UvA-DARE (Digital Academic Repository) Amine-thioether and Amine-pyridine Complexes of Palladium(II) and the Reactivity of the Methyl Complexes towards CO and Allenes Ankersmit, H.A.; Veldman, N.; Spek, A.L.; Eriksen, K.; Goubitz, K.; Vrieze, K.; van Koten, G. DOI 10.1016/S0020-1693(96)05315-7 Publication date 1996 Published in Inorganica Chimica Acta Link to publication Citation for published version (APA): Ankersmit, H. A., Veldman, N., Spek, A. L., Eriksen, K., Goubitz, K., Vrieze, K., & van Koten, G. (1996). Amine-thioether and Amine-pyridine Complexes of Palladium(II) and the Reactivity of the Methyl Complexes towards CO and Allenes. Inorganica Chimica Acta, 252, 203-219. https://doi.org/10.1016/S0020-1693(96)05315-7 General rights It is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), other than for strictly personal, individual use, unless the work is under an open content license (like Creative Commons). Disclaimer/Complaints regulations If you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library: https://uba.uva.nl/en/contact, or a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible. UvA-DARE is a service provided by the library of the University of Amsterdam (https://dare.uva.nl) Download date:22 Dec 2022 ELSEVIER acinagronI acimihC Acta 252 (1996) 912-302 Amine-thioether dna amine-pyridine complexes of palladium(H) dna eht reactivity of eht methyl complexes towards OC dna allenes Hubertus A. Ankersmit ,a Nora Veldman ,b Anthony L. Spek ,1.b Kjetl Eriksen ,c Kees Goubitz ,2.c Kees Vrieze a.., Gerard van Koten d a j.H. van't Hoff Research Instituut, Laboratorium Anorganische Chemie, Universiteit van Ar~terdam. Nieuwe Achtergracht 166, 1018 WV Amsterdam, Netherlands B;.jwJet Center for Biomolecular Research, Laboratorium Kristal- en Structuarchemie. Universiteit Utrecht, Padualaan 8, 3584 CH Utrecht, Netherlands c Amsterdam Institute of Molecular Studies. Laborato~ium Kristallografie, Universiteit van Amsterdam, Nieuwe Achtergracht 166, 1018 WV Amsterdam, Netherlands d Debye Instin~te, Department of Metal-Mediated Synthesis, Utrecht University. Padualann 8. 3584 CH Utrecht, P:etherlands keceived 62 hcraM ;6991 desiver 01 June 6991 Abstract The synthesis and characterization of the complexes PdX2(L) and PdX(Me)(L) (X =CI, Br, I; L =S-methyl-D/L-cysteine methyl ester (HMecysMe-N,S (a)), D/L-methionine methyl ester (HmetMe-N,S (b)), 2-aminomethylpyridine (Pyt-N,N' (e)), 2-2-amino- ethyl pyridine (Py2-N,N' (d)) ) have been reported. A single crystal X-ray determination of PdCI(Me) (HI Me cysMe-N,S) (2at) showed chelate coordination of the NS ligand. The square planar surrounding is completed by the chloride and the methyl group, which is positioned cis to the sulfur atom. The crystal structure determination of PdCI(Me)(HmetMe-N,S) (2b) shows an analogous geometry with the HmetMe-NS ligand forming a six-membered chelate ring with palladium. Again the methyl group is cis to the sulfur atom. The suucuue of PdCI (Me) (Py2-N,N') (2d) shows the presence of an aminc-pyridlne ligand also forming a six-membered chelate ring with Pd(II), with the methyl group positioned cis to the amine group. The unexpectedly stable methylpalladium complexes reacted with CO to give the corresponding acyl complexes. The structure of PdCI(C(O)Me)(HmetMe-N,S) (Sb) in the solid state shows the presence of a six- membered chelate ring. The acyl group is cis to the sulfur atom. The NS and the NN' complexes (la-4b) contain, also in solution, a chelating ligand L as demonstrated by NMR. The complexes PdX(R)(L) (R= Me, C(O)Me; L ~ HmetMe-N,S; HMelcysMe-N,S) exist in two diastereoisomeric forms which differ by the position of the methyl substituent on the S atom and can be distinguished at low terupemtures. The free