formation of the cationic complex may possibly be
due to stabilization of the cationic complex with TMEDA
by its strong electron donation.
Heating of the carbonyl complex 9 in C6D6 at 70 °C
for 1 day caused insertion of CO into the Pt-Me bond,
giving the acetyl complex (Et2NC2H4PPh2-κ2N,P)(Me-
CO)Pt-MoCp(CO)3 (14) as an equilibrium mixture with
9 in a 3:2 ratio (Scheme 2). Further heating of the
mixture did not change the molar ratio but caused only
some decomposition. On the other hand, heating of the
In the 1H NMR of 9, the chemical shift of the
methylene group of the NCH2CH3 moiety was observed
to be very close to that of free Et2NC2H4PPh2. The
methyl group attached to Pt appeared as a singlet with
(13) (a) de Graaf, W.; Boersma, J .; Smeets, W. J . J .; Spek, A. L.;
van Koten, G. Organometallics 1989, 8, 2907. (b) Hughes, R. P.; Overby,
J . S.; Williamson, A.; Lam, K.; Concolino, T. E.; Rheingold, A. L.
Organometallics 2000, 19, 5190.
(14) (a) Anderson, G. K.; Cross, R. J . Acc. Chem. Res. 1984, 17, 67.
(b) Anderson, G. K.; Cross, R. J . Chem. Soc., Dalton Trans. 1979, 1246.

Heterodinuclear Organoplatinum Complexes
Organometallics, Vol. 22, No. 21, 2003 4243
Sch em e 3
independently prepared acetyl complex 14 from Pt-
(COMe)Cl(Et2NC2H4PPh2-κ2N,P) and Na[MoCp(CO)3] at
70 °C in C6D6 for 1 day also gave the same mixture of
9 and 14 in the same ratio. This indicates that the slow
equilibration of this reversible CO insertion is taking
place at 70 °C.
On the other hand, reaction of the Pt-Co complex
having a PN ligand 5 with CO gave only the acetyl
complex 15. However, monitoring the reaction of 5 with
CO by 1H and 31P{1H} NMR spectroscopy in C6D6 at 30
°C revealed the initial formation of the carbonyl complex
16 followed by slow formation of 15, indicating a
successive reaction mechanism (Scheme 3). The CO
insertion reaction of 5 was significantly faster than that
of the DPPE analogue (dppe-κ2P,P′)MePt-Co(CO)4.4e,i
When 5 was treated with 1 atm of CO in C6D6 at 30 °C
for 24 h, the corresponding acetyl complex 15 was
obtained quantitatively, whereas the reaction of (dppe-
κ2P,P′)MePt-Co(CO)4 with CO under the same condi-
tions gave the corresponding acetyl complex (dppe-
κ2P,P′)(MeCO)Pt-Co(CO)4 in only 26% yield. The
following two mechanisms are proposed for this CO
insertion from 16: (i) Methyl migration from Pt to Co
initially takes place, followed by fast CO insertion into
the Co-Me bond, and then migration of the resulting
acetyl group at Co to Pt as previously reported in CO
insertion into the Me-Pd-Co complex.4i (ii) Initial
ionization takes place by heterolytic cleavage of the Pt-
Co bond, and then CO coordinates to Pt cis to the Me
group, leading to facile insertion. Other mechanisms,
including a five-coordinate intermediate as reported in
mononuclear Pt or Pd complexes or direct initial isomer-
ization from trans to cis followed by insertion, are also
possible as reaction pathways.5c,14a,15
F igu r e 4. ORTEP drawing of [PtMe{P(OMe)3}(Et2NC2H4-
PPh2-κ2N,P)]+[MoCp(CO)3]- (21). All hydrogen atoms are
omitted for clarity. Ellipsoids represent 50% probability.
Ta ble 3. Selected Bon d Len gth s a n d An gles for 21
Bond Lengths (Å)
Pt(1)-P(1)
2.306(1)
2.212(4)
1.919(5)
1.912(5)
2.369(6)
2.379(6)
1.178(7)
1.205(7)
Pt(1)-P(2)
2.175(1)
2.091(6)
1.936(6)
2.381(5)
2.377(7)
2.390(6)
1.150(8)
Pt(1)-N(1)
Mo(1)-C(23)
Mo(1)-C(25)
Mo(1)-C(27)
Mo(1)-C(29)
O(4)-C(23)
O(6)-C(25)
Pt(1)-C(1)
Mo(1)-C(24)
Mo(1)-C(26)
Mo(1)-C(28)
Mo(1)-C(30)
O(5)-C(24)
Bond Angles (deg)
P(1)-Pt(1)-P(2)
95.90(5) P(1)-Pt(1)-N(1)
84.1(1)
90.6(2)
89.5(2)
178.1(5)
178.2(6)
P(2)-Pt(1)-C(1)
89.4(2)
88.2(3)
86.1(3)
178.2(7)
N(1)-Pt(1)-C(1)
C(23)-Mo(1)-C(24)
C(24)-Mo(1)-C(25)
Mo(1)-C(24)-O(5)
C(23)-Mo(1)-C(25)
Mo(1)-C(23)-O(4)
Mo(1)-C(25)-O(6)
Rea ction of 1 w ith Ter tia r y P h osp h in e Liga n d s.
When 1 was treated with various tertiary phosphines
(PR3 ) Et2NC2H4PPh2, PMe3, PEt3, PPh3, P(OMe)3),
heterolytic cleavage of the metal-metal bond took place
to give ionic complexes 17-21 (eq 7).
remained intact. This fact prevented us from using the
ligand displacement method for the preparation of
heterodinuclear complexes with a PN ligand. Occur-
rence of preferential ionization of the Pt-Mo bond
rather than ligand displacement on interaction of het-
erodinuclear complexes with tertiary phosphine ligands
is of interest. This could be due to effective stabilization
of cationic platinum(II) species by coordination of phos-
phines, although a more detailed investigation is needed
for a complete understanding of this reaction selectivity.
Single crystals of complex 21 suitable for X-ray
structure analysis were obtained by recrystallization
from THF/ether. The crystal data, selected bond lengths
and distances, and an ORTEP drawing are shown in
Tables 1 and 3 and Figure 4, respectively.
The geometry around Pt is square planar, in which
two P atoms coordinate to Pt in a cis fashion. The Mo
moiety has a three-leg piano-stool geometry. Three Mo-
C-O angles are almost linear and the Pt-Mo distance
is 6.54 Å, indicating no M-M bond. The result is
consistent with the ionic structure involving the Pt
cation and Mo anion. 1H NMR of 17-21 shows two
diasteteotopic methylene protons of NCH2CH3 at δ 3.3-
Such ionization reactions are frequently observed in
the reactions of square-planar d8 transition metal
complexes and heterodinuclear complexes with tertiary
phosphines.4b,d,16,17 It is interesting to note that reaction
of (cod)MePt-MoCp(CO)3 with a stoichiometric amount
of Et2NCH2H4PPh2 caused selective ioinization to give
17 in 50% yield and half of the starting complex
(15) Garrou, P. E.; Heck, R. F. J . Am. Chem. Soc. 1976, 98, 4115.
