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com/locate/ica Inorganica Chimica Acta 327 (2002) 90 97

Synthesis of new (s2-N,N%-diazadiene)(h2-alkene)platinum(0) compounds

Dorette S. Tromp, Marcel A. Duin, Alexander M. Kluwer, Cornelis J. Elsevier *
Institute of Molecular Chemistry, Coordination and Organometallic Chemistry, Uni6ersiteit 6an Amsterdam, Nieuwe Achtergracht 166, 1018 WV Amsterdam, The Netherlands Received 30 April 2001; accepted 14 August 2001 Dedicated to Professor Dr Kees Vrieze in recognition of his many outstanding contributions to organometallic and coordination chemistry, for his guidance and for his friendship during the many fruitful years we worked together

Abstract Novel, thermally stable, dark-red to orange Pt0(s2-N,N%-diazadiene)(h2-alkene) compounds have been synthesized in good yields from Pt0(COD)2 or Pt0(NBE)3, by stepwise substitution of the respective dienes or alkenes by an electron-poor alkene (dimethyl fumarate, maleic anhydride or fumaronitrile), followed by the appropriate diazadiene ligand in dry diethyl ether at 20 C (diazadiene =various N,N%-disubstitued-1,4-diaza-1,3-dienes). The complex Pt(DBA)2 is less suited as a precursor for the synthesis of Pt0(s2-N,N%-diazadiene)(h2-alkene) compounds. These zerovalent Pt(diazadiene)(h2-alkene) compounds constitute a useful category of starting materials for synthetic organoplatinum chemistry and catalysis. 2002 Elsevier Science B.V. All rights reserved.
Keywords: Bidentate nitrogen ligands; Low-valent platinum compounds; Pt(diazadiene) compounds; Pt(alkene) compounds

1. Introduction As shown by several groups, chelating bidentate nitrogen ligands are valid alternatives to phosphines and phosphites as stabilizing entities for the synthesis of zerovalent compounds containing a Group 8, 9 or 10 metal atom [16] and useful directing ligands in their

Fig. 1. Some examples of transition-metal diazadiene compounds. * Corresponding author. Fax: + 31-20-525 6456. E-mail address: else4@anorg.chem.uva.nl (C.J. Elsevier).

reactivity [79]. Nowadays, many examples of late transition metal complexes in low oxidation states containing bidentate nitrogen ligands, such as 1,10-phenanthroline, pyridine-carbaldimine (Pyca) derivatives, N,N%-disubstituted-1,4-diazabutadiene (R-DAB) and bis(arylimino)acenaphthene (Ar-BIAN) ligands, to name just a few, are known. Pioneering work regarding the coordination chemistry of diaza(buta)dienes has been carried out notably by Vrieze and van Koten, tom Dieck, Schurig, Fruhauf, and quite a number of R DAB-complexes of low-valent transition metals, often with CO as co-ligand, have been prepared (for a few examples, see Fig. 1) [13]. An early publication by Cavell et al. [4] reports the isolation of mononuclear zerovalent Pd0(R-DAB)(h2alkene) (A, Fig. 2) for various R and electron-poor alkenes. In many cases, Pd0(R-DAB)(L) complexes derived from open-chain R-DAB exist as mononuclear species with the R-DAB acting as a bidentate chelating entity, notably when the stoichiometry of Pd, R-DAB and alkene is 1:1:1. Dinuclear compounds with a bridging R-DAB ligand are obtained in quite a number of

0020-1693/02/$ - see front matter 2002 Elsevier Science B.V. All rights reserved. PII: S 0 0 2 0 - 1 6 9 3 ( 0 1 ) 0 0 6 7 6 - 4

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Fig. 2. Generic structures of zerovalent Pd(diazadiene)(h2-alkene) and Pd(Ar-BIAN)(h2-alkene) compounds.

Scheme 1. Stereoselective Pd(BIAN)-catalyzed cis-hydrogenation of alkynes to (Z)-alkenes.

been synthesized, e.g. Pt11X2(diazadiene)(h2-alkene) and similar compounds [7]. The interest in our group in low-valent Group 10 metal compounds containing chelating N-ligands, especially palladium compounds containing the rigid ArBIAN ligand (B, Fig. 2), stems largely from their excellent suitability as (pre)catalysts for a number of selective carbonelement coupling reactions [9], such as Suzuki/Negishi type C C bond formation [9a,b], threecomponent coupling reactions [9bd] and stereoselective cis-hydrogenation of alkynes (Scheme 1) [9e]. For modelling purposes of some of these palladiumcatalyzed reactions and for several other reactions currently under investigation, we needed a series of zerovalent platinum compounds similar to A, i.e. containing the simple diimine motif. Contrary to the palladium case, the number of known zerovalent platinum compounds containing bidentate N-ligands is not very large, but several Pt0(NN) compounds have been reported in the literature [5a,6]. Examples are Pt0(RDAB)(h2-alkene) [6a,b], watersoluble analogues containing chiral substituents on the N-atoms, based on a-D-mannose [6c,d], and Pt0(Phen)(h2-alkene) [6e]. In this paper we describe the efcient synthesis of new Pt0(diazadiene)(h2-alkene) complexes of the general formula A (Fig. 2), prepared from readily available Pt0 precursors, various diazadiene ligands and electronpoor alkenes. The complexes obtained are relevant as an (alternative) entry into systems which are capable of carbon element bond-forming (e.g. hydrosilation), bond-breaking and bond-activation reactions (e.g. C H activation) [9,10].