energy values (AG*) of the interconversion varies between 49.5 and 62.1 k! tool- t. Reaction of PdX(R) (L) (R-- Me, C(O)Me); L = HmetMe-N,S; H Me cysMe-N,S; Pyt-N,N') with ailencs afforded Pd('o3-allyl) (L) CI. This insertion reaction is faster for the NS complexes containing the six-membered rings than for the five-memhered NS containing complexes. The kinetics of the allene insertion show a two term rate law, sbok = kt + k: allene, and depend on the nature of both the ligand and the allene substrate; either an allene dependent ( ;2k for 2a + 3-methyl- 1,2-buta~ene, 2b + 3-methyl- 1,2-butadienc and 2b + 1,2-heptadiene ) or an allane independent ( kt; for 2b + 2,4- dimethyl-2,3-pentadiene) pathway is the dominant one. Keywords: muidallaP ;sexelpmoc Amine ruflus noitanidrooc ;sexelpmoc noitresnI ;snoitcaer latsyrC serutcl:us 1. Introduction bonds and the scarcely studied alkene insertion steps in Pd- acyl bonds. Recently, insight has been gained from in situ The perfectly alternating insertion of CO and alkenes studies of catalytic systems by Brookhart et al. lh at low homogeneously catalyzed by Pd(II) complexes 1 has temperatures, while we have investigated model systems of focussed interest on the study of the intimate steps of the the type PdX(R)(L-L) (R=alkyl, C(O)R'; X--halide, catalytic cycle involved, i.e. the CO insertion step in Pd-alkyl O3SCF3-, BF4-), which closely resemble the proposed intermediates le,2, l~oth Brookhart et al. and our group * gnidnopserroC .rohtua 2 have designed systems in which stoichion~lrically CO I sserddA ecnednopserroc gniniatrep to cihpargollatsyrc seiduts (2a, ,b2 and alkenes are coupled alternatingly and which may be 2d) m this .rohtua 2 sserddA ecnednopserroc gniniatrep to cihpargollatsyrc seiduts )115( to regarded as living systems mimicking the actual copolymer- siht .rohtua ization reaction steps as proposed by Drent la and Sen 00.51$/69/3961-0200 © 6991 Elsevier ecneicS S.A. llA sthgir devreser PIISO020-1693 (96)05315-7 204 H.A. Ankersmit et La / hu)rganica Chimica Acta 2.$2 (1996) 203-219 0 0 i 2 6 5 7 6 \2 2fi enietsyc-L/D-Iyhtcm-S lyhtem eninoihtem-L/D methyl enidiryplyhtcmonima|-2 eniddyplyhteonima-2-2 retse )eMsyceMH( retse )eMtemH( (pyl) )2yp( Fig. I. The HMelcysIde, HmetMe, pyl and py2 ligands, with numbering scheme. 1 c . Boersma and co-workers 3 recently discussed similar 2,4-dimethyl-2,3-pentadiene (TMA) are commercially findings on a semi-living system involving the reaction of a available and were used without further purification. palladium-bipy system with norbornene and CO and solved the crystal structure of PdI(COCTHIoCOCTHIoCOMe)- 2.2. Instrumentation (bipy) representing an early stage of the growing polymer chain 3a. IH and 13C{IH} NMR spectra were recorded on Bruker In our model systems a number of problems are addressed AMX 300 and AC 100 spectrometers. Chemical shift values which deal with the influence of the ligands L-L, the anion are in ppm relative to Me4Si. Coupling constants are in Herz Y, the type of R group and last but not least the role of the (Hz). IR spectra were recorded on a Biorad spectro- solvent in these insertion reactions 4. Although insight into photometer. the influence of the various factors is increasing 5 , the role The CO insertion rates were determined using an electronic of L-L as an ancillary ligand in the coordination sphere of the gasburet, which consists of an Inacom Instruments 5860E/ catalytically active metal site needs more detailed study. This 1AB38 mass flow meter (with a range 0.06-9.00 ml min- t) is highlighted by the observation that, whereas PP ligands connected to a high pressure glass reaction vessel of 20 ml. with large bite angles and flexible backbones enhance the rate In order to avoid CO pressure