(16) (a) Clark, H. C.; Ruddick, J . D. Inorg. Chem. 1970, 9, 1226. (b)
Hooton, K. A. J . Chem. Soc. A 1970, 1896. (c) Komiya, S.; Kochi, J . K.
J . Am. Chem. Soc. 1976, 98, 7599.

4244 Organometallics, Vol. 22, No. 21, 2003
Tsutsuminai et al.
Sch em e 4
3.7, indicating rigid bidentate coordination of the PN
ligand to the electron-deficient cationic Pt center. The
Pt-Me group appears as a doublet of doublets with 195Pt
satellites, indicating the existence of two magnetically
inequivalent cis phosphorus nuclei at Pt. Consistently,
the 31P{1H} NMR shows two doublets with a small cis
coupling constant (2J P-P ) 12 Hz) having 195Pt satellites,
the value being similar to that reported for cis-PtPhCl-
(PMe3)2 (14.6 Hz).18a The molar electric conductivity of
one of these complexes, 17, is found to be very large (Λ
) 12.6 S cm2 mol-1), supporting its ionic structure.
To reveal the reaction path of the formation of the
cis product, time courses of the reaction of 1 were
1
followed by H NMR spectroscopy in CD3COCD3 at 50
°C. Immediately after addition of 1 equiv of PPh3,
ionization took place, but the product was only the trans
isomer 22. Then the cis product 20 was slowly formed
as shown in Scheme 4.
31P{1H} NMR of the trans isomer 22 showed two
F igu r e 5. Time-yield curves for trans-cis isomerization
from 22 to 20. Conditions: temp ) 30 °C, [22] ) 1.5 × 10-2
M, solvent ) CD3COCD3. [PPh3]/[22] ) 0 (9), 2 (b), 4 ([).
2
doublets with 195Pt satellites. The observed large J P-P
value of 405 Hz is consistent with the trans configura-
tion of the two P nuclei and is comparable to that
reported for [PtMe(PPh3)(dppe)]+I- (2J P-P ) 381.4 Hz).18b
and heating of the solution at 50 °C for a day, 24 was
completely converted into 25, though a neutral inter-
mediate complex having a κ1-coordinated TMEDA ligand
was not detected.
1
In the H NMR, the methyl group on Pt is observed as
a doublet of doublets (3J P-H ) 8.1, 6.6 Hz) with a 195Pt
satellite. The chemical shift of the Cp resonance of the
trans isomer (22) was identical to that of the cis isomer
(20). When 5 equiv of PPh3 was added to the solution
of 1, the cis-trans isomerization rate was significantly
accelerated, though the ionization process was not
affected at all (Figure 5). The results suggest that the
trans-cis isomerization process involves a prior associa-
tion step of the phosphorus ligand to 22, giving a five-
coordinate intermediate.
Su m m a r y
In the present study, synthesis of a series of novel
heterodinuclear organoplatinum complexes having an
unsymmetrical PN ligand (2-(diphenylphosphino)tri-
ethylamine) or bidentate nitrogen ligand (N,N,N′,N′-
tetramethylethylenediamine) is described. Dynamic
behavior arising from a facile reversible Pt-N bond
rupture was observed for complexes with a PN ligand.
This hemilabile nature of the PN ligand leads to the
high reactivity of (Et2NC2H4PPh2-κ2N,P)RPt-MCp(CO)3
1-4 toward CO to give (Et2NC2H4PPh2-κ1P)(CO)RPt-
MCp(CO)3 9-12 having a monodentate phosphorus
coordination. It is interesting to note that reaction of
dinuclear complexes 1-4 having hemilabile PN ligands
with CO caused substitution of the N ligand, whereas
interaction with phosphorus ligands induced heterolytic
cleavage of the Pt-Mo bond, giving ionic complexes.
This could be due to the strong back-bonding property
of CO on coordination of the stabilizing neutral complex
(Et2NC2H4PPh2-κ1P)(CO)RPt-MoCp(CO)3. In contrast,
strong electron donation to Pt by the phosphorus ligand
may favor an electron-deficient cationic Pt center rather
than the possible neutral complex as above. Facile CO
insertion was observed for the Pt-Co complex having
a PN ligand. The reaction could involve a similar
mechanism of a facile CO insertion process of (dppe-
κ2P,P′)MeM-Co(CO)4 (M ) Pd, Pt),4e,i where an initial
alkyl migration from Pd (or Pt) to Co followed by
insertion of CO at Co and oxidative addition of acetyl-
From these observations, the reaction of 1 with a
tertiary phosphine ligand is considered to proceed by a
facile initial heterolytic M-M′ bond cleavage by coor-
dination of the phosphine ligand to give the trans isomer
22. Then the trans isomer 22 slowly isomerizes to the
cis isomer 20 by an associative process.
It is interesting to note that the reaction of (dppe-
κ2P,P′)MePt-MoCp(CO)3 with PPh3 also caused hetero-
lytic M-M′ bond cleavage to give [PtMe(PPh3)(dppe-
κ2P,P′)]+[MoCp(CO)3]- (23).4d On the other hand, the
reaction of the TMEDA analogue 7 with 3 equiv of PPh3
in CD3COCD3 gave a mixture of two ionic complexes,
[PtMe(PPh3)(tmeda)]+[MoCp(CO)3]- (24) and [PtMe(P-
Ph3)3]+[MoCp(CO)3]- (25), in 12% and 88% yield, re-
spectively. Upon addition of excess PPh3 to the mixture
(17) (a) Bearman, P. S.; Smith, A. K.; Tong, N. C.; Whyman, R.
Chem. Commun. 1996, 2061. (b) Schubart, M.; Mitchell, G.; Gade, L.
H.; Scowen, I. J .; McPartlin, M. Chem. Commun. 1999, 223. (c) Roberts,
D. A.; Mercer, W. C.; Geoffroy, G. L.; Pierpont, C. G. Inorg. Chem. 1986,
25, 1439.
(18) (a) Kayaki, Y.; Tsukamoto, H.; Kaneko, M.; Shimizu, I.; Yama-
moto, A.; Tachikawa, M.; Nakajima, T. J . Organomet. Chem. 2001,
622, 199. (b) You, Y. J .; Chem. J . T.; Cheng, M. C.; Wang, Y. Inorg.
Chem. 1991, 30, 3621.

Heterodinuclear Organoplatinum Complexes
Organometallics, Vol. 22, No. 21, 2003 4245
(82.0 mg, 0.147 mmol). Anal. Calcd for C20H27ClNOPPt: C,
cobalt species to Pd (or Pt) gives the insertion product.
