Acetonyl platinum(II) complexes

Article abstract of DOI:10.1021/om700665n

Me₄N[Pt{CH₂C(O)Me}Cl₂(η²- C₂H₄)] (1), reacts either (1) with neutral ligands to afford cis-Me₄N[Pt{CH₂C(O)Me}Cl₂(L)] (L = CO (2), η²-PhCH=CH₂ (3), η²-PhC=CPh (4), η²-H₂C=C=CMe₂ (5), PPh₃ (6), AsPh₃ (7)), trans- or/and cis-[Pt{CH₂C(O)Me}CIL ₂] (L = PPh₃ (8), AsPh₃ (9), tht (10), XyNC (11), 'BuNC (12), py (17)), [Pt(CH₂C(O)Me)Cl(η²-C ₂H₄)(L)] (L = py (16)), or cIS-[Pt{CH₂C(O)Me} ClL₂] (L₂ = norbornadiene (nbd, 18), 1,5-cyclooctadiene (cod, 19), bis(diphenylphosphino)methane (dppm, 20), 4,4′-di-tert-butyl-2, 2′-bipyridyl (dbbpy, 21)) or (2) with [Tl(acac)] to give [Pt{CH ₂C(O)Me}(O,Oacac)(η²-C₂H₄)] (22) which reacts with neutral ligands to give [Pt{CH₂C(O)Me}(O,O-acac) (L)] (L = CO (23), PPh₃ (24), XyNC (25)). The different behavior of py and stronger π-acceptor ligands, as CO and PR₃ toward 1, has been explained through a DFT study. Reaction of 11trans with 2 equiv of XyNC affords a mixture of trans-[Pt(C(O)NHXy JCl(CNXy)₂] (13) and irans-[Pt{C(NHXy)₂}Cl(CNXy)₂]Cl (14). The first was isolated by recrystallization and the latter by reacting CW-[PtCl2(CNXy)2] with 2 equiv of XyNC. However, cis-[Pt{CH₂C(O)Me}₂(bpy)] reacts with 4 equiv of XyNC to give cis-[Pt(CH₂C(O)Me)₂(CNXy) ₂] (15).

Full text of DOI:10.1021/om700665n

Organometallics 2007, 26, 6155-6169
6155
Acetonyl Platinum(II) Complexes†
Jose´ Vicente,* Aurelia Arcas,* and Jesu´s M. Ferna´ndez-Herna´ndez
Grupo de Qu´ımica Organometa´lica, Departamento de Qu´ımica Inorga´nica, Facultad de Qu´ımica,
UniVersidad de Murcia, Aptdo. 4021, E-30071 Murcia, Spain
Gabriel Aullo´n*
Departament de Qu´ımica Inorga`nica and Centre de Recerca en Qu´ımica Teo´rica,
UniVersitat de Barcelona, Diagonal 647, 08028 Barcelona, Spain
Delia Bautista*
SAI, UniVersidad de Murcia, Aptdo. 4021, E-30071 Murcia, Spain
ReceiVed July 2, 2007
Me4N[Pt{CH2C(O)Me}Cl2(η2-C2H4)] (1), reacts either (1) with neutral ligands to afford cis-Me4N-
[Pt{CH2C(O)Me}Cl2(L)] (L ) CO (2), η2-PhCHdCH2 (3), η2-PhCtCPh (4), η2-H2CdCdCMe2 (5),
PPh3 (6), AsPh3 (7)), trans- or/and cis-[Pt{CH2C(O)Me}ClL2] (L ) PPh3 (8), AsPh3 (9), tht (10), XyNC
t
(11), BuNC (12), py (17)), [Pt{CH2C(O)Me}Cl(η2-C2H4)(L)] (L ) py (16)), or cis-[Pt{CH2C(O)Me}-
ClL2] (L2 ) norbornadiene (nbd, 18), 1,5-cyclooctadiene (cod, 19), bis(diphenylphosphino)methane (dppm,
20), 4,4′-di-tert-butyl-2,2′-bipyridyl (dbbpy, 21)) or (2) with [Tl(acac)] to give [Pt{CH2C(O)Me}(O,O-
acac)(η2-C2H4)] (22) which reacts with neutral ligands to give [Pt{CH2C(O)Me}(O,O-acac)(L)] (L )
CO (23), PPh3 (24), XyNC (25)). The different behavior of py and stronger π-acceptor ligands, as CO
and PR3 toward 1, has been explained through a DFT study. Reaction of 11trans with 2 equiv of XyNC
affords a mixture of trans-[Pt{C(O)NHXy}Cl(CNXy)2] (13) and trans-[Pt{C(NHXy)2}Cl(CNXy)2]Cl
(14). The first was isolated by recrystallization and the latter by reacting cis-[PtCl2(CNXy)2] with 2
equiv of XyNC. However, cis-[Pt{CH2C(O)Me}2(bpy)] reacts with 4 equiv of XyNC to give cis-[Pt-
{CH2C(O)Me}2(CNXy)2] (15).
been obtained by reacting [PtMe2L2] with XCH2C(O)Ph, by light
irradiation of a [PtCl6]2- solution in acetone, by reacting K2-
[PtCl4] with iodoacetone in water, or by a redox transmetallation
reaction using [Hg{CH2C(O)Me}2].7,8 Among ketonyl Pt(II)
derivatives, only five have been characterized by X-ray dif-
fraction studies and four of them are acetonyl complexes.5,9-11
Introduction
The chemistry of ketonylplatinum complexes has been studied
to a lesser extent than that of the palladium analogues. During
the late 1970s and early 1980s Bennett,1,2 Pidcock,3 and Otsuka4
developed most of the chemistry of ketonyl complexes of Pt-
(II). They synthesized these compounds by reacting hydroxo-
complexes with ketones. The reported acetonyl Pt(II) complexes
contained other strongly coordinated ligands, such as phosphines
or pyridine, which make them not appropriate to prepare
derivatives. Acetonyl Pt(II) complexes containing the easily
exchangeable ligand cod (cod ) 1,5-cyclooctadiene) have been
reported but in low yield.5,6 Ketonyl complexes of Pt(IV) have
We are studying the synthesis and properties of acetonyl metal
complexes and finding some interesting results.11-13 Thus, we
(7) Nizova, G. V.; Serdobov, M. V.; Nikitaev, A. T.; Shul’pin, G. B. J.
Organomet. Chem. 1984, 275, 139. Shul’pin, G. B.; Nizova, G. V.; Shilov,
A. J. Chem. Soc., Chem. Commun. 1983, 671. Zamaschikov, V. V.;
Rudakov, E. S.; Mitchenko, S. A.; Nizova, G. V.; Kitaigorodskii, A. N.;
Shul’pin, G. B. Bull. Acad. Sci. USSR, DiV. Chem. Sci. 1984, 33, Part 2,
1520. Shilov, A. E.; Shulpin, G. B. Chem. ReV. 1997, 97, 2879.
(8) Vicente, J.; Arcas, A.; Ferna´ndez-Herna´ndez, J. M.; Bautista, D.
Organometallics. 2006, 25, 4404.
† Dedicated to Dr. Jose-Antonio Abad, with best wishes, on the occasion
of his retirement and to Profs. Juan Fornie´s, Jose´ Gimeno, and Miguel Yus
on the occasion of their 60th birthdays.
* To whom correspondence should be addressed. E-mail: jvs1@um.es
(J.V.); aurelia@um.es (A.A.). Web: http://www.scc.um.es/gqo/. Cor-
respondence regarding the DFT studies should be addressed to G.A
(gabriel.aullon@antares.qi.ub.es); correspondence regarding the X-ray dif-
fraction studies should be addressed to D.B. (dbc@um.es).
(1) Arnold, D. P.; Bennett, M. A. J. Organomet. Chem. 1980, 199, 119.
Bennet, M. A.; Yoshida, T. J. Am. Chem. Soc. 1978, 100, 1750. Bennet,
M. A.; Robertson, G. B.; Whimp, P. O.; Yoshida, T. J. Am. Chem. Soc.
1973, 95, 3028. Appleton, T. G.; Bennet, M. A. J. Organomet. Chem. 1973,
55, C88.
(2) Appleton, T. G.; Bennet, M. A. Inorg. Chem. 1978, 17, 738.
(3) Almeida, J. F.; Piddock, A. J. Organomet. Chem. 1981, 209, 415.
(4) Yoshida, T.; Okano, T.; Otsuka, S. J. Chem. Soc., Dalton Trans.
1976, 993.
(9) Falvello, L. R.; Garde, R.; Miqueleiz, E. M.; Tomas, M.; Urriolabeitia,
E. P. Inorg. Chim. Acta 1997, 264, 297. Lai, S. W.; Chan, M. C. W.;
Cheung, K. K.; Che, C. M. Inorg. Chem. 1999, 38, 4262.
(10) Henderson, W.; Fawcett, J.; Kemmitt, R. D. W.; McKenna, P.;
Russell, D. R. Polyhedron. 1997, 16, 2455.
(11) Vicente, J.; Abad, J. A.; Chicote, M. T.; Abrisqueta, M. D.; Lorca,
J. A.; Ram´ırez de Arellano, M. C. Organometallics. 1998, 17, 1564.
(12) Vicente, J.; Bermu´dez, M. D.; Escribano, J.; Carrillo, M. P.; Jones,
P. G. J. Chem. Soc., Dalton Trans. 1990, 3083. Vicente, J.; Bermu´dez, M.
D.; Carrillo, M. P.; Jones, P. G. J. Chem. Soc., Dalton Trans. 1992, 1975.
Vicente, J.; Bermu´dez, M. D.; Chicote, M. T.; Sa´nchez-Santano, M. J. J.
Chem. Soc., Dalton Trans. 1990, 1945. Vicente, J.; Abad, J. A.; Bergs, R.;
Jones, P. G.; Bautista, D. J. Chem. Soc., Dalton Trans. 1995, 3093. Vicente,
J.; Abad, J. A.; Cara, G.; Jones, P. G. Angew. Chem., Int. Ed. Engl. 1990,
29, 1125. Vicente, J.; Bermu´dez, M. D.; Carrio´n, F. J. Inorg. Chim. Acta
1994, 220, 1.
(5) Suzaki, Y.; Yagyu, T.; Yamamura, Y.; Mori, A.; Osakada, K.
Organometallics. 2002, 21, 5254.
(6) Klein, A.; Klinkhammer, K. W.; Scheiring, T. J. Organomet. Chem.
1999, 592, 128.
(13) Vicente, J.; Arcas, A.; Ferna´ndez-Herna´ndez, J. M.; Bautista, D.
Organometallics. 2001, 20, 2767.
10.1021/om700665n CCC: $37.00 © 2007 American Chemical Society
Publication on Web 11/01/2007