drop a 300 ml buffer flask was of CO and alkene insertion reactions, the use of NN ligands connected. Data points were collected every second. The in complexes PX(R)(NN) results in many instances in system was pressurized with 5 bar CO and the gas flow was increased reaction rates, although the NN ligands all have measured at room temperature. small bite angles and even may be very rigid 2a. These Allene insertion rates were determined by recording the striking differences indicate that different mechanisms are electronic absorption spectra, at suitable wavelengths, on a operating for the PP and NN containing catalytic systems. Perkin-Eimer lambda 5 UV-Vis spectrophotometer. The Considering these results we have extended our ligand experiments were isothermally performed using approxi- L-L ° investigations to NS systems of the type N-(thienyli- mately 1 mM solutions. dene)-L/D-methionylmethyl ester 6, which orginated Elemental analyses were carried out by Dornis und Kolbe from the N-N-(5-methyl-2-thienylmethylidene)-L-meth- in Germany. Field desorption (FD) mass spectrometry was ionyl histamine ligand 7 . Here we report the coordination carried out using a JEOL JMS SX/SX 102A four-sector mass behavior of DIL-methionine methyl ester (HmetlVle-N,S), S- spectrometer, coupled to a JEOL MS-MP7000 data system. methyl-D/L-cysteine methyl ester (HMecysMe-N,S), 2- Conductivity measurements, during the reaction of 2a, 2c aminomethyl pyridine ( Py~-N,N' ) and 2- 2-aminoethyl - and )12 with DMA, )12 with TMA and nBuA in CH2CI2, were pyridine (Py2-N,N'), Fig. 1 ). carried out using a Consort K720 digital conductometer. 2.3. X-ray structure determination 2. Experimental Suitable crystals of 2a, 2b and 2d were mounted on a Lindemann-glass capillary, and transferred into the cold 2.1. Materials nitrogen stream on an Enraf-Nonius CAD4-T diffractometer on a rotating anode (A = 0.71073 A, Mo Kot graphite mono- All reactions were carried out in an atmosphere of purified chromated). Accurate unit-cell parameters and an orientation nitrogen, using standard Schlenk techniques. Solvents were matrix were determined from the setting angles of 25 reflec- dried and distilled prior to use or stored under an inert atmos- tions 10. The unit-cell parameters were checked for the phere, unless denoted otherwise. Ethyl acetate and triethyl- presence of higher lattice symmetry 11 . Crystal data and amine were of P.A. grade, PdCI2(COD) , PdCl(Me) ( 1,5- details on data collection and refinement are collected in COD) 8 (COD = cyelo-l,5-octadiene) and 1,2-hepta- Table .1 Data were corrected for Lp effects and for the diene (nBuA) 9 were synthesized by literature procedures. observed linear 5% decay of the reference reflections, except 2- Methylamine pyridine (Py ~ ), 2- 2-ethylamine pyridine for 2d which showed no decay. An empirical absorption/ (py2), 1,2-propadiene, 3-methyl- 1,2-butadiene (DMA) and extinction correction ',,,as applied on )12 and 2d (DIFABS H.A. Ankersmit et al. I lnorganica Chimica Acta 252 (1996) 203-219 502 elbaT I latsyrC data of 2a, 2b, 2d and 5b 2a 2b alumroF -dPICS,ON4~H~,C :1C2HC2/1 dPICS2OI~s~H1-C raluceloM thgiew 95.843 51.023 latsyrC system cinilconom cinilconom ecapS group 2'1 ~ P2t a ,)~,( b ,)~,( c )~/( 13.4476(13), 14.626(2), 13.7738(12) 8.783(3), 7.123(2), 9.237(3) 3/ (°) )7(360.411 97.04(3) V (,~) 2473.6(4) 573.5(3) Z 8 2 D~ (g cm- )~- 278.1 1.854 .p (cm- ~ ) 20.8 8.91 T(K) 150 150 laniF RI ~ 0.0338 0.0300 (5470 oF > 4o'(Fo) ) ( 1931 Fo> 4o'(Fo) ) Final wR2 ,t no. of data 0570.0 5876l 8260.0 5241 alumroF HsC dPlC:N~.I ,c~HsC dPICS~ON raluceloM weight 80.972 61.843 latsyrC system cinilconom cinilc0nom ecapS group P2 ~ / c P2 ~ / a a (/~), b (/~), c (/~) 10.2417(3), (5592.21 I I ). 