Ligand transfer of the CO ligand from Pt or Co and re-
coordination of the N atom of the PN ligand should also
be involved in this process, although a further detailed
investigation is required. Introduction of the hemilabile
PN ligand would provide a highly reactive specific
reaction site not only in the heterodinuclear complex
but also in various transition metal complexes.
1
42.98; H, 4.87; N, 2.51. Found: C, 42.84; H, 4.84; N, 2.46. H
3
NMR (C6D6): δ 1.27 (6H, t, J H-H ) 6.9 Hz, Me (N-Et)), 1.96
(3H, s, Pt-COMe), 2.4-2.7 (4H, m, CH2-CH2), 3.03 (2H, dq,
3
2J H-H ) 13.0 Hz, J H-H ) 6.9 Hz, CH2 (N-Et)), 3.25 (2H, dq,
3
2J H-H ) 13.0 Hz, J H-H ) 6.9 Hz, CH2 (N-Et)), 7.5 (6H, m, m-
and p-Ph), 7.7 (4H, m, o-Ph). 31P{1H} NMR (C6D6): δ 10.2 (s,
1J Pt-P ) 5031 Hz). IR (KBr, cm-1): 715(m), 1099(m), 1435(m),
1634(s).
(Et2NC2H4P P h 2-K2N,P )MeP t-MoCp (CO)3 (1). PtMeCl-
(Et2NC2H4PPh2-κ2N,P) (211 mg, 0.398 mmol) and AgNO3 (90
mg, 0.52 mmol) were dissolved in THF, and the suspension
was stirred for one night at room temperature to give a pale
yellow solution with a white precipitate of AgCl. The precipi-
tate was filtered off, and the resulting solution was added
dropwise to a THF solution of Na[MoCp(CO)3] (161 mg, 0.598
mmol) under -70 °C. Then the mixture was stirred for 3 h at
-30 °C. All volatile matters were removed by evaporation, and
the resulting brown-yellow solid was extracted with toluene
at -20 °C. After the filtered solution was concentrated under
reduced pressure at -20 °C, excess hexane was added to give
an analytically pure yellow powder. The product was filtered,
washed with hexane, and dried under vacuum at room
temperature. Yield: 87% (258 mg, 0.348 mmol). Anal. Calcd
for C27H32MoNO3PPt: C, 43.79; H, 4.36; N, 1.89. Found: C,
43.88; H, 4.36; N, 1.81. Molar electric conductivity Λ (THF,
20 °C): 0.9 S cm2 mol-1. 1H NMR (CD3COCD3): δ 0.38 (3H, d,
Exp er im en ta l Section
All manipulations were carried out under a dry nitrogen or
argon atmosphere using standard Schlenk and vacuum line
techniques. Solvents were refluxed over and distilled from
appropriate drying agents under N2: benzene, toluene, hexane,
THF, and Et2O from sodium benzophenone ketyl; acetone from
Drierite; CH2Cl2 from P2O5. Deuterated solvents were degassed
by three freeze-pump-thaw cycles and then vacuum trans-
ferred from appropriate drying agents (C6D6 and C6D5CD3 from
sodium wire; CDCl3 and CD2Cl2 from P2O5, CD3COCD3 from
Drierite). PtMeCl(cod),19 PtPhCl(cod),19 Na[MoCp(CO)3],10 Na-
[WCp(CO)3],10 Na[Co(CO)4],20 and Et2NC2H4PPh2 were pre-
21
pared according to literature procedures. NMR spectra were
recorded on a J EOL LA-300 spectrometer (300.4 MHz for 1H,
121.6 MHz for 31P, and 75.5 MHz for 13C) with chemical shifts
1
reported in ppm downfield from TMS for H and 13C and from
85% H3PO4 in D2O. IR spectra were recorded on a J ASCO FT/
IR-410 spectrometer using KBr disks. Elemental analyses were
carried out with a Perkin-Elmer 2400 series II CHN analyzer.
Molar electrical conductivity was measured on a TOA Conduct
Meter CM 7B.
2
3
3J P-H ) 5.4 Hz, J Pt-H ) 74 Hz, Pt-Me), 1.18 (6H, t, J H-H
)
7.0 Hz, Me (N-Et)), 2.2-2.8 (4H, m, CH2-CH2), 3.4 (4H, q, 3J H-H
) 6.9 Hz, CH2 (N-Et)), 5.24 (5H, s, Cp), 7.50-7.60 (6H, m, m-
and p-Ph), 7.84-7.94 (4H, m, o-Ph). 31P{1H} NMR (CD3-
1
COCD3): δ 40.3 (s, J Pt-P ) 4208 Hz). IR (KBr, cm-1): 503-
P t MeCl(E t 2NC2H4P P h 2-K2N,P ). 2-(Diphenylphosphino)-
triethylamine Et2NC2H4PPh2 (0.63 mL, 3.0 mmol) was added
to a benzene solution of PtMeCl(cod) (1.049 g, 2.972 mmol).
After the mixture was stirred for 1 h at room temperature,
the resulting white-yellow precipitate was filtered and washed
with hexane. The product was recrystallized from CH2Cl2 at
-30 °C to give light yellow crystals of PtMeCl(Et2NC2H4PPh2-
(m), 1102(m), 1435(m), 1761(vs), 1788(vs), 1879(s).
The following heterodinuclear complexes 2-6 were prepared
analogously as described for 1.
(Et2NC2H4P P h 2-K2N,P )P h P t-MoCp (CO)3 (2). A pale or-
ange powder was formed. Yield: 77%. Anal. Calcd for C32H34
-
MoNO3PPt: C, 47.89; H, 4.27; N, 1.75. Found: C, 47.52; H,
3
4.50; N, 1.50. 1H NMR (CD3COCD3): δ 1.21 (6H, t, J H-H
)
κ2N,P). Yield: 76% (1.21 g, 2.28 mmol). Anal. Calcd for C19H27
-
7.2 Hz, Me (N-Et)), 2.7-2.9 (4H, m, CH2-CH2), 3.4 (4H, brs,
CH2 (N-Et)), 5.20 (5H, s, Cp), 6.4-6.5 (3H, m, m- and p-Ph
ClNPPt: C, 42.98; H, 5.13; N, 2.64. Found: C, 42.57; H, 5.01;
N, 2.66. 1H NMR (CDCl3): δ 0.58 (3H, d, 3J P-H ) 4.2 Hz, 2J Pt-H
3
4
3
(Pt-Ph)), 6.93 (2H, m, J H-H ) 8.4 Hz, J H-H ) 1.5 Hz, J Pt-H
) 56 Hz, o-Ph (Pt-Ph)), 7.3-7.6 (10H, m, Ph). 31P{1H} NMR
(CD3COCD3): δ 34.4 (s, 1J Pt-P ) 4087 Hz). IR (KBr, cm-1): 739-
(m), 1434(m), 1792(vs), 1891(s).