6156 Organometallics, Vol. 26, No. 25, 2007
Chart 1. View of the Isomers of 3 through the Cl-Pt-Olefin Axis
Vicente et al.
have recently found that the reaction between [Hg{CH2C(O)-
Me}2] and the Pt(II) complex K[PtCl3(η2-C2H4)] (2:1) affords
the Pt(IV) complex K[Pt2{CH2C(O)Me}6(µ-Cl)3]. During the
study carried out to elucidate the mechanism of formation of
this Pt(IV) complex, the intermediate Pt(II) complex K[Pt-
{CH2C(O)Me}Cl2(C2H4)] was detected in solution and isolated
as the Me4N+ salt (1).8 Contrary to the previously reported Pt-
(II) acetonyl complexes, 1 offers the possibility of being used
to prepare other monoacetonyl complexes by replacing any of
the remaining three ligands.
Pt(II) complex has been used to prepare the corresponding
isocyanide complex.22 The nucleophilic addition of amines to
coordinated isocyanides to give amino carbene complexes is a
very well-known process.23
Experimental Section
Unless otherwise stated, the reactions were carried out without
precautions against light or atmospheric oxygen or moisture.
Melting points were determined on a Reicher apparatus and are
uncorrected. Elemental analyses were carried out with a Carlo Erba
1106 microanalyzer. Molar conductivities were measured in Me2-
CO (ca. 5 × 10-4 mol L-1) with a Crison Micro CM2200
conductimeter. IR spectra were recorded on a Perkin-Elmer 16F
PC FT-IR spectrometer with Nujol mulls between polyethylene
sheets. NMR spectra were recorded in a Brucker AC 200, Avance
300 or 400, or Brucker 600 spectrometer at room temperature unless
otherwise stated. Chemical shifts were referred to TMS (1H, 13C),
H3PO4 (31P), or Na2[PtCl6] (195Pt). When needed, NMR assignments
were performed with the help of APT, DEPT, COSY, one
dimension NOE experiments, and HETCOR techniques. cis-[PtCl2-
(CNXy)2] has been prepared from cis-[PtCl2(dmso)2] and XyNC
(1:2). [Hg{CH2C(O)Me}2],24 K[PtCl3(C2H4)],25 cis-(Me4N)[Pt-
{CH2C(O)Me}Cl2(C2H4)] (1),8 [Pt{CH2C(O)Me}2(bpy)] (195Pt{1H}
NMR, δ -3351), and [Pt{CH2C(O)Me}Cl(bpy)]11 were prepared
according to literature methods.
From the studies of the reactivity of 1 toward XyNC we
obtained fortuitously the carbamoyl and carbene complexes [Pt-
{C(O)NHXy}Cl(CNXy)2] and [Pt{C(NHXy)2}Cl(CNXy)2]Cl,
respectively, both resulting after hydrolysis of the acetonyl
ligand and the nucleophilic attack of H2O and XyNH2,
respectively, to a XyNC ligand. Although carbamoyl metal
complexes are well-known,14 no fully characterized [Pt(II){C(O)-
NRR′}(L)(L′)(L′′)]n- complex with R or R′ ) H is known and
only a few with R ) R′ ) Et, n ) 0, L ) L′ ) PPh3, L′′ )
i
Cl,15 C(O)Ph,16 C(O)C(O)Ph, C(O)CO2Me or17 R ) R′ ) Pr,
n ) 1, L ) L′ ) Cl, L′′ ) CO18 have been reported. In addition,
these complexes have been prepared using CO to form the
carbamoyl ligand. As far as we are aware, the only examples
of the synthesis of NH-carbamoyl Pt(II) complexes using
isocyanides as the source of the carbamoyl ligand are the
reaction of (1) nitrite or hydroxide ion with the cationic complex
[Pt(CNMe)2(PPh3)2]+,19,20 or (2) an isocyanide with [Pt-
(CF3)(OH)(cis-Ph2PCHdCHPPh2)].21 Conversely, a carbamoyl
Synthesis of cis-Me4N[Pt{CH2C(O)Me}Cl2(CO)] (2). A stream
of CO was bubbled into a cooled (0 °C) solution of 1 (53.4 mg,
0.13 mmol) in Me2CO (3 mL) for 10 min until a pale yellow
solution was obtained. This solution was filtered through Celite,
and the resulting solution was concentrated (to ca. 1 mL) in a water/
ice bath. Addition of a saturated solution of CO in Et2O (20 mL)
gave a suspension that was filtered off. The filtrate was washed
with Et2O (5 mL) and air-dried to give 2 as a pale yellow solid
that was stored at -34 °C. Yield: 43 mg, 81%; mp 94 °C. IR
(cm-1): ν(CtO) 2086; ν(CdO) 1672; ν(Pt-Cl) 328, 284. 1H NMR
(300 MHz, acetone-d6): δ 3.46 (t, {1:1:1}, 12 H, Me4N) 2.94 (q,
(14) Angelici, R. J. Acc. Chem. Res. 1972, 5, 335. For recent results on
C(O)NR2 carbamoyl complexes, see for example: Aresta, M.; Giannoccaro,
P.; Tommasi, I.; Dibenedetto, A.; Lanfredi, A. M. M.; Ugozzoli, F.
Organometallics 2000, 19, 3879. J. N. C., III; Huffman, J. C.; Caulton, K.
G. Organometallics 2000, 19, 3569. Kolel-Veetil, M. K.; Khan, M. A.;
Nicholas, K. M. Organometallics 2000, 19, 3754. Ragaini, F.; Cenini, S.;
Borsani, E.; Dompe, M.; Gallo, E.; Moret, M. Organometallics 2001, 20,
3390. Anderson, S.; Berridge, T. E.; Hill, A. F.; Ng, Y. T.; White, A. J. P.;
Williams, D. J. Organometallics 2004, 23, 2686. Schobert, R.; Mangold,
A.; Baumann, T.; Milius, W.; Hampel, F. J. Organomet. Chem. 2004, 689,
575. Tomon, T.; Koizumi, T.; Tanaka, K. Angew. Chem., Int. Ed. 2005,
44, 2229. Gibson, D. H.; Andino, J. G.; Mashuta, M. S. Organometallics
2006, 25, 563. For recent results on C(O)NHR carbamoyl complexes, see
for example: Balch, A. L.; Olmstead, M. M.; Vickery, J. C. Inorg. Chem.
1999, 38, 3494. Salzer, A.; Hosang, A.; Knuppertz, J.; Englert, U. Eur. J.
Inorg. Chem. 1999, 1497. Ipaktschi, J.; Uhlig, S.; Dulmer, A. Organome-
tallics 2001, 20, 4840. Ershova, V. A.; Virovets, A. V.; Pogrebnyak, V.
M.; Golovin, A. V. Inorg. Chem. Commun. 2002, 5, 963. Zuo, J.-L.; Fu,
W.-F.; Che, C.-M.; Cheung, K.-K. Eur. J. Inorg. Chem. 2003, 255.
Anderson, S.; Berridge, T. E.; Hill, A. F.; Ng, Y. T.; White, A. J. P.;
Williams, D. J. Organometallics 2004, 23, 2686. Takemoto, S.; Oshio, S.;
Kobayashi, T.; Matsuzaka, H.; Hoshi, M.; Okimura, H.; Yamashita, M.;
Miyasaka, H.; Ishii, T.; Yamashita, M. Organometallics 2004, 23, 3587.
(15) Abram, U.; Belli Dell’Amico, D.; Calderazzo, F.; Marchetti, L.;
Strahle, J. J. Chem. Soc., Dalton Trans. 1999, 4093.
4
2
2 H, CH2, JHH ) 0.8 Hz, JHPt ) 148 Hz), 2.09 (t, MeC(O), 4JHH
2
) 0.8 Hz, JHPt ) 8.8 Hz). 13C{1H} NMR (75.45 MHz, acetone-
d6): δ 209.3 (MeC(O)), 159.3 (CO, 1JCPt ) 1953 Hz), 55.2 (t, {1:
1
1
1:1}, Me4N, JCN ) 4 Hz), 29.0 (MeC(O)), 21.1 (PtCH2, JCPt
)
532 Hz). 195Pt{1H} NMR (85.9 MHz, acetone-d6): δ -3726.3.
Anal. Calcd for C8H17Cl2NO2Pt: C, 22.60; H, 4.03; N, 3.29.
Found: C, 22.61; H, 4.05; N, 3.32. ESI-MS(-): 350.7 [M]-
Synthesis of cis-Me4N[Pt{CH2C(O)Me}Cl2(η2-CH2dCHPh)]
(3). To a solution of 1 (92 mg, 0.22 mmol) in Me2CO (3 mL),
PhCHdCH2 (100 µL, 0.87 mmol) was added. The resulting solution
was heated at 50 °C for 1 h and then was filtered through Celite.
The filtrate was concentrated to dryness, and the solid residue was
stirred with Et2O (10 mL). The suspension was filtered off and the
solid was washed with Et2O (5 mL) and air-dried to give 3 as a
colorless solid. Yield: 80 mg, 74%; mp 147-149 °C. ΛM (Me2-
CO, 2.49 × 10-4 mol L-1): 121 Ω-1 cm2 mol-1. IR (cm-1): ν-
(CdO) 1671, ν(Pt-Cl) 305, 267. 1H NMR (400 MHz, acetone-d6,
-20 °C): 3aa′ (Chart 1), δ 7.56-7.54 (m, 2 H, Ph), 7.32-7.28
(16) Huang, T.-M.; Chen, J.-T.; Lee, G.-H.; Wang, Y. Organometallics
1991, 10, 175.
(17) Huang, T.-M.; You, Y.-J.; Yang, C.-S.; Tzeng, W.-H.; Chen, J.-T.;
Cheng, M.-C.; Wang, Y. Organometallics 1991, 10, 1020.
(18) Belli Dell’Amico, D.; Calderazzo, F.; Pelizzi, G. Inorg. Chem. 1979,
18, 1165.
(19) Treichel, P. M.; Knebel, W. J.; Hess, R. W. J. Am. Chem. Soc.
1971, 93, 5424.
(20) Treichel, P. M.; Knebel, W. J. Inorg. Chem. 1972, 11, 1285.
(21) Michelin, R. A.; Ros, R. J. Organomet. Chem. 1979, 169, C42.
(22) Fehlhammer, W. P.; Mayr, A. Angew. Chem., Int. Ed. 1975, 14,
757.
(23) Michelin, R. A.; Pombeiro, A. J. L.; da Silva, F. M. C. G. Coord.
Chem. ReV. 2001, 218, 75.
(24) Nesmeyanov, A. N. Selected Works in Organic Chemistry; Pergamon
Press: Oxford, England, 1963; p 385.
(25) Chock, P. B.; Halpern, J.; Paulik, F. E. Inorg. Synth. 1973, 14, 90.

Acetonyl Platinum(II) Complexes
Organometallics, Vol. 26, No. 25, 2007 6157
3
3
(m, 3 H, Ph), 6.15 (dd, 1 H, Hc, JHbHc ) 8.4 Hz, JHaHc ) 13.1
CDCl3): δ 7.77-7.73 (m, 6 H, Ph), 7.37 (m, 9 H, Ph), 3.32 (s, 12
3
2
Hz, 2JHcPt ) 81.1 Hz), 4.14 (d, 1 H, Ha, 3JHaHc ) 13.1 Hz, 2JHaPt
)
H, Me4N), 2.37 (d, 2 H, CH2, JHP ) 4 Hz, JHPt ) 111 Hz), 2.01
52.7 Hz), 3.71 (d, 1 H, Hb, JHbHc ) 8.4 Hz, JHbPt ) 76.7 Hz),
(s, 3 H, Me). 13C{1H} NMR (75.45 MHz, CDCl3): δ 214.8 (d,
3
2
2
2
2
2
3.37 (s, Me4N), 2.06 (s, 3 H, Me), 2.96 (d, 1 H, CH2, JHH ) 5.4
CO, JCP ) 4.5 Hz, JCPt ) 52 Hz), 134.7 (d, CHorto, JCP ) 10.5
1
4
Hz, 2JHPt ) 128 Hz), 1.06 (d, 1 H, CH2, 2JHH ) 5.4 Hz, 2JHPt ) 89
Hz); 3bb′, δ 7.50-7.22 (m, 2 H, Ph), 7.22-7.17 (m, 3 H, Ph),
Hz), 130.8 (d, Cipso, JCP ) 43 Hz), 130.1 (d, CHpara, JCP ) 2.3
Hz), 127.7 (d, CHmeta, 3JCP ) 11 Hz), 56.0 (t, {1:1:1}, Me4N, 1JCN
) 3.2 Hz), 31.8 (Me), 20.5 (d, CH2, 2JCP ) 4 Hz, 1JCPt ) 661 Hz).
31P{1H} NMR (162.3 MHz, CDCl3): δ 14.2 (1JPPt ) 4662 Hz).
3
3
2
5.66 (dd, 1 H, Hc, JHbHc ) 8.1 Hz, JHaHc ) 13.3 Hz, JHcPt
)
3
2
73.8 Hz), 4.66 (d, 1 H, Ha, JHaHc ) 13.3 Hz, JHaPt ) 67.8 Hz),
195Pt{1H} NMR (85.88 MHz, CDCl3): δ -4091 (d, JPPt ) 4662
1
3.43 (d, 1 H, Hb, 3JHbHc ) 8.1 Hz, 2JHcPt ) 69 Hz), 3.37 (s, Me4N),
2
2
Hz). Anal. Calcd for C25H32Cl2NOPPt: C, 45.53; H, 4.89; N, 2.12.
Found: C, 45.15; H, 4.96; N, 2.17.
3.05 (d, 1 H, CH2, JHH ) 5.2 Hz, JHPt ) 123 Hz), 2.18 (3 H,
Me), 1.87 (d, 1 H, CH2, JHH ) 5.2 Hz, JHPt ) 99 Hz). 13C{1H}
NMR (100.8 MHz, acetone-d6, -20 °C): 3aa′, δ 211.1 (CO), 139.3
(C, Ph), 129.5 (CH, Ph), 129.1 (CH, Ph), 127.9 (CH, Ph), 79.6
2
2
Synthesis of cis-Me4N[Pt{CH2C(O)Me}Cl2(AsPh3)] (7). To a
suspension of 1 (44 mg, 0.10 mmol) in THF (2 mL), AsPh3 (31.7
mg, 0.10 mmol) was added under N2. The reaction mixture was
stirred for 1 h, and the suspension was filtered. The solid was
washed with Et2O, recrystallized in CH2Cl2/Et2O, and dried for 1
day under vacuum to give 7 as a pale yellow solid. Yield: 54 mg,
75%; mp 196 °C. ΛM (Me2CO, 5 × 10-4 mol L-1): 127 Ω-1 cm2
mol-1. IR (cm-1): ν(CdO) 1649, ν(PdCl) 297, 273. 1H NMR (400
MHz, CDCl3): δ 7.74-7.71 (m, 6 H, Ph), 7.41-7.34 (m, 9 H,
2
1
(dCHPh, JCPt ) 204 Hz), 55.3 (t, {1:1:1}, Me4N, JNC ) 4 Hz),
1
24.2 (CH2, JCPt ) 627 Hz); 3bb′, δ 211.6 (CO), 139.0 (C, Ph),
129.4 (CH, Ph), 128.4 (CH, Ph), 127.7 (CH, Ph), 79.1 (dCHPh,
2JCPt ) 210 Hz), 55.36 (t, {1:1:1}, Me4N, JCN ) 16 Hz), 55.1
1
(CH2d), 23.9 (CH2, 1JCPt ) 591 Hz). 195Pt{1H} NMR (85.9 MHz,
acetone-d6, -20 °C): δ -3167.6, -3186.6. Anal. Calcd for C15H25-
Cl2NOPt: C, 35.94; H, 5.03; N, 2.79. Found: C, 35.95; H, 5.16;
N, 2.88. Single crystals of 3bb′ were obtained by slow diffusion
of Et2O into a solution of 3 in Me2CO.
2
Ph), 3.29 (s, 12 H, Me4N), 2.58 (s, 2 H, CH2, JHPt ) 102 Hz),
2.03 (s, 3 H, Me). 13C{1H} NMR (75.45 MHz, CDCl3): δ 214.3
(CO), 134.1 (CH), 131.7 (C), 129.9 (CH), 128.3 (CH), 55.9
(unresolved t, Me4N), 31.6 (Me), 15.1 (CH2). 195Pt{1H} NMR (85.88
MHz, CDCl3): δ -3950. Anal. Calcd for C25H32AsCl2NOPt: C,
42.70; H, 4.58; N, 1.99. Found: C, 42.37; H, 4.69; N, 2.08.
Synthesis of cis-Me4N[Pt{CH2C(O)Me}Cl2(η2-PhCtCPh)]
(4). To a solution of 1 (56 mg, 0.13 mmol) in Me2CO (3 mL),
PhCtCPh was added (234 mg, 1.31 mmol). The resulting solution
was stirred at 60 °C for 3.5 h and then concentrated to dryness.
The resulting residue was stirred in Et2O (10 mL) until an orange
suspension was obtained and then was filtered off. The solid was
air-dried for 24 h, to give 4 as a yellow solid. Yield: 58 mg, 77%.
IR (cm-1): ν(CdO) 1654; ν(Pt-Cl) 317, 254. 1H NMR (400 MHz,
acetone-d6): δ 8.05-8.03 (m, 4 H, Ph), 7.42-7.36 (m, 6 H, Ph),
Synthesis of cis- and trans-[Pt{CH2C(O)Me}Cl(PPh3)2] (8).
Method a. To a solution of 1 (55 mg, 0.13 mmol) in CH2Cl2 (3
mL), PPh3 (68 mg, 0.26 mmol) was added under N2. The resulting
suspension was filtered to remove Me4NCl, and the filtrate was
concentrated to dryness. The residue was stirred with Et2O (10 mL)
and filtered off. The resulting colorless solid was air-dried to give
8trans. Yield: 85 mg, 81%.
2
3.38 (s, 12 H, Me4N) 2.64 (s, 2 H, PtCH2, JHPt ) 107 Hz), 1.93
(s, MeC(O)). 13C{1H} NMR (50.30 MHz, acetone-d6): δ 209.6
(CO), 131.5 (CH, Ph), 128.9 (CH, Ph), 128.7 (CH, Ph), 124.7 (C,
Ph), 80.2 (CtC), 55.9 (Me4N), 29.7 (Me), 23.0 (CH2). 195Pt{1H}
NMR (85.88 MHz, CDCl3): δ -2606. Anal. Calcd for C21H27Cl2-
NOPt: C, 43.83; H, 4.73; N, 2.43. Found: C, 43.10; H, 4.62; N,
2.48 (see Discussion).
Method b. A suspension of [Pt(PPh3)4] (146 mg, 0.12 mmol) in
toluene (8 mL) was stirred for 24 h with [Hg{CH2C(O)Me}Cl]
(39 mg, 0.13 mmol) under N2. The suspension was filtered. The
solid was stirred in CH2Cl2 and filtered through Celite to remove
Hg. The filtrate was concentrated (to ca. 1 mL) and addition of
Et2O (5 mL) gave a suspension, which was filtered, and the solid
was air-dried to give 8cis contaminated with cis-[PtCl2(PPh3)2]. The
filtrate from the reaction mixture was concentrated (2 mL), Et2O
(5 mL) was added and the resulting suspension filtered off. The
solid was washed with Et2O (2 mL) and air-dried to give a mixture
of 8cis and 8trans contaminated with cis-[PtCl2(PPh3)2]. IR (cm-1):
ν(CdO) 1688 (8trans), 1650 (8cis), ν(Pt-Cl) 276 (8trans), 298
Synthesis of cis-Me4N[Pt{CH2C(O)Me}Cl2(η2-CH2dCdCMe2)]
(5). A solution of 1 (52 mg, 0.12 mmol) in CH2Cl2 (1.5 mL) was
stirred for 2.5 h with CH2dCdCMe2 (25 µL, 0.25 mmol) under
N2 to give a suspension, which was filtered. The solid was washed
with Et2O (5 mL) and air-dried to give 5 as a colorless solid. The
filtrate was concentrated. Et2O was added, and the suspension was
filtered; the solid was washed with Et2O to give a second crop of
5. Yield: 46 mg, 81%; mp 159-161 °C. ΛM (Me2CO, 5.69 × 10-4
mol L-1): 114 Ω-1 cm2 mol-1. IR (cm-1): ν(CdO) 1659, ν(Pt-
1
(8cis). H NMR (400 MHz, CDCl3): 8trans, δ 7.84-7.81 (m, 12
3
H, Ph), 7.41-7.38 (m, 18 H, Ph), 2.14 (t, 2 H, CH2, JHP ) 7.8
1
2
4
Cl) 315, 265. H NMR (400 MHz, acetone-d6): δ 3.45 (s, 12 H,
Hz, JHPt ) 87.6 Hz), 1.51 (s, 3 H, Me, JHPt ) 10.4 Hz); 8cis, δ
2.63 (dd, 2 H, CH2, 3JHP ) 11 Hz, 3JHP ) 5.7 Hz, 2JHPt ) 76 Hz),
Me4N), 3.27 (m, 1 H, 2JHPt ) 76.1 Hz), 3.02 (m, 1 H, 2JHPt ) 64.7
1
2
2.25 (s, 3 H, Me, JHPt ) 10.4 Hz). 31P{1H} NMR (162.29 MHz,
4
Hz), 2.97 (d, 1 H, PtCH2, JHH ) 5.5 Hz, JHPt ) 122.3 Hz), 2.10
CDCl3): 8trans, δ 25.6 (s, PPh3, 1JPPt ) 3065 Hz); 8cis, δ 21.8 (d,
(s, 3 H, MeC(O)), 2.06 (m, 3 H, CMe2), 1.93 (m, 3 H, CMe2), 1.72
(d, 1 H, PtCH2, JHH ) 5.5 Hz, JHPt ) 93.5 Hz). 13C{1H} NMR
1
2
2
1
PPh3 trans to acetonyl, JPP ) 16 Hz, JPPt ) 1973 Hz), 18.5 (d,
(75.45 MHz, acetone-d6): δ 210.7 (CO, 2JCPt ) 47 Hz), 153.9 (C,
PPh3 cis to Cl, JPP ) 16 Hz, JPPt ) 4319 Hz). 195Pt{1H} NMR
2
1
1
2
1
allene, JCPt ) 391 Hz), 106.1 (C, allene, JCPt ) 31 Hz), 56.1 (t,
(85.88 MHz, CDCl3): 8trans, δ -4584.8 (t, JPPt ) 3065 Hz).
1
1
{1:1:1}, Me4N, JCN ) 4 Hz), 31.8 (CH2, allene, JCPt ) 155.3
Hz), 29.4 (MeC(O)), 23.5 (PtCH2, 1JCPt ) 586 Hz), 23.6 (Me, allene,
Single crystals of 8trans‚CHCl3 were obtained by slow diffusion
of Et2O into a CHCl3 solution of 8trans.
3
3JCPt ) 58 Hz), 20.4 (Me, allene, JCPt ) 57 Hz). 195Pt{1H} NMR
Synthesis of [Pt{CH2C(O)Me}Cl(AsPh3)2] (9). To a solution
of 1 (68 mg, 0.16 mmol) in CH2Cl2 (4 mL), AsPh3 (98 mg, 0.32
mmol) was added. The resulting suspension was filtered through
Celite to remove Me4NCl, the filtrate was concentrated (to ca. 1
mL), Et2O (10 mL) was added and the suspension was stirred for
15 min. The resulting suspension was filtered off, washed with Et2O
(2 mL) and air-dried to give 9trans as a colorless solid. Yield: 102
mg, 71%; mp 194-198 °C. IR (cm-1): ν(CdO) 1659. ν(Pt-Cl)
284. A CDCl3 solution of 9trans led, after 16 h at room temperature,
to a mixture of cis/trans isomers (1:1). 1H NMR (400 MHz,
CDCl3): 9trans, δ 7.79-7.76 (m, 12 H, Ph), 7.43-7.38 (m, 18 H,
(86.18 MHz, acetone-d6): δ -3013. Anal. Calcd for C12H25Cl2-
NOPt: C, 30.97; H, 5.42; N, 3.01. Found: C, 30.85; H, 5.40; N,
3.08.
Synthesis of cis-Me4N[Pt{CH2C(O)Me}Cl2(PPh3)] (6). A
suspension of 1 (56 mg, 0.13 mmol) in THF (1 mL) was stirred
for 1.5 h with PPh3 (34.5 mg, 0.13 mmol) under N2. The suspension
was filtered an the solid was recrystallized in CH2Cl2/Et2O and
air-dried to give 6 as a colorless solid. Yield: 68 mg, 78%; mp
225 °C. ΛM (Me2CO, 5 × 10-4 mol L-1): 93 Ω-1 cm2 mol-1. IR
(cm-1): ν(CdO) 1662, ν(Pt-Cl) 293, 270. H NMR (400 MHz,
1