8.5428(6) 8.4339(6), 15.632(2), 10.107(3) 3/ (°) 146.411 (4) 97.14(2) V )~-~( 18.779 ( i 1 ) 1.2231 (5) z 4 4 D,~ (g mc -3) 698.1 947.1 .p (em -~) 0.12 31.941 T(K) 051 392 Final IR a 1120.0 860.0 ( 0881 oF > 4o'(Fo) ) (2672 1>2.5o'(1)) Final wR2" .on of data 6640.0 3322 l Final ~R ~ .on of data 290.0 2762 aRI =El JFol- IGI I/EIFol. wR2 = I Ew(Fo 2 - G-') 2/E l'-)-'oF(w .2J~ c R, = ~w( I loFI - I~FI I )"1/Ew(Fo") I tJ2. 12 as implemented in PLATON 13 ). Compounds 2a the MISSYM algorithm implemented in the program PLU- and 2b were solved by automated Patterson methods and TON. However since all four crystallographically independ- subsequent difference Fourier techniques (SHELXS86) ent molecules have the same absolute configuration this 14. 2d was solved by automated Patterson methods and inversion center can only be approxiamte. Compounds 2b subsequent difference Fourier techniques (DIRDIF-92) and 2d displayed no disorder. Weights were optimized in the 15 . Refinement on F 2 was carded out by full-matrix least- final refinement cycles. Neutral atom scattering factors and squares techniques (SHELXL-93) 16; no observance cri- anomalous dispersion corrections were taken from Interna- terion was applied during refinement. All non-hydrogen tional Tables for Crystallography 17. The unit cell of 2d atoms were refined with anisotropic thermal parameters. The can be transformed to orthorhombic but yields an yaR of 47%. hydrogen atoms were refined with a fixed isotropic thermal The metrical orthorhombic symmetry is also not supported parameter amounting to 1.5 or !.2 times the value of the by the structure as indicated by the MISSYM option as imple- equivalent isotropic thermal parameter of their carrier atoms, mented in PLATON 13. for the methyl hydrogen atoms, and all other hydrogen atoms, A crystal of $b with dimensions 0.03 ×0.45 × 1.10 mm respectively. For one of the independent molecules of 2a a approximately was used for data collection on an Enraf- disorder model was refined for the C3H2SC2H3 part of the Nonias CAD-4 diffractometer with graphite-monochromated molecule with one common isotropic displacement parameter Cu K, radiation and a~-20 scan. A total of 3012 unique for the non-hydrogen atoms, while the hydrogens were reflections was measured, at room temperature, within the refined as described before. Also one of the two independent range - 10_<h< 19, 0<k~ 19, - 12_<l< 12, of these 2672 solvent molecules (CH2CI2) is disordered. The crystal struc- were above the significance level of 2.5o'(1). The maximum ture contains, in addition to the two-fold screw axis, a pseudo- value of sin0/A was 0.63 .~-'. Two reference reflections inversion center, at ( +0.25, 0.320, +0.25) as indicated by (121,122) were measured hourly and showed no decrease 602 .A.H timsreknA tt La / acinagronI acinbhC atcA 252 )6991( 912-302 during the 36 h collecting time. Unit cell parameters were 16.65; H, 2.99; N, 3.23. Calc. for :dPS2ON2rB3~H6C C, 16.78; refined by a least-squares fitting procedure using 23 reflec- H, ;,<.0.3 N, 3.26%. IR (KBr, em-I): 1736 (C=O). lc: tions with 80 < 20 < 90 .° Corrections for Lorentz and polar- PdBr2! (0.545 g; 2.04 mmol) was reacted with ~yP (0.220 ization effects were applied. The structure was solved by g; 2.04 mmol) in CH2CI2 (10 ml). An air stable yellow direct methods. The hydrogens were calculated. Full-matrix complex was obtained in 95% yield. IR (KBr, cm- i): 1617 least-squares refinement was performed on F, anisotropic for (C=N). ld: py2 (0.271 g; 2.22 mmol) reacted with PdBr2 the non-hydrogen atoms and isotropic for the hydrogen (0.592 g; 2.22 mmol) in 21C2HC ( 01 ml) to afford a yellow atoms, restraining the latter in such t. ÷:ay that the distance to air stable complex in 95% yield. IR (KBr, cm-l): 1611 their carrier