2. Results and discussion

2.1. Synthesis
The R-DAB ligands 1ae and similar diazadienes 1fk (Fig. 3) have been synthesized according to literature by condensation of glyoxal or 2,3-butadione with the appropriate primary amine [11]. Synthesis of zerovalent platinum compounds of these diazadiene ligands was attempted starting from the readily available Pt0 precursors Pt(DBA)2 [12a] and (Pt(dipDBA)2 [12b], using dimethyl fumarate (DMFU, x), maleic anhydride (MA, y) or fumaronitrile (FN, z) as the alkene according to Eq. (1). In all cases, rst the alkene was allowed to react with the platinum reagent in dry diethyl ether for a given period of time and then the diazadiene was added in portions. Since the DBA ligands are rather sluggishly substituted, the norbornene complex Pt(NBE)3 and the cyclooctadiene complex Pt(COD)2 were prepared. [Pt0(L)n ]+ alkene [Pt0(L)n 1(h2-alkene)]+ L (1a)

Fig. 3. Diazadienes and zerovalent Pt(diazadiene)(h2-alkene) compounds relevant to this study.

cases as well, for instance, see Refs. [1,4], especially in the presence of more than 1 equiv. of alkene per palladium, and in some cases upon oxidative addition (e.g. of methallyl chloride to Pd0(R-DAB)(h2-alkene)). At a later stage, several other Pd0(diazadiene)(h2-olen) compounds have been reported [5]. Furthermore, numerous divalent palladium and platinum compounds containing the diazadiene entity have

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Table 1 Yields of Pt0(diazadiene)(h2-alkene) compounds synthesized from various precursors a Compound 2ax 2ax 2ax 2ax 2ay 2bx 2cx 2dx 2dx 2dx 2dz 2ex 2fx 2gx 2hx 2hy
a

R H H H H H H H H H H H H CH3 CH3 CH3 CH3

R% i-Pr i-Pr i-Pr i-Pr i-Pr n-Bu t-Bu p-tolyl p-tolyl p-tolyl p-tolyl p-anisyl cyclopropyl n-Bu n-octyl n-octyl

E CO2Me CO2Me CO2Me CO2Me C(O)OC(O) CO2Me CO2Me CO2Me CO2Me CO2Me CN CO2Me CO2Me CO2Me CO2Me C(O)OC(O)

Precursor Pt(DBA)2 Pt(dipDBA)2 Pt(NBE)3 Pt(COD)2 Pt(COD)2 Pt(COD)2 Pt(COD)2 Pt(DBA)2 Pt(NBE)3 Pt(COD)2 Pt(DBA)2 Pt(COD)2 Pt(COD)2 Pt(COD)2 Pt(COD)2 Pt(COD)2

Yield (%) 56 b 0 43 77 c 80 7 47 0 64 49 6 15 91 56 24 19

According to Eq. (1). Puried by column chromatography. c Isolated via Pt(COD)(DMFU).

b

[Pt0(L)n 1(h2-alkene)] +diazadiene [Pt0(diazadiene)(h2-alkene)] +(n 1)L (1b)

Employing diazadiene ligands 1a 1h resulted in the ready formation of the corresponding 1:1:1 complexes Pt0(diazadiene)(h2-alkene) 2ax 2hy (Fig. 3), albeit the ease of work-up and the yields varied drastically, as described below. When using Pt(DBA)2 or Pt(dipDBA)2 as a Pt0 precursor, long reaction times were necessary for the substitution to go to completion for all the complexes investigated. Compounds 2dx, 2dz, 2jx, 2jz, 2kx and 2kz were obtained in very low yields or could not be isolated using this method. Also, because of the slow substitution of DBA and dipDBA by the diazadiene ligand, much metallic platinum was formed in most cases. Furthermore, the similar solubility properties of DBA and the target compounds posed difculties in purication of the complexes. Upon repeated washing with pentane, all of the DBA could be removed, but altogether, the yields of the reactions employing these precursors were rather low. Column chromatography on alumina, eluting with toluene, gave a good separation and provided the pure complex 2ax in much higher yield (56%) as compared to washing the crude product with pentane (17%). Column chromatography also gave a reasonable to good yield for 2dx, but represents a rather tedious and time-consuming work up procedure. Especially because of the long reaction times required for reactions with Pt(DBA)2 (which in several cases led to very low or no yield at all), we decided to apply Pt0 precursors containing more substitution-labile ligands, such as Pt(COD)2 and Pt(NBE)3 [6b,13]. Typically, Pt(COD)2 was reacted with the appropriate alkene in diethyl ether whereupon