6158 Organometallics, Vol. 26, No. 25, 2007
Vicente et al.
2
Ph), 2.35 (s, 2 H, CH2, JHPt ) 96 Hz), 1.34 (s, 3 H, Me); 9cis, δ
air-dried to give 12 (mainly the cis isomer) as a yellow solid.
Yield: 35 mg, 60%. IR (cm-1): ν(CtN) 2223, 2193, ν(CdO)
1662, ν(Pt-Cl) 325 (cis). H NMR (300 MHz, CDCl3, cis/trans
2
7.52-7.08 (m, 30 H, Ph), 2.93 (s, 2 H, CH2, JHPt ) 89.6 Hz),
2.30 (s, 3 H, Me). 195Pt{1H} NMR (85.88 MHz, CDCl3): 9trans,
δ -4467; 9cis, δ -4542. Anal. Calcd for C39H35As2ClOPt: C,
52.04; H, 3.90. Found: C, 51.60; H, 3.70.
1
isomers 1:0.9): 12cis, δ 2.80 (q, 2 H, CH2, 4JHH ) 0.6 Hz, 2JHPt
)
4
t
92 Hz), 2.14 (t, 3 H, MeCO, JHH ) 0.6 Hz), 1.58 (s, 18 H, Bu
co-incident with that of the trans isomer), 1.55 (s, 9 H, tBu); 12trans,
δ 2.73 (q, 2 H, CH2, 2JHPt ) 115 Hz, 4JHH ) 0.6 Hz), 2.14 (t, 3 H,
MeCO, 4JHH ) 0.6 Hz), 1.58 (s, 18 H, tBu co-incident with that of
the cis isomer). 13C{1H} NMR (75.45 MHz, CDCl3): 12cis, δ 213.7
(CO, 2JCPt ) 29 Hz), 31.5 (CH2, 1JCPt ) 420 Hz), 30.7 (MeC(O)),
29.98 (CMe3), 29.95 (CMe3); 12trans, 211.1 (CO, 2JCPt ) 54 Hz),
Synthesis of trans-[Pt{CH2C(O)Me}Cl(tht)2] (10). To a solu-
tion of 1 (61 mg, 0.14 mmol) in CH2Cl2 (3 mL), tht (tetrahy-
drothiophen, 32 µL, 0.36 mmol) was added. The resulting suspen-
sion was concentrated to dryness, the residue was extracted with
Et2O (2 × 5 mL), and the extract was concentrated to dryness.
The resulting yellow oil was washed with n-pentane (2 × 3 mL),
treated in vacuo for 10 h, and stirred with Et2O (1 mL) at 0 °C
followed by the addition of pentane (5 mL) to give 10 as a yellow
solid. Yield: 48 mg, 73%; mp 137 °C. IR (cm-1): ν(CdO) 1645,
ν(Pt-Cl) 285. 1H NMR (400 MHz, CDCl3): δ 3.32 (br, 8 H, CH2,
1
29.95 (CMe3), 29.8 (MeCO), 11.7 (CH2, JCPt ) 523 Hz). 195Pt-
{1H} NMR (128.47 MHz, CDCl3): 12cis, δ -4098 (m, {1:1:3:1:
2
2
3:1:1}, JPtN ) 129 Hz, JNPt ) 64.5 Hz); 12trans, δ -4197
(quintuplet, {1:2:3:2:1}, 2JNPt ) 103 Hz). Anal. Calcd for C13H23-
ClN2OPt: C, 34.40; H, 5.11; N, 6.17. Found: C, 34.03; H, 5.16;
N, 6.30.
2
tht), 2.68 (s, 2 H, PtCH2, JHPt ) 110.1 Hz), 2.20-2.14 (m, 8 H,
CH2, tht), 2.17 (s, 3 H, MeC(O)). 13C{1H} NMR (50.30 MHz,
2
2
CDCl3): δ 210.5 (CO, JCPt ) 49.2 Hz), 37.7 (CH2, tht, JCPt
)
Synthesis of trans-[Pt{CH2C(O)Me}Cl(CNtBu)2] (12trans). To
a cooled solution (0 °C) of 1 (45 mg, 0.11 mmol) in CH2Cl2 (3
mL), tBuNC (22.5 µL, 0.20 mmol) was slowly added. The
suspension was filtered through Celite to remove Me4NCl, and the
filtrate was concentrated to dryness in a cold bath. Et2O (10 mL)
was added to the resulting residue, and the suspension was filtered
off. The filtrate was concentrated to dryness and then was vacuum-
dried to give 12trans as a pale yellow solid. Yield: 35 mg, 60%;
mp 104 °C. IR (cm-1): ν(CtN) 2206, ν(CdO) 1666, ν(Pt-Cl)
3
15.8 Hz), 30.2 (MeC(O)), 30.1 (CH2, tht, JCPt ) 11.7 Hz), 20.3
(PtCH2, JCPt ) 599 Hz). 195Pt{1H} NMR (85.9 MHz, CDCl3): δ
1
-3931. Anal. Calcd for C11H21ClOPtS2: C, 28.48; H, 4.56; S,
13.82. Found: C, 28.08; H, 4.54; S, 13.43.
Synthesis of cis- and trans-[Pt{CH2C(O)Me}Cl(CNXy)2] (11).
To a solution of 1 (75 mg, 0.18 mmol) in CH2Cl2 (2 mL) was
added XyNC (47 mg, 0.36 mmol). The suspension was filtered
through Celite to remove Me4NCl, the filtrate was concentrated to
dryness and n-pentane (10 mL) was added. The suspension was
stirred at 0 °C for 30 min and filtered off. The pale yellow solid
obtained was washed with n-pentane (5 mL) and air-dried to give
11 (mainly the cis isomer). Yield: 77 mg, 80%; mp 121-133 °C.
IR (cm-1): ν(CtN) 2200, 2171, ν(CdO) 1660, ν(Pt-Cl) 326 (cis).
1H NMR (300 MHz, CDCl3, cis:trans isomers 1:0.7): 11cis, δ
7.31-7.12 (m, Ph), 3.09 (q, 2 H, PtCH2, 4JHH ) 0.6 Hz, 2JHPt ) 90
Hz), 2.50 (s, 6 H, Me, Xy), 2.47 (s, 6 H, Me, Xy), 2.25 (t, 3 H,
MeC(O)), 4JHH ) 0.6 Hz); 11trans, δ 7.31-7.12 (m, Ph), 3.04 (q,
2 H, PtCH2, JHH ) 0.9 Hz, JHPt ) 114 Hz), 2.53 (s, 12 H, Me,
Xy), 2.25 (t, 3 H, MeC(O), 4JHH ) 0.9 Hz). 13C{1H} NMR (75.45
MHz, CDCl3): δ 213.3 (CO, cis isomer), 210.8 (CO, trans isomer),
136.3 (C), 135.8 (C), 135.7 (C), 130.3 (CH), 130.2 (CH), 129.7
(CH), 128.2 (CH), 128.1 (CH), 31.4 (CH2, cis isomer, 1JCPt ) 422
Hz), 31.2 (MeC(O), cis isomer), 30.2 (MeC(O), trans isomer), 18.7
(Me, Xy) 11.8 (CH2, trans isomer, 1JCPt ) 522 Hz). 195Pt{1H} NMR
(85.88 MHz, CDCl3): 11cis, δ -3999 (m); 11trans, δ -4130 (m).
Anal. Calcd for C21H23ClN2OPt: C, 45.86; H, 4.22; N, 5.09.
Found: C, 45.50; H, 4.31; N, 5.17.
1
2
292. H NMR (300 MHz, CDCl3): δ 2.73 (q, 2 H, CH2, JHPt
)
4
4
115 Hz, JHH ) 0.6 Hz), 2.14 (t, 3 H, MeC(O), JHH ) 0.6 Hz),
1.57 (s, 9 H, tBu). 13C{1H} NMR (75.45 MHz, CDCl3): δ 211.07
2
(CO, JCPt ) 53 Hz), 29.96 (CMe3), 29.86 (MeCO), 11.74 (CH2,
2JCPt ) 525 Hz).
Synthesis of trans-[Pt{C(O)NHXy}Cl(CNXy)2] (13). Method
A. To a solution of complex 11trans (60 mg, 0.11 mmol) in acetone
(5 mL), XyNC (15 mg, 0.114 mmol) was added and the mixture
was heated at 60 °C for 24 h. The suspension was concentrated to
dryness and acetone (3 mL) was added to the residue. The
suspension was filtered off and the solid was air-dried to give 13
as a colorless solid (29 mg, 40%)
4
2
Method B. To a solution of 11trans (62 mg, 0.11 mmol) in
CHCl3 (5 mL), XyNC (31 mg, 0.24 mmol) was added. After 64 h,
the solution was filtered through Celite and the filtrate was
concentrated to dryness. The solid was stirred with Et2O (5 mL),
the suspension was filtered, and the solid recrystallized in CHCl3/
Et2O and air-dried to give 13 as a colorless solid. Yield: 24 mg,
36%; mp 190 °C. IR (cm-1): ν(N-H) 3296, ν(C-N) 2190, ν(Cd
1
Synthesis of trans-[Pt{CH2C(O)Me}Cl(CNXy)2] (11trans). To
a cooled solution (0 °C) of 1 (52 mg, 0.12 mmol) in CH2Cl2 (2
mL) was slowly added XyNC (31 mg, 0.24 mmol). The suspension
was filtered through Celite to remove Me4NCl. The filtrate was
concentrated to dryness, and Et2O (15 mL) was added. The
suspension was filtered off to give 11trans as a pale yellow solid.
By concentration of the filtrate, a second crop of 11trans was
obtained. Yield: 60 mg, 95%; mp 145 °C. IR (cm-1): ν(CtN)
2186, ν(CdO) 1670, ν(Pt-Cl) 304. 1H NMR (300 MHz, CDCl3):
O) 1626, ν(Pt-Cl) 278. H NMR (400 MHz, CDCl3): δ 7.30-
7.26 (m, 2 H, Xy), 7.15-7.13 (m, 4 H, Xy), 7.06-7.04 (m, 3 H,
Xy), 6.80 (s, 1 H, NH), 2.50 (s, 12 H, XyNC), 2.27 (s, 6 H,
XyNHC(O)). 13C{1H} NMR (100.81 MHz, CDCl3): δ 154.4 (CO,
1JCPt ) 1013 Hz), 136.3, 134.6, 130.4 (CH, XyNC), 128.2 (CH,
XyNC), 128.1 (CH, XyNC), 126.8, 19.1 (Me, XyNH), 18.8 (Me,
Xy). Anal. Calcd for C27H28ClN3OPt: C, 50.59; H, 4.40; N, 6.55.
Found: C, 50.15; H, 4.97; N, 6.62. Single crystals of 13‚1.5CHCl3
were obtained by slow evaporation of a CDCl3 solution of 13.
δ 7.31-7.14 (m, Ph), 3.04 (q, 2 H, PtCH2, 4JHH ) 0.9 Hz, 2JHPt
)
Synthesis of trans-[Pt{C(NHXy)2}Cl(CNXy)2]Cl (14). To a
suspension of cis-[PtCl2(CNXy)2] (74 mg, 0.14 mmol) in CHCl3
(5 mL), XyNC (37 mg, 0.28 mmol) was added. After 72 h, the
yellow solution was filtered, and the filtrate was concentrated to
dryness. The solid was stirred with Et2O (5 mL) and the suspension
was filtered off and air-dried to give 14 as a colorless solid. Yield:
85 mg, 77%; mp 236 °C. IR (cm-1): ν(N-H) 3296, ν(CtN) 2204,
ν(Pt-Cl) 310. 1H NMR (300 MHz, CDCl3): δ 12.04 (s, 2 H, NH,
3JHPt ) 84 Hz), 7.36-7.31 (m, 2 H, Xy), 7.18-7.08 (m, 6 H, Xy),
6.94-6.92 (m, 4 H, Xy), 2.47 (s, 12 H, Me). 13C{1H} NMR (75
114 Hz), 2.53 (s, 12 H, Me, Xy), 2.26 (t, 3 H, MeC(O), 4JHH ) 0.9
Hz). 13C{1H} NMR (75.45 MHz, CDCl3): δ 210.8 (CO), 136.3
(C), 130.3 (CH), 128.1 (CH), 30.2 (MeC(O)), 18.7 (Me, Xy), 11.7
1
(CH2, JCPt ) 521 Hz).
Synthesis of cis- and trans-[Pt{CH2C(O)Me}Cl(CNtBu)2] (12).
To a solution of 1 (57 mg, 0.13 mmol) in CH2Cl2 (3 mL), BuNC
t
(32 µL, 0.28 mmol) was added. After 20 min, the suspension was
filtered through anhydrous MgSO4, and the filtrate was concentrated
to dryness. The resulting oil was washed with n-pentane (3 mL),
stirred with n-pentane (5 mL), and concentrated to dryness. This
treatement was repeated three more times and the resulting yellow
oil was stirred at 0 °C for 3 h. The suspension was filtered off and
1
MHz, CDCl3): δ 171.0 (C carbene, JCPt ) 1131 Hz), 137.6 (C),
136.05 (C), 136.02 (C), 132.1 (CNXy), 131.0 (CH), 128.4 (CH),
128.3 (CH), 127.9 (CH), 19.5 (Me), 18.5 (Me). Anal. Calcd for