3
) 76.0 Hz, Pt-Me), 1.25 (6H, t, J H-H ) 7.0 Hz, Me (N-Et)),
2.4-2.8 (4H, m, CH2-CH2), 3.14 (2H, dq, 2J H-H ) 12.9 Hz, 3J H-H
) 7.0 Hz, CH2 (N-Et)), 3.40 (2H, dq, 2J H-H ) 12.9 Hz, 3J H-H
)
7.0 Hz, CH2 (N-Et)), 7.4-7.6 (10H, m, Ph). 31P{1H} NMR
(Et2NC2H4P P h 2-K2N,P )MeP t-WCp (CO)3 (3). Na[WCp-
(CO)3] was used instead of Na[MoCp(CO)3]. Yellow powder.
Yield: 87%. Anal. Calcd for C27H32NO3PPtW: C, 43.16; H, 3.85;
1
(CDCl3): δ 27.4 (s, J Pt-P ) 4862 Hz).
P tP h Cl(Et2NC2H4P P h 2-K2N,P ). The same procedure was
used as described for PtMeCl(Et2NC2H4PPh2-κ2N,P). Reaction
of PtPhCl(cod) (578.2 mg, 1.391 mmol) with Et2NC2H4PPh2
(0.300 mL, 1.41 mmol) gave 483.3 mg (0.8150 mmol, 59%) of
PtPhCl(Et2NC2H4PPh2-κ2N,P). Anal. Calcd for C24H29ClN-
PPt: C, 48.61; H, 4.93; N, 2.36. Found: C, 48.50; H, 4.79; N,
1
N, 1.57. Found: C, 43.19; H, 4.18; N, 1.42. H NMR (C6D6): δ
3
3
0.88 (6H, t, J H-H ) 7.2 Hz, Me (N-Et)), 0.98 (3H, d, J P-H
)
2
6.3 Hz, J Pt-H ) 79 Hz, Pt-Me), 1.8-2.1 (4H, m, CH2-CH2),
3.29 (4H, q, 3J H-H ) 7.2 Hz, CH2 (N-Et)), 5.05 (5H, s, Cp), 7.0-
7.16 (6H, m, m- and p-Ph), 7.75-7.83 (4H, m, o-Ph). 31P{1H}
NMR (C6D6): δ 41.9 (s, 1J Pt-P ) 4149 Hz). IR (KBr, cm-1): 501-
(m), 693(m), 1103(m), 1434(m), 1779(vs), 1884(s), 1905(s).
(Et2NC2H4P P h 2-K2N,P )P h P t-WCp (CO)3 (4). Pale yellow
powder. Yield: 90%. Anal. Calcd for C32H34NO3PPtW: C,
1
3
2.24. H NMR (CDCl3): δ 1.36 (6H, t, J H-H ) 7.0 Hz, Me (N-
2
Et)), 2.40-2.75 (4H, m, CH2-CH2), 3.20 (4H, dq, J H-H ) 13.0
3
2
Hz, J H-H ) 7.0 Hz, CH2 (N-Et)), 3.46 (4H, dq, J H-H ) 13.0
3
Hz, J H-H ) 7.0 Hz, CH2 (N-Et)), 6.65-6.69 (3H, m, m- and
3
p-Ph (Pt-Ph)), 6.98 (2H, m, J Pt-H ) 46.0 Hz, o-Ph (Pt-Ph)),
1
43.16; H, 3.85; N, 1.57. Found: C, 43.19; H, 4.18; N, 1.42. H
7.30-7.55 (10H, m, Ph). 31P{1H} NMR (CDCl3): δ 23.3 (s, 1J Pt-P
) 4774 Hz).
NMR (CD3COCD3): δ 1.21 (6H, t, 3J H-H ) 7.2 Hz, Me (N-Et)),
3
2.6-2.9 (4H, m, CH2-CH2), 3.29 (4H, q, J H-H ) 7.2 Hz CH2
P t(COMe)Cl(Et2NC2H2P P h 2-K2N,P ). PtMeCl(Et2NC2H4-
PPh2-κ2N,P) (119.5 mg, 0.2251 mmol) was dissolved in CH2-
Cl2, and the solution was evacuated. Carbon monoxide (0.1
MPa) was then introduced. After stirring the solution for 5
days, the dark green reaction mixture was treated with
activated charcoal and filtered to give a pale yellow solution.
The solution was concentrated under reduced pressure and
recrystallized from a mixture of CH2Cl2/hexane. Yield: 65%
(N-Et)), 5.05 (5H, s, Cp), 6.4-6.6 (6H, m, m- and p-Ph (Pt-
Ph)), 6.94 (4H, m, 3J H-H ) 8.1 Hz, 4J H-H ) 1.2 Hz, 3J Pt-H ) 56
Hz, o-Ph (Pt-Ph)), 7.37-7.63 (10H, m, Ph). 31P{1H} NMR (CD3-
1
COCD3): δ 37.5 (s, J Pt-P ) 4058 Hz). IR (KBr, cm-1): 1104-
(m), 1436(m), 1780(vs), 1887(s), 1906(s).
(Et2NC2H4P P h 2-K2N,P )MeP t-Co(CO)4 (5). Na[Co(CO)4]
was used instead of Na[MoCp(CO)3]. Pale yellow powder.
Yield: 88%. Anal. Calcd for C23H27CoNO4PPt: C, 41.45; H,
4.08; N, 2.10. Found: C, 41.85; H, 4.21; N, 2.08. 1H NMR
(19) Clark, H. C.; Manzer, L. E. J . Organomet. Chem. 1973, 59, 411.
(20) Ruff, J . K.; Schlientz, W. J . Inorg. Synth. 1957, 15, 192.
(21) Bianco, V. D.; Doronzo, S. Inorg. Synth. 1976, 16, 155.
3
(C6D6): δ 0.79 (6H, t, J H-H ) 7.2 Hz, Me (N-Et)), 0.91 (3H, d,
2
3J P-H ) 4.1 Hz, J Pt-H ) 73 Hz, Pt-Me), 1.79-1.93 (4H, m,

4246 Organometallics, Vol. 22, No. 21, 2003
Tsutsuminai et al.
3
CH2-CH2), 2.90 (2H, dq, 2J H-H ) 14.1 Hz, 3J H-H ) 7.2 Hz, CH2
d, J H-H ) 7.5 Hz, o-Ph (Pt-Ph)), 7.4 (4H, m, o-Ph). 31P{1H}
2
3
1
(N-Et)), 3.23 (2H, dq, J H-H ) 14.1 Hz, J H-H ) 7.2 Hz, CH2
(N-Et)), 7.0-7.2 (6H, m, m- and p-Ph), 7.55-7.63 (4H, m, o-Ph).