Pt0(COD)(h2-alkene) is formed within 1020 min at 20 C. This could be veried by isolation and characterization of Pt(COD)(DMFU) [13]. The subsequent reaction of this complex with diimines was fast and selective and resulted in Pt0(diazadiene)(DMFU) compounds 2ax2hy. Similar reactions were carried out using maleic anhydride or fumaronitrile for a few cases, see Table 1. In all cases the complexes could simply be puried by evaporating the solvent and free COD and, additionally, one washing with pentane. No column chromatography or repeated washing was necessary to obtain pure complexes in these instances and the yields were generally good. The complexes 2ax2hy are dark-red to orange solids, which are stable in air for a long time. Apparently, the exchange of the COD, compared to substitution of DBA, is much faster and is accompanied by almost no decomposition of the Pt0 precursor. Furthermore, we have evaluated Pt(NBE)3 for the synthesis of the Pt0(diazadiene)(h2-alkene) complexes. The results for Pt(NBE)3 were comparable to the results for Pt(COD)2. Hence, Pt(COD)2 and Pt(NBE)3 are to be preferred as the starting materials. Since the former is obtained via the latter, application of Pt(NBE)3 seems to be more economic. However, Pt(COD)2 is the more stable of the two.1

1 Pt(COD)2 can be safely stored under N2 at 20 C for a long time and can be handled in air, whereas Pt(NBE)3 has to be stored for only a limited period under N2 at 20 C in the presence of some free norbornene to prevent decomposition.

D.S. Tromp et al. / Inorganica Chimica Acta 327 (2002) 9097 Table 2 H NMR data of the Pt0(diazadiene)(h2-alkene) complexes a R R% Alkene C H R Table 2 (Continued) 2hy Complex 2.06 s 4.05 m, NCH2 1.94 m, NCH2CH2 1.21 m, CH3(CH2)5 0.84 t, CH3(CH2)5 3.53 s 3.53 d, 78 Hz

93

2ax

8.90 s 8.90 d, 55 Hz

2ay

8.86 s 8.86 d, 61 Hz

2bx

8.74 s 8.74 d, 58 Hz

2cx

2dx

8.93 s 8.93 d, 53 Hz 9.22 s 9.22 d, 52 Hz

1.60 d, 6.0 Hz, CH3 1.40 d, 6.6 Hz, CH3 4.06 m, CH 1.56 d, 6.3 Hz, CH3 1.49 d, 6.3 Hz, CH3 4.07 m, CH 4.07 m, NCH2 2.03 m, NCH2CH2 1.38 m, CH3CH2 0.97 t, CH2CH3 1.58 s, CH3

3.88 s 3.88 d, 86 Hz 3.76 s 3.76 d, 81 Hz 3.88 s 3.88 d, 87 Hz 3.61 s, CH3 3.60 s, CH3

a Recorded in CDCl3 at 293 K (either at 300.13 or 499.99 MHz). The second line in the second and fourth columns refers to 195Ptsatellites. b Recorded in CDCl3 at 293 K at 300.13 MHz.

2.2. Analysis
The compounds 2ax2hy have been analyzed by means of standard 1H and 13C NMR techniques, infrared, FAB MS, and (in several cases) by elemental analysis. All compounds showed the expected isotopic pattern in the mass spectra of their molecular ions for monomeric Pt0(diazadiene)(h2-alkene) complexes. The NMR data (Table 2) are in agreement with the proposed structures. A normal low-frequency shift of the CH3-imine, of the alkene protons and alkene carbon nuclei was observed. The usual high-frequency shift was observed for the imine protons and N C carbon nuclei. Coupling constants nJ(195Pt, 1H) and nJ(195Pt, 13C) are similar to values found in the literature for other Pt(N,N-chelate)(h2-alkene) complexes [5a,6]. IR spectra (selected compounds, see Section 4) showed a shift of the w(C N) stretch vibration from about 1630 cm 1 for the uncoordinated diazadiene ligand to values around 1550 cm 1 for the complexes, in agreement with the literature [11a,14].

2dz

9.16 s 9.16 d, 48 Hz

2ex

9.12 s 9.12 d, 52 Hz

2fx b

0.98 s

2gx

1.88 s

2hx

1.95 s

2.36 s, ArCH3 7.05 d, 8.1 Hz, ArH 7.62 d, 8.7 Hz, ArH 2.35 s, ArCH3 7.23 d, 9.9 Hz, ArH 7.72 d, 8.1 Hz, ArH 3.54 s, OCH3 7.72 d, 9.0 Hz, ArH 6.73 d, 9.3 Hz, ArH 2.45 m, CH 2.09 m, CH2 1.71 m, CH2 4.07 m, NCH2 1.88 m, NCH2CH2 1.44 m, CH3CH2 0.98 t, CH3CH2 4.03 m, NCH2 1.94 m, NCH2CH2 1.31 br, CH3(CH2)5 0.85 t, CH3(CH2)5