Acetonyl Platinum(II) Complexes
Organometallics, Vol. 26, No. 25, 2007 6159
1
C35H38Cl2N4Pt: C, 53.85; H, 4.91; N, 7.18. Found: C, 53.30; H,
4.96; N, 7.18. Single crystals of 15 were obtained by slow diffusion
of Et2O into a solution of 15 in CDCl3.
IR (cm-1): ν(CdO) 1656, ν(Pt-Cl) 317. H NMR (400 MHz,
2
CDCl3): δ 5.55 (m, 2 H, CH trans to acetonyl, JHPt ) 38.6 Hz),
4.82 (m, 2 H, CH trans to Cl, 2JHPt ) 74.6 Hz), 4.15 (m, 2 H, CH),
2.91 (s, 2 H, PtCH2, 2JHPt ) 121.5 Hz), 2.07 (s, 3 H, Me), 1.78 (m,
2 H, CH2, 4JHPt ) 12 Hz). 13C{1H} NMR (50.30 MHz, CDCl3): δ
209.1 (CO, 2JCPt ) 44 Hz), 99.1 (CH trans to acetonyl, 1JCPt ) 29
Synthesis of cis-[Pt{CH2C(O)Me}2(CNXy)2] (15). XyNC (225
mg, 1.71 mmol) was added to a solution of [Pt{CH2C(O)Me}2-
(bpy)] (200 mg, 0.43 mmol) in CH2Cl2 (7 mL). After 15 min the
suspension was filtered through Celite to remove Me4NCl, and the
filtrate was concentrated to dryness. The residue was extracted with
Et2O (10 mL). The extract was concentrated (4 mL), and n-pentane
(15 mL) was added to precipitate a solid that was stirred for 1 h at
0 °C. The resulting suspension was filtered off, and the yellow solid
obtained was washed with n-pentane (5 mL) and air-dried to give
15. Yield: 160 mg, 65%; mp 104-109 °C. IR (cm-1): ν(CtN)
2182, 2148; ν(CdO) 1659. 1H NMR (400 MHz, CDCl3): δ 7.27-
7.22 (m, 2 H, Xy), 7.12-7.01 (m, 4 H, Xy), 2.88 (s, 4 H, CH2,
2JHPt ) 102 Hz), 2.47 (s, 12 H, Me, Xy), 2.14 (s, 6 H, MeC(O),
4JHPt ) 16 Hz). 13C{1H} NMR (75.45 MHz, CDCl3): δ 213.9 (CO,
2JCPt ) 39 Hz), 143.2 (br, CN), 135.3 (C, Xy), 129.4 (CH, Xy),
128.1 (CH, Xy), 126.6 (br, C, Xy), 32.0 (PtCH2, 1JCPt ) 471 Hz),
30.8 (MeC(O)), 18.7 (Me, Xy). 195Pt{1H} NMR (85.88 MHz,
CDCl3): δ -4167 (m). Anal. Calcd for C24H28N2O2Pt: C, 50.43;
H, 4.94; N, 4.90. Found: C, 50.32; H, 4.95; N, 5.12.
Synthesis of [Pt{CH2C(O)Me}Cl(η2-C2H4)(py)] (16). To a
solution of 1 (62 mg, 0.15 mmol) in CH2Cl2 (3 mL), py (24 µL,
0.29 mmol) was added. The resulting suspension was stirred for
30 min and then was filtered through Celite to remove Me4NCl.
The filtrate was concentrated (to ca. 1 mL) and Et2O (5 mL) was
added. The solution was concentrated until a colorless solid
precipitated. Addition of n-pentane (10 mL) gave more precipitate,
which was filtered off, washed with n-pentane (5 mL), and air-
dried to give 16 as a colorless solid. Yield: 47 mg, 82%; mp 64
°C. IR (cm-1): ν(CdO) 1657; ν(Pt-Cl) 317. 1H NMR (400 MHz,
CDCl3): δ 8.60 (m, 2 H, py), 7.85 (m, 1 H, py), 7.48 (m, 2 H, py),
1
3
Hz), 74.1 (CH trans to Cl, JCPt ) 171.4 Hz), 70.3 (CH2, JCPt
)
109 Hz), 48.8 (CH, 2JCPt ) 51 Hz), 37. 5 (PtCH2, 1JCPt ) 613 Hz),
30.9 (s, Me). 195Pt{1H} NMR (85.88 MHz, CDCl3): δ -3381. Anal.
Calcd for C10H13ClOPt: C, 31.63; H, 3.45. Found: C, 31.96; H,
3.64.
Synthesis of [Pt{CH2C(O)Me}Cl(cod)] (19). Method a. To a
solution of 1 (76 mg, 0.18 mmol) in CH2Cl2 (2 mL) was added
cod (33 µL, 0.27 mmol). After stirring for 30 min, the resulting
suspension was filtered to remove Me4NCl, and the filtrate was
concentrated to dryness. The residue was extracted with Et2O (3
× 5 mL) and the resulting solution was concentrated to dryness
and dried under vacuum for 6 h to give 19 as a colorless solid.
Yield: 36 mg, 51%.
Method b. A suspension of [PtCl2(cod)] (72 mg, 0.19 mmol)
and [Hg{CH2C(O)Me}2] (61 mg, 0.19 mmol) in Me2CO (10 mL)
was refluxed for 28 h. The resulting solution was concentrated to
dryness, and the residue was extracted with Et2O (10 mL) and
filtered through Celite. The filtrate was concentrated to dryness to
give a colorless solid, which was washed with H2O (3 × 5 mL),
dissolved in Et2O (10 mL), stirred with anhydrous MgSO4, and
then filtered off. The filtrate was concentrated to dryness, and the
residue was stirred with n-pentane (5 mL). The suspension was
filtered off, and the resulting colorless solid was air-dried to give
19. Yield: 20 mg, 20%. IR (cm-1): ν(CdO) 1656, ν(Pt-Cl) 316.
1H NMR (300 MHz, CDCl3): δ 5.61 (m, 2 H, CH trans to acetonyl,
2JHPt ) 40 Hz), 4.93 (m, 2 H, CH trans to Cl, 2JHPt ) 71 Hz), 2.91
2
(s, 2 H, PtCH2, JHPt ) 103 Hz), 2.57-2.24 (m, 8 H, CH2, cod),
2.24 (s, 3 H, Me). 13C{1H} NMR (75.45 MHz, CDCl3): δ 211.4
3.89 (s, 4 H, C2H4, 2JHPt ) 68.6 Hz), 2.65 (s, 2 H, PtCH2, 2JHPt
)
1
(CO), 112.6 (CH trans to acetonyl, JCPt ) 48.6 Hz), 90.0 (CH
100.4 Hz), 2.32 (s, 3 H, MeC(O)). 13C{1H} NMR (100.81 MHz,
CDCl3): δ 215.5 (CO), 150.5 (CH, o-py), 139.0 (CH, p-py), 126.8
(CH, m-py, 3JCPt ) 18 Hz), 66.0 (C2H4, 1JCPt ) 221 Hz), 31.5 (MeC-
(O)), 18.4 (s, PtCH2, 1JCPt ) 562 Hz). 195Pt{1H} NMR (85.88 MHz,
CDCl3): δ -3366. Anal. Calcd for C10H15ClNOPt: C, 30.35; H,
3.82; N, 3.54. Found: C, 30.31; H, 3.61; N, 3.52.
trans to Cl, 1JCPt ) 194 Hz), 35.8 (PtCH2, 1JCPt ) 551.4 Hz), 31.9
2
2
(CH2, JCPt ) 18.8 Hz), 31.0 (Me), 28.2 (CH2, JCPt ) 17.7 Hz).
195Pt{1H} NMR (85.88 MHz, CDCl3): δ -3507. Anal. Calcd for
C11H17ClOPt: C, 33.38; H, 4.33. Found: C, 33.73; H, 4.60.
Synthesis of [Pt{CH2C(O)Me}Cl(dppm)] (20). A suspension
of 1 (62 mg, 0.15 mmol) in THF (5 mL) was stirred for 30 min
with dppm (bis(diphenylphosphino) methane, 56.6 mg, 0.15 mmol)
under N2. The resulting yellow suspension was filtered through
Celite to remove Me4NCl, the filtrate was concentrated, and Et2O
(20 mL) was added. The resulting suspension was filtered off, and
the solid was recrystallized from toluene/Et2O to give 20 as a yellow
solid. Yield: 47 mg, 50%; mp 182-184 °C. IR (cm-1): ν(CdO)
Synthesis of [Pt{CH2C(O)Me}Cl(py)2] (17). To a solution of
16 (51.7 mg, 0.13 mmol) in Me2CO (3 mL) was added py (53 µL,
0.65 mmol). The resulting solution was refluxed for 4.5 h, the
suspension was filtered through Celite, and the filtrate was
concentrated to ca. 0.5 mL. Addition of n-pentane (5 mL) gave a
suspension, which was stirred for 30 min at 0 °C and then filtered
off. The solid was air-dried to give 17 as a colorless solid. Yield:
1
1646; ν(Pt-Cl) 293. H NMR (400 MHz, CDCl3): δ 7.85-7.68
1
40 mg, 69%. IR (cm-1): ν(CdO) 1650; ν(Pt-Cl) 332, 290. H
2
(m, Ph), 7.52-7.40 (m, Ph), 4.27 (t, 2 H, CH2, dppm, JHP ) 6.6
RMN: (400 MHz, CDCl3, cis:trans isomers 3:1): 17cis, δ 8.79-
Hz), 2.93 (dd, 2 H, PtCH2, 2JHP ) 12.6 Hz, 2JHP ) 1.8 Hz, 2JHPt
)
3
8.77 (m, 2 H, py, JHPt ) 46 Hz), 8.61-8.60 (m, 2 H, py), 7.81-
90 Hz), 1.90 (s, 3 H, MeC(O)). 31P{1H} NMR (121.5 MHz,
7.75 (m, 2 H, py), 7.36-7.26 (m, 2 H, py), 3.16 (s, 2 H, PtCH2,
2JHPt ) 110 Hz), 2.33 (s, 3 H, Me); 17trans, δ 8.77-8.92 (m, 2 H,
py), 7.81-7.75 (m, 2 H, py), 7.36-7.26 (m, 2 H, py), 2.90 (s, 2 H,
PtCH2, 2JHPt ) 122 Hz), 1.73 (s, 3 H, Me). 13C{1H} (100.81 MHz,
CDCl3): 17cis, δ 215.7 (CO), 152.3 (CH, o-py), 150.4 (CH, o-py),
137.7 (CH, p-py), 126.3 (CH, m-py), 125.5 (CH, m-py), 30.3 (Me),
2
CDCl3): δ -43.7, -45.8 (AB system, P trans to Cl: JPP ) 55
1
2
1
Hz, JPPt ) 3645 Hz, P trans to acetonyl, JPP ) 55 Hz, JPPt
)
1656 Hz). Anal. Calcd for C28H27ClOP2Pt: C, 50.05; H, 4.05.
Found: C, 49.82; H, 4.08.
1
15.2 (CH2, JCPt ) 569 Hz); 17trans, δ 210.9 (CO), 153.5 (CH,
o-py), 137.5 (CH, p-py), 125.6 (CH, m-py), 29.4 (Me), 25.0 (CH2,
1JCPt ) 679 Hz). Anal. Calcd for C13H15ClN2OPt: C, 35.02; H,
3.39; N, 6.28. Found: C, 34.67; H, 3.38; N, 6.28.
Synthesis of [Pt{CH2C(O)Me}Cl(nbd)] (18). To a solution of
1 (65 mg, 0.15 mmol) in CH2Cl2 (2 mL) was added norbornadiene
(30 µL, 0.29 mmol). After 2 h, the suspension was filtered through
Celite to remove Me4NCl, and the filtrate was concentrated to
dryness. The residue was dissolved in Et2O (10 mL) and filtered
off. The filtrate was concentrated to dryness and dried under vacuum
to give 18 as a colorless solid. Yield: 41 mg, 71%; mp 91-94 °C.
Synthesis of [Pt{CH2C(O)Me}Cl(dbbpy)] (21). To a solution
of 1 (100 mg, 0.24 mmol) in CH2Cl2 (3 mL), dbbpy (4,4′-
ditertbutyl-2,2′-bipyridine, 65 mg, 0.24 mmol) was added. The
resulting suspension was filtered through Celite to remove Me4-