NMR (C6D6): δ 18.9 (s, J Pt-P ) 2762 Hz).
(Et2NC2H4P P h 2-K1P )(CO)MeP t-WCp(CO)3 (11). The same
procedure was used as described for 9. 3 was used instead of
1. Yellow powder. Yield: 13%. Anal. Calcd for C28H32NO4-
PPtW: C, 39.27; H, 3.77; N, 1.64. Found: C, 38.94; H, 4.25;
1
31P{1H} NMR (C6D6): δ 30.7 (s, J Pt-P ) 4565 Hz). IR (KBr,
cm-1): 1106(m), 1436(m), 1867(s), 1897(s), 1936(vs), 2017(vs).
(Et2NC2H4P P h 2-K2N,P )P h P t-Co(CO)4 (6). Orange plates
N, 1.63. 1H NMR (C6D6): δ 0.94 (6H, t, J H-H ) 7.2 Hz, Me
3
from benzene/hexane. Yield: 35%. Anal. Calcd for C28H29
-
3
2
(N-Et)), 1.58 (3H, d, J P-H ) 8.7 Hz, J Pt-H ) 61 Hz, Pt-Me),
2.40 (4H, q, J H-H ) 7.2 Hz, CH2 (N-Et)), 2.52-3.10 (4H, m,
CH2-CH2), 4.90 (5H, s, Cp), 6.9-7.1 (6H, m, m- and p-Ph),
7.51-7.58 (4H, m, o-Ph). 31P{1H} NMR (C6D6): δ 26.8 (s, 1J Pt-P
) 2811 Hz). IR (KBr, cm-1): 694(m), 1101(m), 1435(m), 1832-
(vs), 1931(vs), 2037(s).
CoNO4PPt: C, 46.16; H, 4.01; N, 1.92. Found: C, 46.19; H,
3
3
3.89; N, 1.96. 1H NMR (CD3COCD3): δ 1.32 (6H, t, J H-H
)
7.5 Hz, Me (N-Et)), 2.7-2.9 (4H, m, CH2-CH2), 3.33 (2H, dq
3
2J H-H ) 14.4 Hz, J H-H ) 7.5 Hz, CH2 (N-Et)), 3.49 (2H, dq,
3
2J H-H ) 14.4 Hz, J H-H ) 7.5 Hz, CH2 (N-Et)), 6.4-6.5 (6H,
3
4
m, m- and p-Ph (Pt-Ph)), 6.91 (4H, m, J H-H ) 7.8 Hz, J H-H
(Et2NCH2CH2P P h 2-K1P )(CO)P h P t-WCp (CO)3 (12). The
same procedure was used as described for 10. 4 was used
instead of 2. Complex 12 was characterized spectroscopically.
) 1.5 Hz, 3J Pt-H ) 49 Hz, o-Ph (Pt-Ph)), 7.4-7.6 (10H, m, Ph).
1
31P{1H} NMR (CD3COCD3): δ 27.3 (s, J Pt-P ) 4476 Hz). IR
(KBr, cm-1): 1022(m), 1436(m), 1570(m), 1877(vs), 1952(vs),
2026(vs).
Yield: 89%. 1H NMR (C6D6): δ 0.80 (6H, t, J H-H ) 6.9 Hz,
3
3
Me (N-Et)), 2.1 (2H, m, CH2-CH2), 2.22 (4H, q, J H-H ) 6.9
(tm ed a -K2N,N′)MeP t-MoCp (CO)3 (7). (cod)MePt-MoCp-
(CO)3 (121.5 mg, 0.216 mmol) was placed in a Schlenk tube
under nitrogen, and toluene was added. Then TMEDA (100
µL, 0.663 mmol) was added and stirred at room temperature
for 5 h. After removal of all volatile matters in a vacuum, the
resulting black solid was washed with hexane and recrystal-
lized from benzene/hexane to give brown crystals of 7 in 64%
yield (78.4 mg, 0.137 mmol). Anal. Calcd for C15H24MoN2O3-
Pt: C, 31.53; H, 4.23; N, 4.90. Found: C, 31.72; H, 4.12; N,
Hz, CH2 (N-Et)), 2.6 (2H, m, CH2-CH2), 4.61 (5H, s, Cp), 6.65
(1H, t, 3J H-H ) 7.5 Hz, p-Ph (Pt-Ph)), δ 6.9 (8H, m-Ph (Pt-Ph),
3
m- and p-Ph), δ 7.22 (2H, d, J H-H ) 7.5 Hz, o-Ph (Pt-Ph)), δ
7.4 (4H, m, o-Ph). 31P{1H} NMR (C6D6): δ 17.8 (s, J Pt-P
)
1
2674 Hz).
[P tMe(CO)(tm ed a -K2N,N′)]+[MoCp (CO)3]- (13). Complex
7 (5.2 mg, 0.0091 mmol) was placed in a NMR tube into which
CD3COCD3 (0.6 mL) was added by bulb-to-bulb distillation,
and then 2 equiv of TMEDA (2.7 µL, 0.018 mmol) was added.
Then CO (1 atm) was introduced into the NMR tube. Complex
1
2
4.74. H NMR (CD3COCD3): δ 0.07 (3H, s, J Pt-H ) 74.8 Hz,
Pt-Me), 2.45 (6H, s, 3J Pt-H ) 15.6 Hz, N-Me), 2.8 (2H, m, CH2-
1
13 was characterized spectroscopically. Yield: 98%. H NMR
(CD3COCD3): δ 0.90 (3H, s, J Pt-H ) 69.1 Hz, Pt-Me), 2.94
3
CH2), 2.82 (6H, s, J Pt-H ) 37.6 Hz, N-Me), 3.14 (2H, m, CH2-
2
CH2), 5.17 (5H, s, Cp). IR (KBr, cm-1): 594(m), 802(m),
3
3
(6H, s, J Pt-H ) 39.4 Hz, N-Me), 3.24 (6H, s, J Pt-H ) 22.8 Hz,
N-Me), 3.2-3.5 (4H, m, CH2-CH2), 4.99 (5H, s, Cp).
1462(m), 1742(vs), 1781(vs), 1866(vs).
(tm ed a -K2N,N′)P h P t-MoCp (CO)4 (8). The same proce-
dure was used as described for 7. (cod)PhPt-MoCp(CO)3 was
used instead of (cod)MePt-MoCp(CO)3. Orange powder.