3.78 s 3.78 d, 73 Hz 4.01 s 4.01 d, 84 Hz

3.58 s, CH3

3.52 s, CH3

3.01 s 3.01 d 89.4 Hz 3.97 s 3.97 d, 85 Hz 3.83 s, CH3

4.17 s 4.17 d, 81 Hz

3. Conclusions
3.60 CH3

3.66 s 3.66 d, 87 Hz 3.57 s, CH3

3.67 s 3.67 d, 88 Hz 3.58 s, CH3

Novel, thermally stable Pt0(diazadiene)(h2-alkene) complexes have been synthesized in good yield from Pt0(COD)2 or Pt0(NBE)3 as a Pt0 precursor, via stepwise substitution of the labile alkenes by an electronpoor alkene, followed by the appropriate diazadiene ligand. The exchange of DBA and dipDBA, when using Pt(DBA)2 or Pt(dipDBA)2, with the alkenes and diazadiene-ligand is slow, much metallic platinum is formed, and separation of the Pt(0)-complex from DBA or dipDBA is difcult, resulting in very low yields of the desired complexes. The Pt0(diazadiene)(h2-alkene) complexes are dark-red to orange compounds and can, as solids, be safely handled and stored in air without decomposition. Normal coordination-induced shifts and coupling constants of Pt to the diazadiene ligand and alkene are observed in their NMR spectra and the expected shifts of the asymmetric C N stretching mode

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are observed in the IR spectra. The compounds obtained are members of a very useful category of starting materials for various endeavors in synthetic organoplatinum chemistry and catalysis. Not only may these be employed in oxidative additions of organic halides, to give models for related C C bond forming Pd-catalysts, but also, by addition of appropriate acids, provide an alternative approach to systems suitable for activation of C H bonds [10,15].

4.2.2. 5,8 -Diaza-dodeca-5,7 -diene (N,N%-di-n-butylDAB; 1b) 13 C NMR (CDCl3): l 162.0 (HC N), 61.3 (NCH2), 32.7 (CH2), 20.5 (CH2), 13.9 (CH3). 4.2.3. 3,6 -Diaza-2,2,7,7 -tetramethyl-octa-3,5 -diene (N,N%-t-butylDAB; 1c) 13 C NMR (CDCl3): l 158.0 (HC N), 58.3 (C(CH3)), 29.5 (CH3). 4.2.4. 1,4 -Di(4 -methylphenyl) -1,4 -diaza-1,3 -butadiene (N,N%-di-p-tolylDAB; 1d) 13 C NMR (CDCl3): l 159.3 (HC N), 147.8+ 138.4 (ArCH), 130.3+ 121.6 (ArCH), CH3 21.4. 4.2.5. 1,4 -Di(4 -methoxyphenyl) -1,4 -diaza-1,3 -butadiene (N,N%-di-p-anisylDAB; 1e) 13 C NMR (CDCl3): l 160.0 (ArC N), 157.8 (CH N), 123.3 (ArCH), 114.8 (ArCH), 55.7 (OCH3). 4.2.6. 5,8 -Diaza-6,7 -dimethyl-dodeca-5,7 -diene (N,N%-di-n-butylDAB-Me; 1g) IR (KBr, cm 1): 1636 (C N). 1H NMR (CDCl3): l 2.01 (s, 6H, N C(CH3)), 3.38 (t, 4H, J(1H 1H) =7.1 Hz, NCH2), 1.62 (p, 4H, NCH2CH2), 1.39 (s, 4H, CH3CH2), 0.92 (t, 6H, CH2CH3). 13C NMR (CDCl3): l 167.8 (N C(CH3)), 52.2 (NCH2), 33.1 (NCH2CH2), 20.8 (CH2CH3), 14.0 (CH2CH3), 12.5 ((CH3)C N). 4.2.7. 9,12 -Diaza-10,11 -dimethyl-eicosa-9,11 -diene (N,N%-di-n-octylDAB-Me; 1h) IR (KBr, cm 1): 1635 (C N). 1H NMR (CDCl3): l 2.03 (s, 6H, N C CH3), 3.40 (t, 4H, J(1H 1H) =7.2 Hz, NCH2), 1.32 (br, 10H, CH3(CH2)5), 0.87 (t, 6H, CH3(CH2)5). 13C NMR (CDCl3): l 168.0 (N C(CH3)), 52.9 (NCH2), 32.1 (NCH2CH2), 31.0+ 29.6+ 27.9+ 22.9 (CH2), 14.3 (CH3), 12.8 ((CH3)C N). 4.2.8. 6,9 -Diaza-7,8 -dimethyl-tetradeca-1,6,8,13 tetraene (N,N%-di(4 -pentenyl)DAB-Me; 1k) 1 H NMR (CDCl3): l 2.22 (s, 6H, N C(CH3)), 4.13 (m, 4H, NCH2), 5.75 (m, 2H, CH2 CH), 5.09 (m, 4H, CH2 CH), 2.13 (m, 4H, CHCH2 CH2), 1.59 (m, 4H, CHCH2CH2). 13C NMR (CDCl3): l 136.2 (CH CH2), 125.6 (N C(CH3)), 116.9 (CH CH2), 45.5 (NCH2), 30.6 ( CHCH2), 28.8 (NCH2CH2), 9.1 (CH3). 4.2.9. Pt 0 precursors The Pt0 precursors employed were synthesized according to literature procedures: platinum dibenzylideneacetone (Pt(DBA)2) [12a], platinum diisopropyldibenzylideneacetone (Pt(dipDBA)2) [12b], platinum trisnorbornene (Pt(NBE)3) [16a] from Pt(COD)Cl2 obtained according to Ref. [17], platinum bis(cyclooctadiene (Pt(COD)2) [16a,16b] and platinum(cyclooctadiene) dimethylfumarate (Pt(COD)(DMFU)) [13].