6160 Organometallics, Vol. 26, No. 25, 2007
Vicente et al.
NCl, and the filtrate was concentrated (1 mL). Addition of Et2O
(10 mL) gave a suspension that was filtered off, washed with Et2O
(5 mL), and air-dried to give 21 as a yellow solid. Yield: 113 mg,
86%; mp 295-300 °C. IR (cm-1): ν(CdO) 1650, ν(Pt-Cl) 326.
1H NMR (400 MHz, CDCl3): δ 9.68 (d, 1 H, H6′, 3JHH ) 6.3 Hz,
Hz). 31P{1H} NMR (121 MHz, CDCl3): δ 8.86 (1JPPt ) 4601 Hz).
195Pt{1H} NMR: δ (85.88 MHz, CDCl3): -3648 (d, 1JPPt ) 4601
Hz). Anal. Calcd for C26H27O3PPt: C, 50.90; H, 4.44. Found: C,
51.40; H, 4.63.
Synthesis of [Pt{CH2C(O)Me}(acac)(CNXy)] (25). To a solu-
tion of 22 (32 mg, 0.08 mmol) in CH2Cl2 (1 mL) was added XyNC
(11 mg, 0.08 mmol). The pale yellow solution was concentrated to
dryness, and the residue was extracted with n-pentane (2 mL) and
filtered. The filtrate was concentrated to dryness under vacuum for
5 h to give 25 as a colorless solid. Yield: 20 mg, 50%; mp 80-83
°C. IR (cm-1): ν(CtN) 2179; ν(CdO) 1675, 1582, 1521. 1H NMR
(400 MHz, CDCl3): δ 7.18 (m, 1 H, Xy), 7.10 (m, 2 H, Xy), 5.52
3
2JHPt ) 44.9 Hz), 9.47 (d, 1 H, H6, JHH ) 5.9 Hz), 7.88 (d, 1 H,
4
4
H3, JHH ) 1.4 Hz), 7.84 (d, 1 H, H3′, JHH ) 1.4 Hz), 7.59 (dd,
1 H, H5, 4JHH ) 1.4 Hz, 3JHH ) 5.9 Hz), 7.56 (dd, 1 H, H5’, 4JHH
3
2
) 1.4 Hz, JHH ) 6.3 Hz), 3.34 (s, 2 H, PtCH2, JHPt ) 108 Hz),
2.31 (s, MeC(O)), 1.43 (s, 9 H, Bu), 1.41 (s, 9 H, Bu). 13C{1H}
t
t
2
NMR (100.8 MHz, CDCl3): δ 216.3 (CO, JCPt ) 42 Hz), 163.4
(C, dbbpy), 162.3 (C, dbbpy), 157.1 (C, dbbpy), 154.9 (C, dbbpy,
2
2JCPt ) 40 Hz), 151.3 (C6′, 2JCPt ) 34 Hz), 147.8 (C6), 124.9 (C5′,
(s, 1 H, CH, acac), 3.14 (s, 2 H, CH2, JHPt ) 112 Hz), 2.47 (s, 6
3JCPt ) 49 Hz), 123.9 (C5), 119.0 (C3′, 3JCPt ) 25 Hz), 118.3 (C3),
H, Me, Xy), 2.21 (s, 3 H, MeC(O)CH2), 2.02 (s, 3 H, Me, acac),
1.99 (s, 3 H, Me, acac). 13C{1H} NMR (75.45 MHz, CDCl3): δ
213.8 (CO, 2JCPt ) 47 Hz), 186.8 (CO, acac, 2JCPt ) 21 Hz), 183.7
1
35.6 (CMe3), 30.0 (MeC(O)), 30.0 (CMe3), 19.7 (PtCH2, JCPt
)
594 Hz). 195Pt{1H} NMR (86.18 MHz, CDCl3): δ -2953. Anal.
Calcd for C21H29ClN2OPt: C, 45.36; H, 5.26; N, 5.04. Found: C,
45.03; H, 5.36; N, 5.03.
2
(CO, acac, JCPt ) 16 Hz), 135.5 (C, Xy), 128.8 (CH, Xy), 127.8
3
(CH, Xy), 101.9 (CH, acac, JCPt ) 67 Hz), 30.3 (MeC(O)), 27.8
3
3
(Me, acac, JCPt ) 12 Hz), 27.1 (Me, acac, JCPt ) 34 Hz), 18.2
Synthesis of [Pt{CH2C(O)Me}(acac)(C2H4)] (22). To a solution
of 1 (52 mg, 0.12 mmol) in CH2Cl2 (4 mL), [Tl(acac)] (39 mg,
0.13 mmol) was added. After stirring for 15 min, the suspension
was concentrated to dryness, and the residue was extracted with
Et2O (2 × 5 mL). The resulting solution was concentrated to
dryness, and the solid treated for 2 h under vacuum to give 22 as
a pale yellow solid that was stored at -30 °C. Yield: 44 mg, 95%;
(Me, Xy), 14.1 (PtCH2, JCPt ) 612 Hz). 195Pt{1H} NMR (85.88
1
MHz, CDCl3): δ -3355 (t {1:1:1}, 2JPtN ) 146 Hz). Anal. Calcd
for C17H21NO3Pt: C, 42.32; H, 4.39; N, 2.90. Found: C, 42.70;
H, 4.49; N, 3.07.
Crystallography. Crystals were measured on a Bruker Smart
APEX machine. Data were collected using monochromated Mo KR
radiation in w scan. The structures of 3, 13, 14, and [PtCl2(CNXy)2]
were solved by direct methods, that of 1 and 8trans by the heavy
atom method. All were refined anisotropically on F2. Restraints to
local aromatic-ring symmetry or light-atom displacement factor
components were applied in some cases. The ordered methyl groups
were refined using rigid groups, the NH (13 and 14) was refined
as free, and the other hydrogens were refined using a riding mode.
The methyl (C3) of the acetonyl ligand of compound 8trans is
disordered over two positions, ca. 54:46.
Computational Details. Density functional calculations were
carried out using the Gaussian 03 package.26 The hybrid density
functional B3LYP method was applied.27 Effective core potentials
(ECP) and their associated double-ú basis set, LANL2DZ, were
used for platinum atoms.28 Similar description was used for heavy
elements as Cl or P, supplemented with an extra d-polarization
function.29 The basis set for the light elements as C, N, O, and H
was 6-31G*.30 Geometry optimizations were carried out on the full
potential-energy surface, without symmetry restrictions, and they
were characterized by a vibrational analysis. Since decoordination
of chloride from TPBC is always unfavored in gas phase for
1
mp 44 °C. IR (cm-1): ν(CdO) 1674, 1581, 1518. H NMR (400
MHz, CDCl3): δ 5.49 (s, 1 H, CH), 3.86 (s, 4 H, C2H4, 2JHPt ) 67
2
Hz), 2.53 (s, 2 H, PtCH2, JHPt ) 106.4 Hz), 2.15 (s, 3 H, MeC-
(O)CH2), 2.10 (s, 3 H, Me, acac), 1.95 (s, 3 H, Me, acac). 13C{1H}
2
NMR (100.8 MHz, CDCl3): δ 213.7 (CO, JCPt ) 49 Hz), 188.5
3
(CO, acac), 183.4 (CO, acac), 101.3 (CH, JCPt ) 61 Hz), 62.5
1
(C2H4, JCPt ) 238 Hz), 30.4 (MeC(O)CH2), 28.3 (s, Me, acac),
26.8 (s, Me, acac), 16.2 (PtCH2, 1JCPt ) 663 Hz). 195Pt{1H} NMR
(86.18 MHz, CDCl3): δ -3204.7. Anal. Calcd for C10H16O3Pt: C,
31.66; H, 4.25. Found: C, 31.52; H, 4.22.
Synthesis of [Pt{CH2C(O)Me}(acac)(CO)] (23). A stream of
CO was bubbled at atmospheric pressure into a solution of 22 (60
mg, 0.16 mmol) in CH2Cl2 (3 mL) for 15 min. The mixture was
filtered through Celite, and the filtrate was concentrated to dryness
under vacuum to give 23 as a pale yellow solid that was stored at
-30 °C. Yield: 50 mg, 84%; mp 81-84 °C. IR (cm-1): ν(CtO)
1
2093, ν(CdO) 1681, 1573, 1523. H NMR: (400 MHz, CDCl3):
2
δ 5.60 (s, 1 H, CH), 3.14 (s, 2 H, CH2, JHPt ) 109 Hz), 2.21 (s,
3 H, MeC(O)CH2), 2.08 (s, 3 H, Me, acac), 2.06 (s, 3 H, Me, acac).
13C{1H} NMR (75.45 MHz, CDCl3): δ 212.1 (MeC(O)CH2, 2JCPt
) 46 Hz), 188.6 (CO, acac, 2JCPt ) 22 Hz), 183.7 (CO, acac, 2JCPt
) 16 Hz), 157.4 (CO), 102.4 (CH, 3JCPt ) 66 Hz), 30.5 (MeC(O)-
(26) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb,
M. A.; Cheeseman, J. R.; Montgomery, J. A., Jr.; Vreven, T.; Kudin, K.
N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.;
Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.;
Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.;
Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li,
X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Bakken, V.; Adamo, C.;
Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.;
Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.;
Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich,
S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A.
D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A.
G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.;
Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham,
M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.;
Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian
03, revision C.02; Gaussian, Inc.: Wallingford, CT, 2004.
(27) Becke, A. D. J. Chem. Phys. 1993, 98, 5648. Lee, C.; Yang, W.;
Parr, R. G. Phys. ReV. B 1988, 37, 785.
(28) Hay, P. J.; Wadt, W. R. J. Chem. Phys. 1985, 82, 299.
(29) Wadt, W. R.; Hay, P. J. J. Chem. Phys. 1985, 82, 284. Ho¨llwarth,
A.; Bo¨hme, M.; Dapprich, S.; Ehlers, A. W.; Gobbi, A.; Jonas, V.; Ko¨hler,
K. F.; Stegman, R.; Veldkamp, A.; Frenking, G. Chem. Phys. Lett. 1993,
208, 237.
(30) Hariharan, P. C.; Pople, J. A. Theor. Chim. Acta 1973, 28, 213.
Francl, M. M.; Petro, W. J.; Hehre, W. J.; Binkley, J. S.; Gordon, M. S.;
DeFrees, D. J.; Pople, J. A. J. Chem. Phys. 1982, 77, 3654.
3
3
CH2), 27.8 (Me, acac, JCPt ) 14 Hz), 26.7 (Me, acac, JCPt ) 38
Hz), 16.9 (CH2, JCPt ) 595 Hz). 195Pt{1H} NMR (85.88 MHz,
CDCl3): δ -3598. Anal. Calcd for C9H12O4Pt: C, 28.50; H, 3.19.
Found: C, 28.60; H, 3.35.
1
Synthesis of [Pt{CH2C(O)Me}(acac)(PPh3)] (24). To a solution
of 22 (27.7 mg, 0.07 mmol) in CH2Cl2 (2 mL), PPh3 (19.5 mg,
0.07 mmol) was added. The reaction mixture was filtered through
Celite, and the filtrate was concentrated to dryness. The residue
was stirred with Et2O (2 mL), and the solvent was removed under
vacuum for 6 h to give 24 as a colorless solid. Yield: 44 mg, 97%;
mp 112-119 °C. IR (cm-1): ν(CdO) 1657, 1571, 1521. 1H NMR
(300 MHz, CDCl3): δ 7.71-7.64 (m, 9 H, Ph), 7.44-7.39 (m, 6
H, Ph), 5.40 (s, 1 H, CH, acac), 2.58 (d, 2 H, CH2, 3JHP ) 3.3 Hz,
2JHPt ) 100 Hz), 2.03 (s, 3 H, MeC(O)CH2), 1.97 (s, 3 H, Me,
acac), 1.57 (s, 3 H, Me, acac). 13C{1H} NMR (100.81 MHz,
CDCl3): δ 215.6 (MeC(O)CH2), 184.9 (CO, acac), 183.4 (CO,
acac), 134.6 (d, Corto, PPh3, 2JCP ) 11 Hz), 130.6 (d, CHpara, PPh3,
1
4JCP ) 2 Hz), 128.7 (d, Cipso, PPh3, JCP ) 48 Hz), 101.1 (CH,
4
3JCPt ) 61 Hz), 31.6 (Me, acac), 27.8 (d, MeC(O)CH2, JCP ) 6
2
1
Hz), 27.5 (Me, acac), 14.0 (d, PtCH2, JCP ) 6 Hz, JCPt ) 672.7