(Et2NC2H4P P h 2-K2N,P )(MeCO)P t-MoCp (CO)3 (14). The
compound was prepared by the same procedure described for
1, but characterized spectroscopically. Pt(COMe)Cl(Et2NC2H4-
PPh2-κ2N,P) was used instead of PtMeCl(Et2NC2H4PPh2-
3
Yield: 74%. 1H NMR (CD2Cl2): δ 2.50 (6H, s, J Pt-H ) 44.2
3
Hz, N-Me), 2.56 (6H, s, J Pt-H ) 14.7 Hz, N-Me), 2.74 (2H, m,
κ2N,P). Orange needles. Yield: 27%. H NMR (C6D6): δ 0.83
1
CH2-CH2), 2.98 (2H, m, CH2-CH2), 4.69 (5H, s, Cp), 6.72 (1H,
(6H, t, 3J H-H ) 7.2 Hz, Me (N-Et)), 1.9-2.1 (4H, m, CH2-CH2),
3
3
t, J H-H ) 7.2 Hz, p-Ph (Pt-Ph)), 6.91 (2H, t, J H-H ) 7.2 Hz,
3
3
1.92 (3H, d, J P-H ) 1.2 Hz, Pt-COMe), 3.15 (4H, q, J H-H
)
3
3
m-Ph (Pt-Ph)), 7.23 (2H, d, J H-H ) 7.2 Hz, J Pt-H ) 42.1 Hz,
o-Ph (Pt-Ph)). IR (KBr, cm-1): 585(m), 799(m), 1460(m), 1775-
(vs), 1875(s).
7.2 Hz, CH2 (N-Et)), 5.09 (5H, s, Cp), 6.99-7.14 (6H, m, m-
and p-Ph), 7.68-7.75 (4H, m, o-Ph). 31P{1H} NMR (C6D6): δ
29.8 (s, J Pt-P ) 4399 Hz). IR (KBr, cm-1): 1040(m), 1101(m),
1
(Et2NC2H4P P h 2-K1P )(CO)MeP t-MoCp (CO)3 (9). 1 (86.9
mg, 0.117 mmol) was dissolved in acetone, and the solution
was degassed. Carbon monoxide (1 atm) was then introduced.
After stirring for 3 h, the color of the solution was changed
from orange to pale yellow. All the volatile matters were
removed by evaporation, and the resulting brown-yellow solid
was extracted with hexane. After the solution was concen-
trated under reduced pressure, the yellow solution was filtered
and cooled to -30 °C to give pale yellow crystals of 9. Yield:
58% (52.7 mg, 0.0687 mmol). Anal. Calcd for C28H32MoNO4-
PPt: C, 43.76; H, 4.26; N, 1.82. Found: C, 43.94; H, 4.55; N,
1.79. Molar electrical conductivity Λ (THF, 24.5 °C): 0.24 S
1437(m), 1646(s), 1782(vs), 1798(vs), 1899(s).
Tim e Cou r se of Rea ction of 5 w ith CO. Complex 5 (7.0
mg, 0.011 mmol) and Ph3CH (5.5 mg, 0.023 mmol) as an
internal standard were placed in a NMR tube into which C6D6
(0.5 mL) and then CO (0.1 MPa) were introduced. The acetyl
and carbonyl complexes (Et2NC2H4PPh2-κ2N,P)(MeCO)Pt-Co-
(CO)4 (15) and (Et2NC2H4PPh2-κ1P)(CO)MePt-Co(CO)4 (16)
were characterized by H NMR and 31P{1H} NMR, and their
1
amounts were periodically monitored based on the internal
standard. Initially the carbonyl complex 16 was formed in 10
min in quantitative yield, and then the acetyl complex 15 was
slowly formed. After 24 h at 30 °C, complex 15 was formed in
1
3
cm2 mol-1. H NMR (C6D6): δ 0.95 (6H, t, J H-H ) 7.2 Hz, Me
100% yield. 15: 1H NMR (C6D6): δ 0.79 (6H, t, J H-H ) 6.9
3
3
2
(N-Et)), 1.33 (3H, d, J P-H ) 8.7 Hz, J Pt-H ) 61 Hz, Pt-Me),
2.39 (4H, q, J H-H ) 7.2 Hz, CH2 (N-Et)), 2.55-3.05 (4H, m,
Hz, Me (N-Et)), 1.7-2.0 (4H, m, CH2-CH2), 1.94 (3H, s, Pt-
COMe), 2.76 (2H, br, CH2 (N-Et)), 2.99 (2H, br, CH2 (N-Et)),
7.0 (6H, m, m-, p-Ph), 7.63 (4H, m, o-Ph). 31P{1H} NMR
(C6D6): δ 21.9 (s, 1J Pt-P ) 4797 Hz). IR (KBr, cm-1): 1103(m),
1436(m), 1644(m), 1888(vs), 1948(vs), 2029(s). 16: 1H NMR
3
CH2-CH2), 4.94 (5H, s, Cp), 6.9-7.1 (6H, m, m- and p-Ph), 7.5-
1
7.6 (4H, m, o-Ph). 31P{1H} NMR (C6D6): δ 27.4 (s, J Pt-P
)
2906 Hz). 13C{1H} NMR (C6D6): δ 189.2 (s, 1J Pt-C ) 1031 Hz).
IR (KBr, cm-1): 1841(s), 1934(s), 2039(s).
3
(C6D6): δ 0.87 (6H, t, J H-H ) 7.2 Hz, Me (N-Et)), 1.04 (3H, d,
2
3
(Et2NC2H4P P h 2-K1P )(CO)P h P t-MoCp (CO)3 (10). Com-
plex 2 (5.8 mg, 0.072 mmol) was placed in a NMR tube, and
CD3COCD3 (0.6 mL) was added by bulb-to-bulb distillation.
Then CO (1 atm) was introduced into the NMR tube. Complex
10 was characterized spectroscopically. The compound was
3J P-H ) 6.6 Hz, J Pt-H ) 73 Hz, Pt-Me) 2.32 (4H, q, J H-H
)
7.2 Hz, CH2 (N-Et)), 2.5 (2H, m, CH2-CH2), 2.8 (2H, m, CH2-
CH2), 7.0-7.5 (10H, m, Ph). 31P{1H} NMR (C6D6): δ 19.0 (s,
1J Pt-P ) 3394 Hz).
[P t Me (E t 2NC2H 4P P h 2-K1P )(E t 2NC2H 4P P h 2-K2N ,P )]+-
[MoCp (CO)3]- (17). To a solution of 1 (73.1 mg, 0.099 mmol)
in a minimum quantity of toluene (ca. 1 mL) was added Et2-
NC2H4PPh2 (22 µL, 0.103 mmol) at -30 °C, and the solution
was stirred for 1 day at room temperature. Then hexane (ca.