4. Experimental

4.1. General
All reactions were carried out under nitrogen atmosphere in dry solvents. Acetone was distilled from CaSO4. Diethyl ether, THF and toluene were distilled from sodium metal and dichloromethane was distilled from CaH2. Chemicals were purchased from Acros Chimica, Aldrich and Fluka. The 1H and 13C NMR spectra were recorded at appropriate frequencies in Varian Mercury 300 and Varian Inova 500 spectrometers. The IR spectra were recorded in a BioRad FTS-7 spectrometer. Elemental analyses were carried out by Kolbe, Mikroanalitisches Laboratorium, Mulheim a.d. Ruhr, Germany. Compounds 1a1f, 1j are known [11,15], 1g 1i, 1k and 2a 2h (x, y, z) are new compounds. Synthesis and selected spectral data of these compounds are given below.

4.2. Synthesis of R-DAB and other diazadiene ligands

The syntheses were carried out in analogy to Ref. [11]: 2 equiv. of the primary amine was stirred in MeOH at 0 C with 1 equiv. of glyoxal (30% in H2O), or in dry MeOH at 20 C with 1 equiv. of 2,3-butadione. A catalytic amount of formic or p-toluene sulfonic acid was added for condensations with 2,3-butadione. Upon completion of the reaction, solid diazadiene ligands were ltered off and washed. For liquid diazadiene ligands, the solvent was evaporated and the diazadiene distilled if necessary. Yields of new diazadiene ligands 1g: 98%, 1i: 41%, 1k: 64%. The NMR and some IR data of the diazadiene ligands 1a 1k which have not yet been published have been compiled below.

4.2.1. 3,6 -Diaza-2,7 -dimethyl-octa-3,5 -diene (N,N%-diisopropylDAB; 1a) IR (KBr, cm 1): 1623 (C N). 13C NMR (CDCl3): l 159.5 (HC N), 61.1 (CH), 23.7 (CH3).

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4.3. Synthesis of [Pt 0(diazadiene)(p 2-alkene)] compounds 4.3.1. A. Using Pt(DBA)2 or Pt(dipDBA)2 An amount of 1.0 equiv. of Pt0 precursor and 1.0 1.5 equiv. of the appropriate alkene (DMFU, MA or FN) were stirred in dry diethyl ether at 20 C under N2 for 10 min. An amount of 1 equiv. of the diazadiene ligand was then added in small portions to this solution. After stirring at 20 C during 12 24 h, the reaction mixture was ltered over Celite, the solvent evaporated and the residue washed several times with pentane. The complex was then puried by column chromatography on Al2O3 (deactivated with 7% H2O, eluting with toluene, followed by dichloromethane) and evaporation of the solvent. 4.3.2. B. Using Pt(NBE)3 or Pt(COD)2 The same procedure as above was followed up to and including the addition of diazadiene, but using 1.0 1.1 equiv. of the alkene. After a reaction time of 1 2 h, the solvent was evaporated in vacuo and the residue was washed once with a small amount of pentane and dried to yield the pure products. 4.3.3. (|-N,|-N%-3,6 -Diaza-2,7 -dimethyl-octa3,5 -diene)(p 2-(E) -dimethylbut-2 -ene-1,4 -dioate)platinum(0) (2ax) FAB MS: M+ = 480.1. IR (KBr. cm 1): 1547 (C N). 1 H NMR (CDCl3): l 8.90 (s, 2H, N CH), 8.90 (d, 3 J(195Pt 1H) = 55.5 Hz, 2H, N CH), 4.05 (m, 2H, CH(iPr)), 3.85 (s, 2H, HC CH), 3.85 (d, 2J(195Pt 1H) =86.4 Hz, 2H, HC CH), 3.59 (s, 6H, OCH3), 1.60 (d, J(1H 1 H) = 6 Hz, 6H, (CH3)2CH), 1.38 (d, J(1H 1H) =6.3 Hz, 6H, CH3(i-Pr)). 13C NMR (CDCl3): l 177.7 (C O), 177.7 (d, 2J(195Pt 13C) = 56 Hz, C O), 160.3 (C N), 64.7 (CH3)2CH, 64.7 (d, 2J(195Pt 13C) = 73 Hz, CH(CH3)2), 51.0 (OCH3), 25.4 (C C), 25.4 (d, 1J(195Pt 13C) = 399 Hz, C C), 24.05 ((CH3)2CH), 24.05 (d, 3J(195Pt 13C) = 13.4 Hz, (CH3)2CH), 23.7 ((CH3)2-CH). Elemental analysis: Calc. for C14H24N2O4Pt (479.14): C, 35.07; H, 5.05; N, 5.84. Found: C, 34.98; H, 5.12; N, 5.79%. 4.3.4. (|-N,|-N%-3,6 -Diaza-2,7 -dimethyl-octa3,5 -diene)(p 2-(Z) -but-2 -ene-1,4 -dicarboxylic acid anhydride)platinum(0) (2ay) 1 H NMR (CDCl3): l 8.86 (s, 2H, N CH), 8.86 (d, 3 J(195Pt 1H) = 60.9 Hz, 2H, N CH), 4.08 (m, 2H, CH(CH3)2), 3.76 (s, 2H, HC CH), 3.76 (d 3J(195Pt 1 H) = 81 Hz, 2H, HC CH), 1.56 (d, J(1H 1H) =6.3 Hz, 6H (CH3)2CH), 1.49 (d, J(1H 1H) =6.3 Hz, 6H, (CH3)2CH). 13C NMR (CDCl3): l 175.4 (C O), 161.3 (C N), 65.5 ((CH3)2CH), 24.8 ((CH3)2CH), 24.4 (C C), 24.4 (d, J(195Pt 13C) =237 Hz, C C), 23.6 ((CH3)2CH). Elemental analysis: Calc. C14H24N2O4Pt (479.14): C, 33.26; H, 4.19; N, 6.46. Found: C, 30.25; H, 3.64; N, 5.71%.