Acetonyl Platinum(II) Complexes
Scheme 1
Organometallics, Vol. 26, No. 25, 2007 6161
a smaller molar ratio, a mixture of 4 and 1 was obtained.
However, even when a strong excess of alkyne was used, an
analytically pure sample of 4 could not be isolated (see
Experimental Section). Complexes 3-5 are stable at room
temperature in the solid state and in organic solvents solutions.
The room-temperature reaction of a THF suspension of 1 with
PPh3 or AsPh3, in 1:1 molar ratio, took place with precipitation
of cis-Me4N[Pt{CH2C(O)Me}Cl2(L)] [L ) PPh3 (6), AsPh3 (7)]
(Scheme 1). When these reactions were carried out in CH2Cl2
or Me2CO, Me4NCl precipitated and a mixture of trans-[Pt-
{CH2C(O)Me}Cl(L)2] [L ) PPh3 (8trans), AsPh3 (9trans)], and
1 + 6 or 1 + 7, respectively, was isolated. This suggests that
the precipitation of 6 or 7 in THF is crucial to isolate them. In
fact, when the mixture 1 + 6 + 8 or 1 + 7 + 9, obtained in
CH2Cl2, was stirred in THF and Me4NCl was added, complex
6 or 7, respectively, was obtained. The attempts to prepare cis-
Me4N[Pt{CH2C(O)Me}Cl2(tht)] (tht ) tetrahydrothiophene) by
reacting 1 with 1 equiv of tht in THF led to a complex mixture,
containing trans-[Pt{CH2C(O)Me}Cl(tht)2] (10) and 1.
Synthesis of Neutral Acetonyl Platinum(II) Complexes
from 1. By reacting a CH2Cl2 solution of 1 with two or more
equiv of PPh3, AsPh3, or tht, complex 8trans, 9trans, or 10,
respectively, was obtained (Scheme 1). The complex 8trans or
9trans was also obtained by reacting 6 or 7 with 1 equiv of the
corresponding neutral ligand. A CDCl3 solution of 9trans led
to a mixture of cis/trans isomers (1:1) after 16 h at room
temperature. In the same conditions, no isomerization was
observed for 8trans. The room-temperature reaction of [Hg-
{CH2C(O)Me}Cl] with [Pt(PPh3)4] in toluene gave Hg, an 1:3
mixture of 8cis and 8trans, and traces of cis-[PtCl2(PPh3)2]. It
has been reported that 8cis is obtained by oxidative addition of
ClCH2C(O)Me to [Pt(PPh3)4] at room temperature and that
8trans, impurified with cis-[PtCl2(PPh3)2], is isolated by re-
fluxing 8cis in benzene, in the presence of PPh3.10,37
carbonyl as entering ligand, their corresponding transition states
SPY2C are not available. Solvent effects were taken into account
through the PCM algorithm,31 using standard options of PCM and
cavity keywords,26 by calculating the energies at the geometries
optimized for gas phase.
Results and Discussion
Synthesis of Anionic Acetonyl Pt(II) Complexes from
Me4N[Pt{CH2C(O)Me}Cl2(C2H4)] (1). Complex 1 has been
used as starting material to prepare other anionic acetonyl
complexes by replacing ethylene by CO, styrene, diphenylacety-
lene, 1,1-dimethylallene, PPh3, or AsPh3. Thus, after bubbling
CO for a few minutes through a cooled (0 °C) Me2CO solution
of 1, cis-Me4N[Pt{CH2C(O)Me}Cl2(CO)] (2) was obtained
(Scheme 1). In the solid state, this carbonyl complex must be
stored below -30 °C as it decomposes at room temperature.
When the reaction was carried out in CH2Cl2, complex 2 was
also formed but it decomposed faster than in Me2CO. Similarly,
the room-temperature reaction between 1 and an excess of H2Cd
CdCMe2 (1:2) in CH2Cl2 gave cis-Me4N[Pt{CH2C(O)Me}Cl2-
(η2-H2CdCdCMe2)] (5), as the result of the η2 coordination
of the allene through the less substituted double bond, as shown
in Scheme 1. A similar behavior has been reported for a Pt(II)
complex.32 Insertion of allenes into alkyl metal bonds to give
η3-allylic complexes have been described.33-36 However, com-
plex 5 was recovered unchanged when it was heated in Me2-
CO for 24 h (80 °C, Carius tube). Substitution of ethylene in
1 by styrene (1:5, 50 °C, Me2CO) or diphenylacetylene (1:10,
60 °C, Me2CO or room temperature, CHCl3) gave cis-Me4N-
[Pt{CH2C(O)Me}Cl2(η2-L)] (L ) PhCHdCH2 (3), PhCtCPh
(4); Scheme 1). When the latter reaction was carried out using
We have reported the synthesis of complexes [Pd{CH2C(O)-
Me}Cl(CNR)n] (n ) 1, 2) and [Pd{CH2C(O)Me}(CNR)3]+ (R
) tBu, Xy ) 2,6-dimethylphenyl) and the easy transformation
of these compounds into C-palladated â-ketoenamine complexes
after insertion of one molecule of isocyanide into the C-Pd
bond followed by a â-ketoimine to â-ketoenamine tautomer-
ization process.38 However, fast addition at room temperature
of 2 equiv of RNC to 1 in CH2Cl2 gave almost inmediately a
mixture of cis- and trans-[Pt{CH2C(O)Me}Cl(CNR)2] (R ) Xy
t
(11; 1:0.4), Bu (12; 1:0.3)) (Scheme 2) without insertion
products. The cis isomer transformed gradually into the trans
in CDCl3 until the equilibrium was reached at 1:0.7 for 11 (after
5 h at room temperature or 80 °C in a Carius tube for 4 days in
CH2Cl2) or 1:0.9 for 12 (after 48 h at room temperature). The
slow addition of 1 equiv of isocyanide to a stirred and cooled
(0 °C) solution of 1 gave 11trans (in THF) or 12trans (in CH2-
Cl2) and unreacted 1. When 2 equiv were slowly added at 0 °C
in CH2Cl2, only the trans isomer was obtained and no isomer-
ization after 2 days in a CDCl3 solution was observed. The
addition of 0.3 equiv of isocyanide to a CDCl3 solution of
11trans led to the 1:0.7 cis/trans equilibrium mixture. This
means that the local excess of isocyanide produced in the fast
addition reaction is responsible for the trans to cis isomerization.
(31) Tomasi, J.; Persico, M. Chem. ReV. 1994, 94, 2027. Amovilli, C.;
Barone, V.; Cammi, R.; Cance`s, E.; Cossi, M.; Mennucci, B.; Pomelli, C.
S.; Tomasi, J. AdV. Quantum Chem. 1998, 32, 227.
(32) De Renzi, A.; Di Blasio, B.; Panunzi, A.; Pedone, C.; Vitagliano,
A. J. Chem. Soc., Dalton Trans. 1978, 1392.
(33) Hartley, F. R. In ComprehensiVe Organometallic Chemistry; Wilkin-
son, G., Stone, F. G. A., Abel, E. W., Eds.; Pergamon Press: Oxford, U.
K., 1982; Vol. 6, p 471
t
However, the addition of 0.3 equiv of BuNC to a CDCl3
solution of 12trans led to a mixture of unidentified products.
Another attempt to insert XyNC into the Pt-acetonyl bond
was carried out by reacting 11trans with 1 equiv of XyNC at
(34) Bowden, B. F.; Giles, R. Coord. Chem. ReV. 1976, 20, 81.
(35) Yagyu, T.; Suzaki, Y.; Osakada, K. Organometallics 2002, 21, 2088.
(36) De Felice, V.; Cucciolito, M. E.; De Renzi, A.; Ruffo, F.; Tesauro,
D. J. Organomet. Chem. 1995, 493, 1.
(37) Suzuki, K.; Yamamoto, H. Inorg. Chim. Acta 1993, 208, 225.
(38) Vicente, J.; Arcas, A.; Ferna´ndez-Herna´ndez, J. M.; Bautista, D.;
Jones, P. G. Organometallics 2005, 24, 2516.

6162 Organometallics, Vol. 26, No. 25, 2007
Vicente et al.
Scheme 2
Scheme 3. Proposed Reaction Pathway (Dashed Arrows) for
the Synthesis of 13 and 14a
a The solid arrows indicate the reagents and isolated products.
suitable for a nuclephilic attack, could not be formed. Heating
a CDCl3 solution of 15 for 3 days at 40 °C did not produce
insertion of the isocyanide into the Pt-C bond, isomerization,
or hydrolysis. The greater stability of the cis isomer can be a
consequence of a stronger transphobia39,40 between the pair of
acetonyl ligands than that between an acetonyl and an isocyanide
ligand.
60 °C for 24 h in acetone. However, we obtained the insoluble
carbamoyl complex trans-[Pt{C(O)NHXy}Cl(CNXy)2](13) and
a solution containing a complex mixture of compounds. The
reaction with 2 equiv of XyNC in CHCl3 (room temperature,
64 h) gave a mixture insoluble in Et2O that, after recrystalli-
zation, led to pure 13 and a mixture of 13 and [Pt{C(NHXy)2}-
Cl(CNXy)2]Cl(14). Complex 13 could be formed through the
intermediate [Pt{CH2C(O)Me}(CNXy)3]Cl (A; Scheme 3)
which, in the presence of H2O might afford acetone (detected
in the reaction mixture), [PtCl(CNXy)3]+, and OH- (B‚OH) that
may well attack an isocyanide ligand to give 13. The previously
reported OH- attack to [Pt(CNMe)2(PPh3)2]2+, to give [Pt{C(O)-
NHMe}(CNMe)(PPh3)2]+,20 is a precedent for this process.
Formation of 14 requires the presence of an additional chloride
and XyNH2. We propose that HCl, formed from CHCl3, could
give acetone and C which might react with 1 equiv of XyNC
to give the cationic complex [PtCl(CNXy)3]Cl (B‚Cl). Its
reaction with (H3O)Cl is expected to give CO + (XyNH3)Cl20
+ C. This complex would react again with another equiv of
XyNC and XyNH2 giving 14, recovering half of the HCl used
in the process. To support our proposal we have succeeded in
preparing 14 by reacting [PtCl2(CNXy)2] with two equiv of
XyNC in CHCl3.
Complex 1 reacted with 2 equiv of py (1:2) in CH2Cl2 leading
to the precipitation of Me4NCl and formation of [Pt{CH2C(O)-
Me}Cl(η2-C2H4)(py)] (16; Scheme 2). This complex was also
obtained using Me2CO as solvent. When an Me2CO solution
of 16 and py (1:1) was refluxed for 4.5 h, ethylene was displaced
and a 3:1 mixture of cis- and trans-[Pt{CH2C(O)Me}Cl(py)2]
(17) was obtained. No reaction was observed between a CDCl3
solution of 1 and OPPh3 or pyridine N-oxide, after 2 days at
room temperature.
Complexes 6-17 are stable in the solid state and dissolved
in organic solvents (Me2CO, CH2Cl2, CHCl3, THF) at room
temperature.
On the Mechanism of Substitution Reactions from Com-
plex 1. Starting from complex 1, ethylene is replaced by various
ligands (CO, PhCHdCH2, PhCtCPh, H2CdCdCMe2, PPh3,
AsPh3) to give complexes 2-7 (Scheme 1). However, a chloro
ligand is displaced when the entering ligand is py (Scheme 2).
DFT calculations on the reactions with CO, PMe3 and py have
been carried out to explain this difference. Because the results
for CO and PMe3 are similar, we will discuss here only those
with PMe3 and py. The data for the reaction with CO will also
(39) Vicente, J.; Arcas, A.; Bautista, D.; Jones, P. G. Organometallics
1997, 16, 2127. Vicente, J.; Abad, J. A.; Frankland, A. D.; Ram´ırez de
Arellano, M. C. Chem. Eur. J. 1999, 5, 3066. Vicente, J.; Abad, J. A.;
Herna´ndez-Mata, F. S.; Jones, P. G. J. Am. Chem. Soc. 2002, 124, 3848.
Vicente, J.; Abad, J. A.; Mart´ınez-Viviente, E.; Jones, P. G. Organometallics
2002, 21, 4454.
After these unexpected results, we consider of interest to
explore the reaction of 4 equiv of XyNC with our previously
reported diacetonyl isocyanide complex [Pt{CH2C(O)Me}2-
(bpy)].11 However, the substitution product cis-[Pt{CH2C(O)-
Me}2(CNXy)2] (15) was obtained (Scheme 2), probably because
formation of a cationic complex, as that proposed above, more
(40) Vicente, J.; Arcas, A.; Ga´lvez-Lo´pez, M. D.; Jones, P. G. Orga-
nometallics 2006, 25, 4247.

Acetonyl Platinum(II) Complexes
Organometallics, Vol. 26, No. 25, 2007 6163
Figure 1. Energy profile for the reaction pathway of substitution of chloride (path C) or ethylene (path E) by PMe3 in CH2Cl2 as solvent.
Figure 2. Energy profile for the reaction pathway of substitution of chloride (path C) or ethylene (path E) by pyridine in CH2Cl2 as
solvent.
be used here to compare the three ligands and have been
included in the Supporting Information.
Chart 2
Figures 1 and 2 show the energies of intermediates and final
products (P) with respect to the reagents (R) when the entering
ligand L is PMe3 or py, respectively, and the leaving ligand is
ethylene (path E) and Cl- (path C). The optimized geometries
for the intermediates agree with those usually proposed for
square-planar substitution reactions (see Figures 1 and 2 and
Supporting Information), except in the case of TBPC. The
expected intermediate TBPC′ (Chart 2) proves to be unstable
because the energy of the structure resulting after closing up to
135° the R-Pt-Cl from SPY1 is around 20-26 kcal/mol higher
than that of TBPC, and if an additional closing is forced,
removal of L occurs. The geometry of the TBPC intermediate
can be better described as distorted octahedral because the Pt

6164 Organometallics, Vol. 26, No. 25, 2007
Vicente et al.
Figure 4. Comparative of energetic pathway for the substitution
of chloro by pyridine, CO and PMe3. The donor atom of the entering
ligand is represented by an orange ball.
Scheme 4
Figure 3. Comparative of energetic pathway for the substitution
of ethylene by pyridine, CO and PMe3. The donor atom of the
entering ligand is represented by an orange ball.
Although this substitution is slightly endoergonic (Figures 2 and
3) the precipitation of Me4NCl in CH2Cl2 forces the substitution.
When L is the strong π-acceptor ligand PMe3 or CO, there are
not kinetic barriers for chloro or ethylene substitution (the energy
of all intermediates is e5 kcal/mol; Figures 3 and 4) but the
very low energy of the resulting products of the ethylene
substitution favors this process.
The influence of solvents (CHCl3, THF, CH2Cl2, Me2CO,
MeCN) and the direction of the attack of the ligand with respect
to the acetonyl substituent are negligible (see Supporting
Information).
Reactions of Me4N[Pt{CH2C(O)Me}Cl2(C2H4)] (1) with
Bidentate Ligands. Reaction of 1 with excess of norbornadiene
(nbd) or cyclooctadiene (cod) (Scheme 4) took place with
precipitation of Me4NCl and formation of complex [Pt{CH2C-
(O)Me}Cl(L2)] (L2 ) nbd (18), cod (19)). The precipitate in
the reaction of 1 with cod contained, along with Me4NCl, a
platinum complex, that could not be identified; this is the reason
for the moderate yield of 19 (51%). Complex 19 was also
obtained in low yield (20%) by refluxing an Me2CO solution
of [PtCl2(cod)] and [Hg{CH2C(O)Me}2] in a molar ratio of 1:1.
Reactions of 1 with bidentate ligands bis(diphenylphosphino)-
methane (dppm) or 4,4′-di-tert-butyl-2,2′-bipyridyl (dbbpy) in
the molar ratio 1:1 gave complexes [Pt{CH2C(O)Me}Cl(L2)]
[L2 ) dppm (20), dbbpy (21)]. Complex 20 was contaminated
atom and both carbon atoms of ethylene and chloro ligands are
almost coplanar (see Chart 2): the angles between Cl-Pt-Cl
and C-Pt-C planes are around 5° and the calculated Cl-Pt-
Cl angles are around 97°; similar values are obtained for TBPE
structures. This is not unexpected as this is the preferred mode
of coordination for ethylene in trigonal bipyramidal com-
plexes.41,42
Figures 3 and 4 compare the substitution of the ethylene and
chloro ligands, respectively, by the three studied ligands L. From
our calculations the substitution of ethylene by pyridine (Figures
2 and 3) is kinetically inhibited because of the high energy of
the intermediate SPY2E (Figure 2), containing the ethylene
ligand in the apical position. This contrasts with the moderate
energy of SPY2C having the ethylene in the pyramidal base
which, therefore, favors the substitution of the chloro ligand.
This was, from a kinetic point of view, the expected process
because the order of trans influence is C2H4 > R > Cl.41
(41) Lin, Z. Y.; Hall, M. B. Inorg. Chem. 1991, 30, 646.
(42) Albano, V. G.; Natile, G.; Panunzi, A. Coord. Chem. ReV. 1994,
133, 67. Albright, T. A.; Hoffmann, R.; Thibeault, J. C.; Thorn, D. L. J.
Am. Chem. Soc. 1979, 101, 3801. Albright, T. A.; Burdett, J. K.; Whangbo,
M.-H. In Orbital Interactions in Chemistry; Wiley: New York, 1985, p
320