20 mL) was added to precipitate an analytically pure pale
1
obtained in quantitative spectroscopic yield. H NMR (C6D6):
3
δ 0.80 (6H, t, J H-H ) 6.9 Hz, Me (N-Et)), 2.1 (2H, m, CH2-
3
CH2), 2.22 (4H, q, J H-H ) 6.9 Hz, CH2 (N-Et)), 2.6 (2H, m,
3
CH2-CH2), 4.67 (5H, s, Cp), 6.68 (1H, t, J H-H ) 7.5 Hz, p-Ph
(Pt-Ph)), 6.9 (8H, m, m-Ph (Pt-Ph), m- and p-Ph), 7.27 (2H,

Heterodinuclear Organoplatinum Complexes
Organometallics, Vol. 22, No. 21, 2003 4247
yellow powder of 17, which was filtered, washed with hexane,
and dried under vacuum at room temperature. Yield: 75%
(76.7 mg, 0.075 mmol). Anal. Calcd for C45H56MoN2O3P2Pt: C,
52.68; H, 5.50; N, 2.73. Found: C, 53.04; H, 5.63; N, 2.46.
PPh3 (39.4 mg, 0.150 mmol), and the solution was stirred for
3 day at room temperature. Then hexane (ca. 20 mL) was
added to precipitate a pale yellow powder of 23, which was
filtered, washed with hexane, and recrystallized from CH2Cl2/
hexane to give pale yellow crystals in 86% yield (98.7 mg,
Molar electrical conductivity Λ (THF, 21 °C): 12.6 S cm2 mol-1
.
3
1
3
1H NMR (CD3COCD3): δ 0.55 (3H, dd, J P-H ) 5.1, 3.3 Hz,
0.0885 mmol). H NMR (CD3COCD3): δ 0.55 (3H, q, J P-H )
2J Pt-H ) 51 Hz, Pt-Me), 0.87 (6H, t, J H-H ) 7.2 Hz, Me (N-
6.3 Hz, J Pt-H ) 58.8 Hz, Pt-Me), 2.4-2.8 (4H, m, CH2-CH2),
3
2
3
Et)), 1.42 (6H, t, J H-H ) 6.9 Hz, Me (Pt-N-Et)), 2.38 (4H, q,
4.98 (5H, s, Cp), 7.2-7.8 (35H, m, Ph). 31P{1H} NMR (CD3-
3J H-H ) 7.2 Hz, CH2 (N-Et)), 2.4-3.1 (8H, m, CH2-CH2), 3.3
(2H, m, CH2 (Pt-N-Et)), 3.5 (2H, m, CH2 (Pt-N-Et)), 4.96 (5H,
s, Cp), 7.2-7.7 (20H, m, Ph). 31P{1H} NMR (CD3COCD3): δ
COCD3): δ 26.7 (dd, J P-P ) 380, 17 Hz, J Pt-P ) 2769 Hz),
2 1 2
2
1
50.6 (dd, J P-P ) 17, 5 Hz, J Pt-P ) 1824 Hz), 54.5 (dd, J P-P
) 380, 5 Hz, J Pt-P ) 2743 Hz). IR (KBr, cm-1): 690(m), 110-
1
2
1
2
5.3 (d, J P-P ) 12 Hz, J Pt-P ) 3741 Hz), 46.6 (d, J P-P ) 12
Hz, 1J Pt-P ) 1962 Hz). IR (KBr, cm-1): 800(m), 1022(m), 1102-
(m), 1261(m), 1435(m), 1763(s), 1892(s).
(m), 1436(m), 1767(vs), 1897(vs).
Rea ction of 7 w ith P P h 3. Complex 7 (6.3 mg, 0.011 mmol)
was placed in a NMR tube, and CD3COCD3 (0.6 mL) was added
by bulb-to-bulb distillation. Then PPh3 (9.4 mg, 0.035 mmol)
was introduced into the NMR tube. Two ionic complexes,
[PtMe(PPh3)(tmeda-κ2N,N′)]+[MoCp(CO)3]- (24) and [PtMe-
(PPh3)3]+[MoCp(CO)3]- (25), were characterized by 1H and 31P-
{1H} NMR. Yield: 12% (24) and 88% (25). 24: 1H NMR (CD3-
The following complexes 18-21 were prepared analogously.
[P tMe(P Me3)(Et2NC2H4P P h 2-K2N,P )]+[MoCp(CO)3]- (18).
Pale yellow powder. Yield: 75%. Anal. Calcd for C30H41
-
MoNO3P2Pt: C, 44.12; H, 5.06; N, 1.72. Found: C, 43.82; H,
1
3
4.98; N, 1.64. H NMR (CD3COCD3): δ 0.64 (3H, dd, J P-H
)
3
2
2
3
COCD3): δ 0.27 (3H, d, J P-H ) 3.3 Hz, J Pt-H ) 68.5 Hz, Pt-
6.9, 3.0 Hz, J Pt-H ) 52 Hz, Pt-Me), 1.29 (6H, t, J H-H ) 7.2
4
3
3
2
Me), 2.35 (6H, s, N-Me), 2.94 (6H, d, J P-H ) 3.0 Hz, J Pt-H
)
Hz, Me (N-Et)), 1.44 (9H, d, J P-H ) 11.4 Hz, J Pt-H ) 56 Hz,
PMe3), 2.7-3.05 (4H, m, CH2-CH2), 3.1-3.5 (4H, m, CH2 (N-
Et)), 4.96 (5H, s, Cp), 7.65-7.71 (6H, m, m- and p-Ph), 7.89-
7.96 (4H, m, o-Ph). 31P{1H} NMR (CD3COCD3): δ -27.1 (d,
2J P-P ) 13 Hz, 1J Pt-P ) 3531 Hz), 46.0 (d, 2J P-P ) 14 Hz, 1J Pt-P
) 1935 Hz).
33.6 Hz, N-Me), 2.9-3.2 (4H, m, CH2-CH2), 4.98 (s, Cp), Ph
resonances of PPh3 ligand obscured by signals due to 25 and
free PPh3. 31P{1H} NMR (CD3COCD3): δ 18.5 (s). 25: 1H NMR
(CD3COCD3): δ 0.34 (3H, dt, 3J P-H ) 8.1, 5.7 Hz, 2J Pt-H ) 56.5
Hz, Pt-Me), 4.98 (s, Cp), Ph resonances of PPh3 ligand obscured
by signals due to 24 and free PPh3. 31P{1H} NMR (CD3-
[P tMe(P Et3)(Et2NC2H4P P h 2-K2N,P )]+[MoCp (CO)3]- (19).
White yellow powder. Yield: 93%. Anal. Calcd for C33H47
2
1
COCD3): δ 20.8 (t, J P-P ) 20 Hz, J Pt-P ) 1937 Hz), 28.7 (d,
-
2J P-P ) 20 Hz, J Pt-P ) 2937 Hz).
1
MoNO3P2Pt: C, 46.16; H, 5.52; N, 1.63. Found: C, 45.72; H,
1
3
X-r a y Str u ctu r e Deter m in a tion s. A single crystal was
selected by using a monochromated microscope and sealed in
a thin-glass capillary (GLAS, 0.7 mm φ) under N2. Diffraction
experiments were performed on a Rigaku RASA-7R diffracto-
meter with graphite-monochromated Mo KR radiation (λ )
0.71069 Å) and a rotating anode generator. The intensities of
three representative reflections were measured after every 150
reflections. No decay correction was applied for 21. These
structures were solved by direct methods, expanded using
Fourier techniques,22 and refined by full-matrix least squares.