4.3.5. (|-N,|-N%-5,8 -Diaza-dodeca-5,7 -diene)(p 2-(E) -dimethylbut-2 -ene-1,4 -dioate)platinum(0) (2bx) 1 H NMR (CDCl3): l 8.74 (s, 2H, N CH), 8.74 (d, 2H, 3 J(195Pt 1H) =58.5 Hz, N CH), 4.05 (m, 4H, NCH2), 3.88 (s, 2H, HC CH), 3.88 (d, 2H, 2J(195Pt 1H) =87 Hz, HC CH), 3.61 (s, 6H, OCH3), 2.03 (m, 4H, NCH2CH2), 1.38 (s, 4H, CH2CH3), 0.97 (t, 6H, CH2CH3). 4.3.6. (|-N,|-N%-3,6 -Diaza-2,2,7,7 -tetramethyl-octa3,5 -diene)(p 2-(E) -dimethylbut-2 -ene-1,4 -dioate)platinum(0) (2cx) 1 H NMR (CDCl3): l 8.92 (s, 2H, N CH), 8.92 (d, 3 J(195Pt 1H) =53 Hz, 2H, N CH), 3.79 (s, 2H, HC CH), 3.79 (d2, J(195Pt 1H) =73.2 Hz, 2H, HC CH), 3.58 (s, 6H, OCH3), 1.57 (s, 18H, CH3(t-Bu)). 13C NMR (CDCl3): l 177.9 (C O), 159.2 (C N), 65.3 (C(CH3)3), 50.9 (OCH3), 30.0 (C(CH3)3), 25.7 (C C), 25.7 (d, J(195Pt 1H) =412.5 Hz, C C). 4.3.7. (|-N,|-N%-1,4 -Di(4 -methylphenyl) 1,4 -diaza-1,3 -butadiene)(p 2-(E) -dimethylbut-2 -ene1,4 -dioate)platinum(0) (2dx) FAB MS: M+ = 576.1. 1H NMR (CDCl3): l 9.22 (s, 2H, N CH), 9.22 (d, 3J(195Pt 1H) =52 Hz, 2H, N CH), 7.62 (d, J(1H 1H) =8.7 Hz, 8H, p-tolylH), 7.05 (d, J(1H 1H) =8.1 Hz, 8H, p-tolylH), 4.01 (s, 2H, HC CH), 4.01 (d, 2J(195Pt 1H) =84 Hz, 2H, HC CH), 3.52 (s, 6H, CH3(COOMe)), 2.36 (s, 6H, CH3C6H4). 4.3.8. (|-N,|-N%-1,4 -Di(4 -methylphenyl) 1,4 -diaza-1,3 -butadiene)(p 2-(E) -1,2 -dicyano-ethene)platinum(0) (2dz) 1 H NMR (CDCl3): l 9.16 (s, 2H, N CH), 9.16 (d, 3 J(195Pt 1H)=48 Hz, 2H, N CH), 7.72 (d, J(1H 1H)= 8.1 Hz, 8H, p-tolylH), 7.23 (d, J(1H 1H) =9.9 Hz, 8H, p-tolylH), 3.01 (s, 2H, HC CH), 3.01 (d, 2J(195Pt 1H)= 89.4 Hz, 2H, HC CH), 2.35 (s, 6H, CH3(p-tolyl)). 4.3.9. (|-N,|-N%-1,4 -Di(4 -methoxyphenyl) -1,4 diaza-1,3 -butadiene)(p 2-(E) -dimethylbut-2 -ene-1,4 dioate)platinum(0) (2ex) 1 H NMR (CDCl3): l 9.12 (s, 2H, N CH), 9.12 (d, 3 J(195Pt 1H) =52.2 Hz, 2H, N CH), 7.72 (d, J(1H 1H) =9 Hz, 4H, ArH), 6.73 (d, J(1H 1H) =9.3 Hz, 4H, ArH), 3.97 (s, 2H, HC CH), 3.97 (d, 2 J(195Pt 1H) =85.2 Hz, 2H, HC CH), 3.83 (s, 6H, OCH3), 3.54 (s, 6H, CH3(p-anisyl)). 4.3.10. (|-N,|-N%-1,4 -Dicyclopropyl) -1,4 diaza-2,3 -dimethyl-1,3 -butadiene)(p 2-(E) -dimethylbut-2 ene-1,4 -dioate)platinum(0) (2fx) FAB MS: M+ = 504.1. 1H NMR (C6D6): l 4.17 (s, 2H, HC CH), 4.17 (d, 2J(195Pt 1H) =81.3 Hz, 2H, HC CH), 3.60 (s, 6H, OCH3), 2.45 (m, 2H, CH(cyclopr.)), 2.09 (m, 4H, CH2(cyclopr.)), 1.66 (m, 4H, H2(cyclopr.)), 0.98 (s, 6H, N C(CH)3). 13C NMR