Acetonyl Platinum(II) Complexes
Organometallics, Vol. 26, No. 25, 2007 6165
Figure 6. Ellipsoid representation of complex 3 (50% probability).
Selected bond lengths (Å) and angles (deg): Pt(1)-C(3) ) 2.069-
(4), Pt(1)-C(2) ) 2.095(4), Pt(1)-C(1) ) 2.164(4), Pt(1)-Cl(1)
) 2.3364(11), Pt(1)-Cl(2) ) 2.4106(11), O(1)-C(4) ) 1.221(5),
C(1)-C(2) ) 1.412(6), C(1)-C(11) ) 1.474(6), C(3)-C(4) )
1.482(6), C(4)-C(5) ) 1.522(6), C(3)-Pt(1)-C(2) ) 89.93(18),
C(3)-Pt(1)-C(1) ) 87.62(17), C(2)-Pt(1)-C(1) ) 38.68(16),
C(3)-Pt(1)-Cl(1) ) 89.37(13), C(2)-Pt(1)-Cl(2) ) 89.86(13),
C(1)-Pt(1)-Cl(2) ) 93.95(12), Cl(1)-Pt(1)-Cl(2) ) 89.78(4),
C(2)-C(1)-C(11) ) 126.2(4).
Figure 5. Ellipsoid representation of complex 1 (50% probability).
Selected bond lengths (Å) and angles (deg): Pt(1)-C(1) ) 2.075-
(4), Pt(1)-C(5) ) 2.118(4), Pt(1)-C(4) ) 2.125(4), Pt(1)-Cl(1)
) 2.3267(9), Pt(1)-Cl(2) ) 2.3845(10), O(1)-C(2) ) 1.225(4),
C(1)-C(2) ) 1.490(5), C(2)-C(3) ) 1.502(5), C(4)-C(5) )
1.396(5), C(1)-Pt(1)-C(5) ) 90.52(15), C(1)-Pt(1)-C(4) )
90.06(15), C(5)-Pt(1)-C(4) ) 38.41(14), C(1)-Pt(1)-Cl(1) )
90.55(10), C(5)-Pt(1)-Cl(2) ) 88.52(12), C(4)-Pt(1)-Cl(2) )
89.98(11), Cl(1)-Pt(1)-Cl(2) ) 89.88(3), C(2)-C(1)-Pt(1) )
109.6(2), O(1)-C(2)-C(1) ) 121.8(3), O(1)-C(2)-C(3) ) 120.8-
(3), C(1)-C(2)-C(3) ) 117.4(3).
with traces of [PtCl2(dppm)] (1H and 31P NMR spectra) in the
reaction mixture, but it could be obtained with moderated yield
(50%) by recrystallization in toluene/Et2O. Complexes 18-21
are stable at room temperature, in the solid state, and in solution
of common organic solvents.
The reaction of 1 with [Tl(acac)] gives [Pt{CH2C(O)Me}-
(acac)(C2H4)] (22), which is a suitable precursor for the synthesis
of other acetonyl complexes containing the acac ligand. Thus,
the reactions with XyNC, CO, or PPh3 gave the corresponding
complex [Pt{CH2C(O)Me}(acac)L] (L ) CO (23), PPh3 (24),
XyNC (25); Scheme 4). However, 22 does not react with
pyridine even when a molar ratio of 1:4 was used. This behavior
can be explained, like in the case of the reaction of 1 with
pyridine, as the consequence of the high activation energy
required to form the square-pyramid complex necessary for
ethylene substitution. Complexes 24 and 25 are stable solids at
room temperature; however, 22 and 23 are not stable and must
be stored below -30 °C.
Figure 7. Ellipsoid representation of complex 8trans (50%
probability). Selected bond lengths (Å) and angles (deg): Pt-C(1)
) 2.061(2), Pt-P(2) ) 2.2943(5), Pt-P(1) ) 2.3028(5), Pt-Cl-
(1) ) 2.4070(5), O(1)-C(2) ) 1.209(3), C(1)-C(2) ) 1.495(3),
C(1)-Pt-P(2) ) 91.29(6), C(1)-Pt-P(1) ) 90.85(6), P(2)-Pt-
Cl(1) ) 87.307(17), P(1)-Pt-Cl(1) ) 90.469(17), C(2)-C(1)-
Pt ) 113.42(14).
Structure of Complexes. The X-ray crystal structures of
complexes 1, 3, 8trans, 13, 14 and cis-[PtCl2(CNXy)2] have
been determined (Figures 5-10 and Table 1). The structure of
3 was refined as a racemate. In the anionic complexes 1 and 3,
the platinum atom shows slightly distorted square planar
coordination with the chloro ligands in the mutually cis position.
In both complexes, the two Pt-Cl distances are different, the
Pt-Cl trans to the acetonyl ligand [1, 2.3845(10); 3, 2.4106-
(11) Å] being longer than the Pt-Cl trans to olefin (1, 2.3267-
(9); 3, 2.3364(11) Å), showing the stronger trans influence of
the acetonyl group than the olefin ligand. In both complexes,
the olefin is, as usual,33 perpendicular to the platinum coordina-
tion plane (88.5° and 85.1°, respectively). The C-O distance
in the acetonyl complexes (mean value 1.218(5) Å) is similar
to that in complex 13 (1.224(3) Å); therefore, the C-O bond
order in 13 is ca. two and the corresponding C-N (1.371(3)
Å) bond order ca. 1, which is lower than those in the carbene
ligand of complex 14 (mean value 1.330(4) Å) in accord with
the electron delocalization present in this ligand.
In 3, the phenyl group of the styrene ligand is oriented away
from the bulkier acetonyl ligand (3bb′, Chart 1). A similar
arrangement has been found in analogous cis-[PtCl2L(RCHd
CH2)].33,43,44 In solution at -20 °C, the other pair of enantioners
3aa′ (Chart 1) is slightly more abundant than 3bb′ (1:0.8; see
Spectroscopic Properties). The olefinic C-C distances in 1
(1.396(5) Å) and 3 (1.412(6) Å) are longer than those found
for free ethylene [1.337(2) Å]45 or styrene [1.317 Å],46
respectively, and shorter than a Csp3-Csp3 single bond [1.514
Å].47 The two Pt-C olefin distances in 1 are similar [2.125(4)
and 2.118(4) Å], as is the case for other ethylene complexes
(43) Briggs, J. R.; Crocker, C.; McDonald, W. S.; Shaw, B. L. J. Chem.
Soc., Dalton Trans. 1980, 64. Pryadun, R.; Sukumaran, D.; Bogadi, R.;
Atwood, J. D. J. Am. Chem. Soc. 2004, 126, 12414.
(44) Ashley-Smith, J. Z.; Douek, Z.; Johnson, B. F. G.; Lewis, J. J. Chem.
Soc., Dalton Trans. 1974, 128.
(45) Bartell, L. S.; Roth, E. A.; Hollowel, C. D.; Kuchitsu, K.; Young,
J. E. J. Chem. Phys. 1965, 42, 2683.
(46) Bond, A. D.; Davies, J. E. Acta Crystallogr. Sect. E 2001, 57, O1191.

6166 Organometallics, Vol. 26, No. 25, 2007
Vicente et al.
Figure 8. Ellipsoid representation of complex 13 (50% probability).
Selected bond lengths (Å) and angles (deg): Pt(1)-C(19) ) 1.955-
(3), Pt(1)-C(29) ) 1.959(3), Pt(1)-C(10) ) 2.004(3), Pt(1)-Cl-
(1) ) 2.4117(6), C(19)-N(1) ) 1.147(3), C(29)-Ν(2) ) 1.150(3),
O(1)-C(10) ) 1.224(3), N(9)-C(10) ) 1.371(3), C(19)-Pt(1)-
C(10) ) 91.45(10), C(29)-Pt(1)-C(10) ) 87.47(11), C(19)-Pt-
(1)-Cl(1) ) 90.07(7), C(29)-Pt(1)-Cl(1) ) 90.98(8), N(1)-
C(19)-Pt(1) ) 177.9(2), N(2)-C(29)-Pt(1) ) 178.1(2), C(10)-
N(9)-C(1) ) 123.2(2), O(1)-C(10)-N(9) ) 121.2(2), O(1)-
C(10)-Pt(1) ) 121.22(19), N(9)-C(10)-Pt(1) ) 117.56(19),
C(19)-N(1)-C(11) ) 175.4(3), C(29)-N(2)-C(21) ) 175.6(3).
Figure 10. Ellipsoid representation of complex cis-[PtCl2(CNXy)2]
(50% probability). Selected bond lengths (Å) and angles (deg): Pt-
(1)-C(9) ) 1.908(3), Pt(1)-C(19) ) 1.912(3), Pt(1)-Cl(1) )
2.3182(7), Pt(1)-Cl(2) ) 2.3209(7), N(1)-C(9) ) 1.149(4), N(2)-
C(19) ) 1.144(4), C(9)-Pt(1)-C(19) ) 91.78(12), C(19)-Pt(1)-
Cl(1) ) 88.12(8), C(9)-Pt(1)-Cl(2) ) 88.63(8), Cl(1)-Pt(1)-
Cl(2) ) 91.48(3), C(9)-N(1)-C(1) ) 172.2(3), C(19)-N(2)-
C(11) ) 177.2(3), N(1)-C(9)-Pt(1) ) 179.3(3), N(2)-C(19)-
Pt(1) ) 177.2(3).
Figure 11. Association of two molecules of 13 via N-H‚‚‚Cl and
C-H‚‚‚Cl hydrogen bonds.
Figure 9. Ellipsoid representation of complex 14 (50% probability).
Selected bond lengths (Å) and angles (deg): Pt(1)-C(1) ) 1.953-
(3), Pt(1)-C(11) ) 1.957(3), Pt(1)-C(21) ) 1.996(3), Pt(1)-Cl-
(1) ) 2.3595(8), N(1)-C(1) ) 1.151(4), N(2)-C(11) ) 1.147(4),
N(3)-C(21) ) 1.323(4), N(4)-C(21) ) 1.336(4), C(1)-Pt(1)-
C(21) ) 90.29(12), C(11)-Pt(1)-C(21) ) 91.66(12), C(1)-Pt-
(1)-Cl(1) ) 89.94(9), C(11)-Pt(1)-Cl(1) ) 88.03(9), C(1)-
N(1)-C(2) ) 172.2(3), C(11)-N(2)-C(12) ) 172.0(3), C(21)-
N(3)-C(22) ) 127.1(3), C(21)-N(4)-C(32) ) 126.5(3), N(1)-
C(1)-Pt(1) ) 178.3(3), N(2)-C(11)-Pt(1) ) 173.7(3), N(3)-
C(21)-N(4) ) 115.1(3), N(3)-C(21)-Pt(1) ) 123.4(2), N(4)-
C(21)-Pt(1) ) 121.5(2).
Complex 8trans shows a square-planar coordination around
the platinum atom. As expected, the Pt-P bond distances are
similar (2.3028(5) and 2.2943(5) Å) and the Pt-C bond length
(2.061(2) Å) is like those observed in complexes 1 and 3 (2.075-
(4) and 2.069(4) Å), because all are trans to Cl ligand. However,
the Pt-Cl trans to acetonyl distances are sligthly different in
the three complexes [1, 2.3845(10); 3, 2.4106(11); 8trans,
2.4070(5) Å].
Several C-H‚‚‚X (X ) Cl, Pt, O) hydrogen bonds are
observed in the three complexes (see Supporting Information).
The H atoms involved are those of the cation (1, 3), the acetonyl
ligand (1), or the phenyl group (3, 8trans).
Complexes 13, 14, and cis-[PtCl2(CNXy)2] (Figures 8-10)
show a square-planar coordination around the platinum atom.
In 14, the carbene moiety is in a Z,Z configuration. As expected,
the Pt-CNXy distances are similar in complexes 13 (1.955(3)
and 1.959(3) Å) and 14 (1.957(3) and 1.953(3) Å) and longer
than those found in cis-[PtCl2(CNXy)2] (1.912(3) and 1.908-
(3)] Å), which shows the stronger trans influence of the
reported.33 In 3 both Pt-C olefin distances are significantly
different [2.164(4) and 2.095(4) Å], being longer the corre-
sponding to Pt-CPh. This could be due to the different
electronic effects of the substituents bound to either C atom of
the styrene. A similar distortion has been reported in complexes
with CH2dCHR ligands (R ) CH2OH, Ph, OCHMeCMe3).33
(47) Allen, F. H.; Kennard, O.; Watson, D. G.; Brammer, L.; Orpen, A.
G.; Taylor, R. J. Chem. Soc., Perkin Trans. 2 1987, S1.

Acetonyl Platinum(II) Complexes
Organometallics, Vol. 26, No. 25, 2007 6167
Table 1. Crystallographic Data for Complexes 1, 3, 8trans‚CHCl3, 13‚1.5CHCl3, 14 and cis-[PtCl2(CNXy)2]
1
3
8trans‚CHCl3
13‚1.5CHCl3
14
cis-[PtCl2(CNXy)2]
formula
Mr
C9H21Cl2NOPt
425.26
C15H25Cl2NOPt
501.35
C40H36Cl4OP2Pt
931.52
C28.5H29.5Cl5.5N3OPt
820.12
C35H38Cl2N4Pt
780.68
C18H18Cl2N2Pt
528.33
cryst habit
cryst size (mm3)
cryst syst
space group
lath
block
prism
prism
prism
prism
0.26 × 0.17 × 0.09
monoclinic
P2(1)/n
0.32 × 0.12 × 0.11
monoclinic
P2(1)/n
0.27 × 0.15 × 0.11
monoclinic
P2(1)/c
cell constants
12.2711(5)
11.3098(4)
27.4801(11)
90
99.633(2)
90
3760.0(3)
4
0.28 × 0.21 × 0.11
monoclinic
C2/c
0.17 × 0.06 × 0.03
0.17 × 0.10 × 0.08
triclinic
triclinic
P1h
P1h
a, Å
b, Å
c, Å
R, deg
â, deg
γ, deg
V (Å3)
Z
12.4295(6)
7.6154(4)
15.0557(8)
90
105.857(2)
90
15.6536(9)
6.8386(4)
16.5090(9)
90
102.075(2)
90
33.0213(19)
15.9116(9)
11.9507(7)
90
92.638(2)
90
10.0835(6)
12.9030(8)
13.2332(8)
100.728(2)
99.835(2)
100.983(2)
1622.24(17)
2
8.0409(4)
10.4023(5)
10.8166(5)
85.016(2)
80.162(2)
87.287(2)
887.58(7)
2
1370.88(12)
4
1728.17(17)
4
6272.5(6)
8
λ (Å)
0.71073
2.060
10.599
808
0.71073
1.927
8.424
0.71073
1.646
4.133
0.71073
1.737
4.970
0.71073
1.598
4.520
0.71073
1.977
8.205
F
calcd (Mg m-3
)
µ mm-1
F(000)
968
1840
3208
776
504
T (K)
2θmax (deg)
no. of reflns measd
no. of independent
reflns
100(2)
53.46
8018
100(2)
52.74
18229
3542
100(2)
54.2
42123
8266
100(2)
54.2
34349
6881
100(2)
56.32
18876
7258
100(2)
56.16
10074
3933
2896
transmissions
Rint
0.4488, 0.1692
0.0207
0.4576, 0.1735
0.0271
0.6592, 0.4016
0.0203
0.6109, 0.3367
0.0587
0.8763, 0.5138
0.0279
0.5598, 0.3360
0.0188
no. rest/params
Rw(F2, all reflns)
R(F, > 4σ(F))
S
0/132
0.0457
0.0212
1.185
131/186
0.0562
0.0256
1.252
48/433
0.0433
0.0179
1.059
4/380
0.0613
0.0235
1.058
0/395
0.0566
0.0259
1.080
0/212
0.0475
0.0189
1.084
max ∆F (e Å-3
)
0.855, -1.180
1.585, -0.922
0.736, -0.390
2.000, -1.147
1.160, -0.918
1.789, -0.771
isocyanide than the chloro ligand. The Pt-C(O)NHXy distance
in 13 (2.004(3) Å), is similar to the Pt-C(NHXy)2 distance in
14 (1.996(3) Å). In the three complexes, the Pt-Cl distances
are decreasing in the series 13 (2.4117(6) Å), 14 (2.3595(8)
Å), and cis-[PtCl2(CNXy)2] (2.3209(7) and 2.3182(7) Å),
following the scale of trans influence: C(O)NHXy > C(NHXy)2
> CNXy.
In 13, dimers due to N(9)-H(9)‚‚‚Cl and C(8)-H(8)‚‚‚Cl
hydrogen bonds (Figure 11) are connected via O(1)‚‚‚H(25)
hydrogen bonds (see Supporting Information) to afford a zigzag
catena structure. The angle between the mean planes of the two
phenyl groups is 6.5°, and the distance between centroids is
4.13 Å, which is above the range found in other complexes
with π-π stacking (3.3-3.8 Å).48 In complex 14, an anion-
cation pair is formed by means of N-H‚‚‚Cl‚‚‚H-N hydrogen
bonds (see Supporting Information).
The 13C{1H} NMR spectra of acetonyl complexes show the
expected singlet for the methylene carbon atom, with the
1
corresponding 195Pt satellites. The JCPt values increase as the
trans influence of the ligand in trans decreases:2,50 tBuNC
(12cis: 420 Hz) < XyNC (11cis, 15: 422, 471 Hz) < AsPh3
(9cis: 474 Hz) < N- (16, 21: 562, 594 Hz) ≈ olefin (19, 18:
551, 613 Hz) ≈ Cl (2, 3, 5, 6, 9trans, 10, 11trans, 12trans,
17trans: 522-679 Hz) ≈ O- (22-25: 595-673 Hz). The
t
same is observed for 2JPtC(O): BuNC (12cis: 29 Hz) < XyNC
(15cis: 39 Hz) < N-donor (21: 42 Hz) ≈ olefin (18: 44 Hz)
≈ Cl (5, 6, 10, and 12trans: 47-54 Hz) ≈ O-donor (22, 23,
and 25: 46-49 Hz).
The 1H NMR spectrum of 3 at 25 °C shows broad resonances
which coalesce at 45 °C. At -20 °C the resonances resolve
into two sets of signals because of the two possible pairs of
enantiomers (see Chart 1) in 1:0.8 molar ratio, resulting from
the rotation around the Pt-olefin axis. A phase-sensitive 1H,1H-
NOESY spectrum measured at -20 °C shows that the two sets
of resonances are in slow exchange. The NOE cross-peaks in
the same spectrum allow the assignment of the major set of
signals to the pair of enantiomers 3aa′ (see Chart 1), where the
phenyl group is oriented toward the acetonyl ligand (there are
NOE contacts between a methylene proton of the acetonyl and
both Ha and the ortho phenyl protons of the olefin). For the
other pair of enantiomers, 3bb′, the NOE cross-peaks are found
between the methylene proton and Hb,c of the olefin. In
complexes [PtCl2(L)(RCHdCH2)] it is more usual that the R
group is closer to the ligand L33,43,44 than the contrary.51
Spectroscopic Properties. Methyl protons of the acetonyl
1
ligand appear in the H NMR spectra in the range δ 1.90-
2.33, except for 8trans (1.34) and 9trans (1.51), in which they
are more shielded owing to the PPh3 and AsPh3 neighboring
aromatic rings. They form a triplet, by coupling with the
methylene protons in 2, 11, and 12 (Schemes 1 and 2) or a
singlet in the others, The methylene protons are observed in
the range δ 2.14-3.34 with 195Pt satellites with 1JHPt in the range
76-148 Hz. The NH proton in complex 13 (6.80 ppm) is much
more shielded than those in 14 (12.04 ppm) because in the latter
the N-H‚‚‚Cl hydrogen bonds observed in the solid state must
persist in solution. The 1H NMR spectrum of 14 shows that the
Z,Z configuration is retained in CDCl3 solution because the 3JHPt
value (84 Hz) is similar to those reported for N-H trans to Pt
(80-90 Hz) and different to those reported for N-H cis to Pt
(ca. 30 Hz).49
The 13C{1H} NMR spectrum of complex 4 shows the alkyne
carbons shielded with respect to those in the free ligand,
1
although JCPt coupling was not observed due to its low
solubility.
(48) Janiak, C. Dalton Trans. 2000, 3885. Ionkin, A. S.; Marshall, W.
J.; Wang, Y. Organometallics 2005, 24, 619. Vicente, J.; Gonza´lez-Herrero,
P.; Garc´ıa-Sa´nchez, Y.; Jones, P. G.; Bardaj´ı, M. Inorg. Chem. 2004, 43,
7516. Smucker, B. W.; Hudson, J. M.; Omary, M. A.; Dunbar, K. R. Inorg.
Chem. 2003, 42, 4714. Vicente, J.; Gonza´lez-Herrero, P.; Pe´rez-Cadenas,
M.; Jones, P. G.; Bautista, D. Inorg. Chem. 2007, 46, 4718.
(49) Crociani, B.; Di Bianca, F.; Fontana, A.; Forsellini, E.; Bombieri,
G. J. Chem. Soc., Dalton Trans. 1994, 407. Crociani, B. J. Chem. Soc.,
Dalton Trans. 1974, 693.
(50) Appleton, T. G.; Clark, H. C.; Manzer, L. E. Coord. Chem. ReV.
1973, 10, 335.