For complex 2, all non-hydrogen atoms were refined with
anisotropic displacement parameters except for the Cp ring,
and the incorporated solvent molecule was treated as rigid
groups. All hydrogen atoms were included in theoretical
positions. All non-hydrogen atoms for 21 were anisotropic, and
the hydrogen atoms were included in theoretical positions.
These data were processed using the teXsan crystal solution
package23 operating on a SGI O2 workstation. The crystal-
lographic data and details associated with data collection for
2 and 21 are given in Table 1. Crystallographic thermal
parameters and bond distances and angles have been deposited
as Supporting Information.
5.32; N, 1.59. H NMR (CD3COCD3): δ 0.11 (3H, dd, J P-H
)
2
3
6.9, 3.0 Hz, J Pt-H ) 51 Hz, Pt-Me), 1.44 (9H, dt, J H-H ) 7.5
3
3
Hz, J P-H ) 17.4 Hz, Me (PEt3)), 1.30 (6H, t, J H-H ) 7.2 Hz,
Me (N-Et)), 1.70 (6H, dq, 3J H-H ) 7.5 Hz, 3J P-H ) 9.6 Hz, CH2
(PEt3)), 3.2 (2H, m, CH2 (N-Et)), 3.5 (2H, m, CH2 (N-Et)), 2.7-
3.0 (4H, m, CH2-CH2), 4.97 (5H, s, Cp), 7.6-7.7 (6H, m, m-
and p-Ph), 7.85-7.9 (4H, m, o-Ph). 31P{1H} NMR (CD3-
2
1
COCD3): δ 8.1 (d, J P-P ) 14 Hz, J Pt-P ) 3576 Hz), 45.4 (d,
2J P-P ) 14 Hz, J Pt-P ) 1819 Hz). IR (KBr, cm-1): 774(m),
1
1103(m), 1436(m), 1763(vs), 1887(vs).
[P tMe(P P h 3)(Et2NC2H4P P h 2-K2N,P )]+[MoCp(CO)3]- (20).
Pale yellow powder. Yield: 77%. Anal. Calcd for C46H48
-
MoNO3P2Pt: C, 54.39; H, 4.76; N, 1.38. Found: C, 54.10; H,
1
3
4.65; N, 1.38. H NMR (CD3COCD3): δ 0.11 (3H, dd, J P-H
)
3
6.3, 3.3 Hz, Pt-Me), 1.45 (6H, t, J H-H ) 6.9 Hz, Me (N-Et)),
2.9-3.1 (4H, m, CH2-CH2), 3.35 (2H, m, CH2 (N-Et)), 3.62 (2H,
m, CH2 (N-Et)), 4.97 (5H, s, Cp), 7.28-7.62 (25H, m, Ph). 31P-
{1H} NMR (CD3COCD3): δ 16.3 (d, J P-P ) 12 Hz, J Pt-P
)
2
1
2
1
3876 Hz), 48.1 (d, J P-P ) 12 Hz, J Pt-P ) 2004 Hz).
[P t M e {P (O M e )3 }(E t 2 N C 2 H 4 P P h 2 -K2 N ,P )]+[M o C p -
(CO)3]- (21). White yellow plate. Yield: 32% after recrystal-
lization from THF/ether. Anal. Calcd for C30H41MoNO6P2Pt:
C, 41.67; H, 4.78; N, 1.62. Found: C, 41.47; H, 4.65; N, 1.58.
1H NMR (CD3COCD3): δ 0.67 (3H, dd, J P-H ) 6.6, 1.2 Hz,
3
Ack n ow led gm en t. This work was financially sup-
ported by a Grant-in-Aid for Scientific Research from
the Ministry of Education, Sports, Culture, Science and
Technology, J apan, and the 21st Century COE (Center
of Excellence) program of “Future Nano-materials” at
Tokyo University of Agriculture and Technology.
2J Pt-H ) 51 Hz, Pt-Me), 1.34 (6H, t, J H-H ) 6.9 Hz, Me (N-
3
Et)), 2.8-3.3 (4H, m, CH2-CH2), 3.3 (2H, m, CH2 (N-Et)), 3.4
3
(2H, m, CH2 (N-Et)), 3.54 (9H, d, J P-H ) 12.9 Hz, P(OMe)3),
4.96 (5H, s, Cp), 7.60-7.64 (6H, m, m- and p-Ph), 7.76-7.83
(4H, m, o-Ph). 31P{1H} NMR (CD3COCD3): δ 50.6 (d, J P-P
)
2
21 Hz, 1J Pt-P ) 1836 Hz), 87.6 (d, 2J P-P ) 21 Hz, 1J Pt-P ) 6186
Hz).
Su p p or tin g In for m a tion Ava ila ble: Tables of atomic
coordinates, anisotropic displacement parameters, and bond
distances and angles for 2 and 21. This material is available
free of charge via the Internet at http://pubs.acs.org.
[t r a n s-P t Me (P P h 3)(E t 2NC2H 4P P h 2-K2N ,P )]+[MoCp -
(CO)3]- (22). Complex 22 was characterized spectroscopically.
Yield: 97%. 1H NMR (CD3COCD3): δ 0.17 (3H, dd, J P-H
)
3
3
8.1, 6.6 Hz, Pt-Me), 1.02 (6H, t, J H-H ) 6.9 Hz, Me (N-Et)),
2.6-3.0 (8H, m, CH2-CH2 and CH2 (N-Et)), 4.97 (5H, s, Cp),
7.2-8.0 (25H, m, Ph). 31P{1H} NMR (CD3COCD3): δ 31.9 (d,
OM030477U
2J P-P ) 405 Hz, J Pt-P ) 2975 Hz), 43.0 (d, J P-P ) 405 Hz,
1
2
(22) DIRDIF94: Beurskens, P. T.; Admiraal, G.; Beurskens, G.;
Bosman, W. P.; de Gelder, R.; Israel, R.; Smits, J . M. M. The DIRDIF-
94 Program System; Technical Report of the Crystallography Labora-
tory; University of Nijmegen: The Netherlands, 1994.
(23) teXsan: Crystal Structure Analysis Package; Molecular Struc-
ture Corp.: The Woodlands, TX, 1985 and 1992.
1J Pt-P ) 3239 Hz).
[P tMe(P P h 3)(d p p e-K2P ,P ′)]+[MoCp (CO)3]- (23). To a
solution of (dppe-κ2P,P′)MePt-MoCp(CO)3 (87.5 mg, 0.103
mmol) in a minimum quantity of toluene (ca. 1 mL) was added