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D.S. Tromp et al. / Inorganica Chimica Acta 327 (2002) 9097 (b) A. Togni, L.M. Venanzi, Angew. Chem., Int. Ed. Engl. 33 (1994) 497. (a) H. Bock, H. tom Dieck, Chem. Ber. 100 (1967) 228; (b) E. Bayer, E. Breitmaier, V. Schurig, Chem. Ber. 101 (1968) 1594; (c) H. tom Dieck, I.W. Renk, Chem. Ber. 104 (1971) 92; (d) M. Svoboda, H. tom Dieck, C. Kruger, Y.-H. Tsay, Z. Naturforsch., Teil B 36 (1981) 814; (e) H.-W. Fruhauf, F. Seils, R.J. Goddard, M.J. Romao, Organometallics 4 (1985) 948; (f) W.P. Mul, C.J. Elsevier, H.-W. Fruhauf, K. Vrieze, I. Pein, M.C. Zoutberg, C.H. Stam, Inorg. Chem. 29 (1990) 2336. K.J. Cavell, D.J. Stufkens, K. Vrieze, Inorg. Chim. Acta 47 (1980) 67. (a) R. van Asselt, C.J. Elsevier, W.J.J. Smeets, A.L. Spek, R. Benedix, Recl. Trav. Chim. Pays-Bas 113 (1994) 88; (b) R. van Asselt, C.J. Elsevier, W.J.J. Smeets, A.L. Spek, Inorg. Chem. 33 (1994) 1521; (c) R.A. Klein, R. van Belzen, K. Vrieze, C.J. Elsevier, R.P. Thummel, J. Fraanje, K. Goubitz, Coll. Czech. Chem. Commun. 62 (1997) 238; (d) M.L. Ferrara, F. Giordano, I. Orabona, A. Panunzi, F. Ruffo, Eur. J. Inorg. Chem. (1999) 1939; (e) C. Boriello, M.L. Ferrara, I. Orabona, A. Panunzi, F. Ruffo, J. Chem. Soc., Dalton Trans. (2000) 2545. (a) P. Overbosch, G. van Koten, O. Overbeek, J. Am. Chem. Soc. 102 (1980) 2091; (b) V. De Felice, A. De Renzi, F. Ruffo, D. Tesauro, Inorg. Chim. Acta 219 (1994) 169; (c) M.L. Ferrara, L. Orabona, F. Ruffo, Organometallics 17 (1998) 3832; (d) F. Ruffo, A. de Renzi, A. Panunzi, Inorg. Synth. 32 (1998) 158; (e) M. Bigioni, P. Ganis, A. Panunzi, F. Ruffo, C. Salvatore, A. Vito, Eur. J. Inorg. Chem. (2000) 1717. (a) L. Maresca, G. Natile, M. Calligaris, P. Delise, L. Randaccio, J. Chem. Soc., Dalton Trans. (1976) 2386; (b) A. De Renzi, A. Panunzi, A. Saporito, A. Vitagliano, Gazz. Chim. Ital. 107 (1977) 549; (c) H. van der Poel, G. van Koten, K. Vrieze, M. Kokkes, C.H. Stam, J. Organomet. Chem. 175 (1979) C21; (d) H. van der Poel, G. van Koten, J. Organomet. Chem. 187 (1980) C17; (e) G. Albano, F. Demartin, A. De Renzi, G. Morelli, A. Saporito, Inorg. Chem. 24 (1985) 2032; (f) V. De Felice, M. Funicello, A. Panunzi, F. Ruffo, J. Organomet. Chem. 403 (1991) 243; (g) K. Yang, J. Lachicotte, R. Eisenberg, Organometallics 16 (1997) 5234; (h) P.J. Albietz, K. Yang, J. Lachicotte, R. Eisenberg, Organometallics 18 (2000) 3543; (i) G.F. Hill, L.M. Rendina, R.J. Puddephatt, J. Chem. Soc., Dalton Trans. (1996) 1809. (a) M. Barsacchi, G. Consiglio, L. Medici, G. Petrucci, U.W. Suter, Angew. Chem., Int. Ed. Engl. 30 (1991) 989; (b) W. Cabri, I. Candiani, S. Debernadinis, F. Franchalanci, S. Penco, R. Santi, J. Org. Chem. 56 (1991) 5796; (c) M. Brookhart, F.C. Rix, J.M. DeSimone, J.C. Barborak, J. Am. Chem. Soc. 114 (1995) 5894; (d) L.K. Johnson, C.M. Killian, M. Brookhart, J. Am. Chem. Soc. 117 (1995) 6414; (e) L. Johansson, O.B. Ryan, C. Rmming, M. Tilset, Organometallics 17 (1998) 3957; (f) B. Milani, A. Anzilutti, L. Vincettini, A. Sessanta o Santi, E. Zangrando, S. Geremia, G. Mestroni, Organometallics 16 (1997) 5064.