6168 Organometallics, Vol. 26, No. 25, 2007
Vicente et al.
The proposed structure for 5 (Scheme 1), with the allene
ν(CtO) in the carbonyl complexes 2 and 23 appears at 2086
and 2093 cm-1, respectively, lower than that in CO (2143 cm-1).
The cis geometry of 1 was proposed on the basis of the IR
spectrum, since it shows two bands at 276 and 311 cm-1 that
we assign to ν(Pt-Cl) trans to acetonyl [ν(Pt-Cl)acetonyl] and
trans to ethylene [ν(Pt-Cl))] ligands, respectively.8 The X-ray
diffraction study of 1 we report here confirms both the geometry
and the IR assignment (see above). Similarly, in accordance
with the crystal structure of 3, the bands at 267 and 305 cm-1
must be assigned to ν(Pt-Cl)acetonyl and ν(Pt-Cl)), respectively.
Therefore, a cis geometry is proposed for 2, 4-7, since they
show two bands at 254-284 and 293-328 cm-1 that can be
assigned to ν(Pt-Cl)acetonyl and ν(Pt-Cl)L, respectively. In
complex 2, the ν(Pt-Cl)CO (328 cm-1) appears in the same
region as our palladium complexes cis-Me4N[PdRCl2(CO)]
[R ) C6H3Me-2-NO2-6 (315 cm-1), C6H2(NO2)3-2,4,6 (335
cm-1)].53
coordinated through the less-substituted double bond, is based
2
on (1) the high values of JHPt (76.1 and 64.7 Hz) of the CH2
protons of the allene, similar to that in complex 1 (68 Hz),8
and 1JCPt of CH2 (155.3 Hz) with respect to that of CMe2 (2JCPt
) 31 Hz), as observed in similar complexes,32-34,36 and (2) the
CH2 carbon nucleous is more shielded (31.8 ppm) than that in
1
the free allene (72.55 ppm). The H NMR spectra of some
reported allene Pt(II) complexes reveal free rotation around the
Pt-allene bond at room temperature.34 In the case of 5, the
presence of two distinct resonances for the methylene protons
(3.27 (2JHPt ) 76.1 Hz) and 3.02 ppm (2JHPt ) 64.7 Hz)) and
other two for the methylene protons of the acetonyl ligand (2.97
2
(1JHH ) 5.5 Hz, JHPt ) 122.3 Hz) and 1.72 ppm (1JHH ) 5.5
2
Hz, JHPt ) 93.5 Hz) indicates restricted rotation around the
Pt-allene bond in the range of studied temperatures (0 to
50 °C). A similar behavior has been described for complexes
cis-[PtCl2(η2-CH2dCdCMe2)(L)] (L ) AsPh3, PPh3).32
The following trans influence scale can be deduced from the
position of the bands due to ν(Pt-Cl)L in cis-[Pt{CH2C(O)-
Me}Cl2L]- complexes (1-7): PPh3 (293 cm-1) g AsPh3 (297
cm-1) > PhCHdCH2 (305 cm-1) g H2CdCH2 (311 cm-1) g
H2CdCdCMe2 (315 cm-1) g PhCtCPh (317 cm-1) > CO
(328 cm-1), which is similar to that deduced on the basis of
the 195Pt{1H} NMR spectra, except for the CO ligand. In our
opinion, this IR-base scale is more appropriate because it gives
account of the strenghening of the Pt-Cl bond due to the
π-acceptor character of CO while the σparamagnetic value is also
influenced by the changes in C-O and C-Pt bond energies.
From the data of neutral complexes [Pt{CH2C(O)Me}ClL2] (8-
12, 16-21) the order of trans influence would be: MeC(O)-
The 13C{1H} NMR spectra of complex 10 (Scheme 1) shows
only two resonances for the tht ligands, which supports the
proposed trans geometry. For complexes 9, 11, and 12 (Scheme
1 and 2) the 1H and 13C resonances corresponding to the
methylene group in the cis and trans isomers were assigned on
the basis of 2JHPt and 1JCPt coupling constants, since they should
be higher for the trans than for the cis isomers, because AsPh3
and RNC ligands have stronger trans influence than chloro
ligand.50 The geometry of complex 16 was elucidated by
NOESY 2D experiments. The ethylene protons show NOE with
the CH2 protons of the acetonyl and the o-pyridine protons. No
effect between acetonyl protons and the pyridine protons was
observed. The olefinic 1H and 13C{1H} nuclei are more shielded
in complexes 18, 19, and 22 than in the free ligands.33,44,52 NOE
experiments for complexes 18 and 19, carried out to assign the
CH cis or trans to the acetonyl ligand, revealed NOE between
the acetonyl CH2 protons and the adjacent CH protons of the
diolefin moiety. The 1H NMR spectrum of 22 at room
temperature shows the resonances of the ethylene protons as a
singlet with 195Pt satellites because of the fast rotation about
the Pt-ethylene bond.
The 195Pt{1H} chemical shifts of the anionic complexes 1-7
seem to be inversely related with the trans influence of the L
ligand (Scheme 1): PPh3 (-4091 ppm) > AsPh3 (-3950 ppm)
> CO (-3726 ppm) > H2CdCH2 (-3379 ppm) > PhCHd
CH2 (-3167 and 3186 ppm) > H2CdCdCMe2 (-3013 ppm)
> PhCtCPh (-2606 ppm). Something similar occurs with
complexes 22-25: PPh3 (-3647 ppm) > CO (-3598 ppm) >
XyNC (-3355) > H2CdCH2 (-3204 ppm). This effect could
be related to the paramagnetic component of the shielding
constant.
CH2 (6, 7, 8trans, 9trans, 10, 11trans, 12trans, 276-304 cm-1
)
> dppm (20, 293 cm-1) g PPh3 (8cis, 298 cm-1) > cod (19,
316 cm-1) ≈ norbordiene (18, 317 cm-1) ) H2CdCH2 (16,
317 cm-1) > dbbpy (21, 326 cm-1) ≈ BuNC (12cis, 325 cm-1
)
t
≈ XyNC (11cis, 326 cm-1). Similarly, from the data of 13 (278
cm-1) and 14 (310 cm-1), C(O)NHXy > C(NHXy)2, which is
in accord with the X-ray crystal data.
The ν(Pt-Cl) band in complex 16 at 317 cm-1 supports the
mutual trans position of Cl and ethylene in the solid state,
because it appears at the same frequency than in 18 and 19
(316-317 cm-1) and not in the region 276-304 cm-1 (ν(Pt-
Cl)acetonyl) or around 326 cm-1 (ν(Pt-Cl)Cl). The ν(Pt-Cl)acetonyl
,
ν(Pt-Cl)P, and ν(Pt-Cl)) bands in the neutral complexes [Pt-
{CH2C(O)Me}Cl(L)2] are shifted to higher wavenumbers (276-
304, 298, and 305-311 cm-1, respectively) with respect to the
corresponding ones in the anionic complexes (254-276, 293,
and 316-317 cm-1, respectively), because the strength of the
pπ(Cl)fdπ(Pt) bond is smaller in the anionic complexes. We
have observed a similar relationship in palladium(II)54 and gold-
(III)55 complexes.
The platinum nucleus of Pt(II) complexes is more shielded
than the related Pt(IV) complexes previously reported for us.
Thus, in [Pt{CH2C(O)Me}2(bpy)] δ(195Pt{1H}) ) -3351 ppm
while in the family of Pt(IV) complexes [Pt{CH2C(O)Me}n-
Cl4-n(bpy)], δ(195Pt{1H}) ) -937 to -2692.8 In 15, δ(195Pt-
The expected two absorptions assignable to ν(CtN) in the
IR spectra of cis complexes are observed in 11cis (2200, 2171
cm-1), 12cis (2223, 2193 cm-1), and 15 (2182, 2148 cm-1).
Complexes cis- and trans-[PtR2(CNXy)2] [R ) κ1-C-C6(NO2)2-
{1H}) ) -4167 while in [Pt{CH2C(O)Me}3Cl(CNXy)2] δ(195
-
Pt{1H}) ) -3307.
2,6-(OMe)3] show two (2199, 2179 cm-1) and one (2196 cm-1
bands, respectively.40
)
The IR spectra show one band, assignable to ν(CdO), in the
region 1681-1645 cm-1, which is similar to that reported for
terminal acetonyl palladium(II) complexes.13 The band due to
(53) Vicente, J.; Arcas, A.; Borrachero, M. V.; Tiripicchio, A.; Tiripic-
chio-Camellini, M. Organometallics. 1991, 10, 3873.
(51) Briggs, J. R.; Crocker, C.; McDonald, W. S.; Shaw, B. L. J.
Organomet. Chem. 1979, 181, 213. Lazzaroni, R.; Uccellobarretta, G.;
Bertozzi, S.; Salvadori, P. J. Organomet. Chem. 1984, 275, 145.
(52) Ashley-Smith, J.; Johnson, B. F. G.; Lewis, J.; Douek, I. J. Chem.
Soc., Dalton Trans. 1972, 1776.
(54) Vicente, J.; Arcas, A.; Borrachero, M. V.; de Goicoechea, M. L.;
Lanfranchi, M.; Tiripicchio, A. Inorg. Chim. Acta 1990, 177, 247.
(55) Vicente, J.; Chicote, M. T.; Bermu´dez, M. D. Inorg. Chim. Acta
1982, 63, 35. Vicente, J.; Chicote, M. T.; Arcas, A.; Artigao, M.; Jime´nez,
R. J. Organomet. Chem. 1983, 247, 123.

Acetonyl Platinum(II) Complexes
Conclusions
Organometallics, Vol. 26, No. 25, 2007 6169
solvents moisture or HCl afford acetone and, respectively,
platinum carbamoyl or amino carbene complexes.
We have isolated and characterized the first families of neutral
(containing isocyanides, PPh3, AsPh3, dppm, dbbpy, py, tht, nbd,
cod, CH2dCH2, CO, acac) and anionic acetonyl Pt(II) com-
plexes. They could be prepared due to the versatility of Me4N-
[Pt{CH2C(O)Me}Cl2(η2-CH2dCH2)] (1). Monosubstitution re-
actions occur differently depending on the π-acceptor ability
of the ligands. Thus, when L ) CO, PhCHdCH2, PhCtCPh,
H2CdCdCMe2, PPh3, AsPh3 the anionic complexes Me4N[Pt-
{CH2C(O)Me}Cl2(L)] result after ethylene substitution, while
when L ) pyridine, the product of chloro substitution [Pt{CH2C-
(O)Me}Cl(py)(η2-CH2dCH2)] is obtained. A DFT study con-
cludes that the first ligands give the thermodynamic products
while pyridine affords the kinetic product, due to the high
activation energy required to form the square-pyramid complex
necessary for ethylene substitution. Reactions of an acetonyl
isocyanide complex with excess of XyNC in the presence of
Acknowledgment. We thank Direccio´n General de Inves-
tigacio´n, Ministerio de Educacio´n y Ciencia and FEDER for
financial support (Grant CTQ2004-05396). J.M.F.-H thanks
Grants from Fundacio´n Se´neca and Fundacio´n Cajamurcia.
Financial support to this work was provided by the Direccio´n
General de Investigacio´n (MECD) through Grant CTQ2005-
08123-C02-02/BQU and Generalitat de Catalunya through Grant
2005SGR-0036. Computing resources used were available at
the Centre de Supercomputacio´ de Catalunya (CESCA).
Supporting Information Available: Data obtained in the DFT
study, hydrogen bond parameters, and CIF files for 1, 3, 8trans,
13, 14, and cis-[PtCl2(CNXy)2]. This material is available free of
charge via the Internet at http://pubs.acs.org.
OM700665N