(CDCl3): l 176.9 (C O), 169.6 (C N), 50.3 (OCH3), 38.7 (CH-cyclopropyl), 25.1 (C C), 17.5 (N C(CH3)), 12.6, 10.8 (2 CH2-cyclopropyl). Elemental analysis: Calc. for C16H24N2O4Pt (503.45): C, 38.17; H, 4.88; N, 5.56. Found: C, 38.52; H, 4.75; N, 5.64%.

[3]

4.3.11. (|-N,|-N%-5,8 -Diaza-6,7 -dimethyl-dodeca5,7 -diene)(p 2-(E) -dimethylbut-2 -ene-1,4 -dioate)platinum(0) (2gx) FAB MS: M+ = 536.2. IR (KBr, cm 1): 1558 (C N). 1 H NMR (CDCl3): l 4.07 (m, 4H, NCH2), 3.66 (s, 2H, HC CH), 3.66 (d, 2J(195Pt 1H) =87 Hz, 2H, HC CH), 3.57 (s, 6H, OCH3), 1.88 (m, 4H, NCH2CH2), 1.88 (s, 6H, N C(CH3)), 1.44 (m, 4H, CH3CH2), 0.98 (t, J(1H 1 H) = 6.9 Hz, 6H, CH3 CH2). 13C NMR (CDCl3): l 177.6 (C O), 170.0 (C N), 59.0 (NCH2), 51.1 (OCH3), 32.6 (NCH2CH2), 25.7 (N C(CH3)), 20.7 (CH3CH2), 17.6 (C C), 14.2 (CH3CH2). Elemental analysis: Calc. for C18H32N2O4Pt (535.6): C, 40.37; H, 6.02; N, 5.23. Found: C, 40.29; H, 5.97; N, 5.14%. 4.3.12. (|-N,|-N%-9,12 -Diaza-10,11 -dimethyl-eicosa9,11 -dience)(p 2-(E) -dimethylbut-2 -ene-1,4 -dioate)platinum(0) (2hx) FAB MS: M+ = 648.3. IR (KBr, cm 1): 1558 (C N). 1 H NMR (CDCl3): l 4.06 (m, 4H, NCH2), 3.67 (s, 2H, HC CH), 3.67 (d, 2J(195Pt 1H) =88.2 Hz, 2H, HC CH), 3.58 (s, 6H, OCH3), 1.95 (m, 4H, NCH2CH2), 1.95 (s, 6H, N C(CH3)), 1.31 (m(b), 20H, CH3(CH2)5), 0.85 (t, 6H, CH3(CH2)5). 13C NMR (CDCl3): l 177.6 (C O), 170.0 (C N), 59.3 (NCH2), 59.3 (d, 2J(195Pt 13C) =70.7 Hz, NCH2), 51.1 (OCH3), 32.0 (NCH2CH2), 30.6 + 29.6 + 27.6 + 22.9 (CH3(CH2)5), 25.7 (C C), 25.7 (d, 1J(195Pt 13C) = 370 Hz, C C), 17.6 (N C(CH3)), 14.3 (CH3(CH2)5). 4.3.13. (|-N,|-N%-9,12 -Diaza-10,11 -dimethyl-eicosa9,11 -diene)(p 2-(Z) -but-2 -ene-1,4 -dicarboxylic acid anhydride)platinum(0) (2hy) FAB MS: M+ = 602.3. 1H NMR (CDCl3): l 4.05 (m(b), 4H, NCH2), 3.53 (s, 2H, HC CH), 3.53 (d, 1 J(195Pt 1H) = 78 Hz, 2H, HC CH), 2.06 (s, 6H, N C(CH3)), 1.94 (m(b), 4H, NCH2CH2), 1.21 (m(b), 20H, CH3(CH2)5), 0.84 (t, 6H, CH3(CH2)5). 13C NMR (CDCl3): l 175.5 (C O), 171.6 (C N), 59.4 (NCH2), 31.99 (NCH2CH2), 30.6+29.5 +27.4 +22.9 (CH3(CH2)5), 25.1 (C C), 22.9, 17.9 (N C(CH3)), 14.3 (CH3(CH2)5).

[4] [5]

[6]

[7]

[8]

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