remained constant at approximately 1.09 ,A, (C=N). which converged to R=0.067, R~=0.088, (A/o')m~x = Because of the low solubility of the bis bromide complexes 0.70. A weighting scheme w = (2.7 + ~boF + 0.0047 {C3t }H~ NMR experiments were not performed. ~hoF )2 - ~ was used. An empirical absorption correction 12 was applied, with coefficients in the range 0.57-I .75. The secondary isotropic extinction coefficient 18 refined to 2.5.2. PdCl(Me)(L)I (L = HlMe lcysMe-N,S (2a); HmetMe- EXT=0.08(6). A final difference Fourier map revealed a N,S (2b); Py'-N,N' (2c); Py2-N,N' (2d)) residual electron density between -- 3.1 and 4.1 e .~-3, the To a stirred solution of PdCI(Me)(COD) (0.652 g; largest values occurring in the vicinity of the palladium atom. 2.58 mmol) in 21C2HC ( 10 ml) a solution of HMecysMe Scattering factors were taken from Cromer and Mann 19. (0.384 g; 2.58 mmoi) in CH2CI2 ( i0 ml) was added. The The anomalous scattering of palladium, chlorine and sulfur mixture was stirred for 3 h at room temperature, after which was taken into account. All calculations were performed with the solvent was evaporated. The resulting yellow sticky solid XTAL 20, unless stated otherwise. The crystal data of 2a, was washed with Et20 (2× 01 ml), in order to remove the 2b, 2d and 5b are presented in Table !; the fractional coor- COD, and dried. A yellow solid was obtained in 92% yield. dinates are listed in Table 2. Slow diffusion, at room temperature, of Et20 into a concen- trated solution of 2a in CH2CIz afforded yellow crystals.Anal. 2.4. Synthesis of the ligands Found: C, 23.59; H, 4.64; N, 4.60. Calc. for H6C :dPS2ONIC41 C, 23.54; H, 4,61; N, 4.58%. IR (CH2C12, cm-t): 1746 2.4.1. l_/D-methionine methyl ester (HmetMe) (C=O). 13C{tH} NMR (CDCI3, 293 K, 8): -7.33 (Pd- Following literature procedures 12 , using L-methionine CH3) 22.0 (C2); 43.6 (C3); 55.8 (C6); 63.7 (C4); 171.8 (20.0 g; 0.13 mol), HmetMe was obtained as a yellow oil in (C5). Complexes 2b, 2c and 2d were obtained in a similar 60% yield (HmetMe: t~ 2°= -2.43). Anal. Found: C, way. 2b: PdC! (Me) (COD) (0.286 g; I. ! 3 mmol) reacted 43.85; H, 7.69; N, 8.66. Calc. for C6HI3NO28: C, 44.15; H, with HmetMe (0.184 g; 1.13 mmol) in CH2Ci2 (10 ml) to 8.03; N, 8.88%. IR (KBr, cm-I): 1739 (C=O). }HI{C31 afford an air stable yellow complex in 95% yield. Yellow NMR (CDCI3, 293 K, ~): 15.4 (C2); 30.2 (ca); 32.4 (C3); crystals were obtained by slow diffusion of Et20 into a con- 53.1 (C7); 52.8 (C5); 173.8 (C6). HMecysMe: IR (KBr, centrated solution of 2b in CH2C!2. Anal. Found: C, 26.35; cm-1): 1740 (C=O). 13C{IH} NMR (CDCI3, 293 K, tS): H, 4.97; N, 4.26. Calc. for CTHI6CINO2SPd: C, 26.26; H, 16.5 (C2); 39.9 (C3); 52.7 (C6); 54.3 (C4); 175.1 (C5). 5.04; N, 4.38%. IR ,21C2HC( cm - i ): 1735 (C=O). {C31 IH} NMR (CDC! ,3 293 K, 8): -3.5 (Pd-CH3) 21.4 (C2); 34.3 2.5. Synthesis of the complexes (C4); 29.7 (C3); 53.5 (C7); 54.6 (C5); 173.5 (CO). 2e: 2.5J. PdBr2(L) (L = HIMecysMe-N,S(Ia); HmetMe- starting with PdCI(Me) (COD) (0. ! 69 g; 0.75 mmol) and N,S (lb); Py~-N,N' (lc); Py2-N,N' (ld)) ~yP (0.081 g; 0.75 mmol) an off white, air stable solid was To a stirred suspension of PdBr2 (0.806 g; 3.01 mmol) obtained in 95% yield. Anal. Found: C, 31.74; H, 4.20; N, in CH2CI2 (10 ml) a solution of HMelcysMe (0.448 g; 10.59. Calc. for tHTC tCINzPd: C, 31.72; H, 4.19; N, 10.57%. 3.01 mmol) in CH2CI2 ( 51 mi) was added. The mixture was IR (KBr, cm-I): 1616 (C=N). '3C{IH} NMR (CD3CN, stirred for 81 h at room temperature, after which the solvent 343 K, 8): 2.2 (Pd--CH3); 33.5 (Ct); 112.4 (C4); 118.9 was evaporated. The resulting orange sticky solid was washed (C3); 144.3 (CS); 156.3 (C6); 164.6 (C2). 2d: starting with with Et20 (2×10 ml) and subsequently dried, which PdCI (Me) (COD) (0.201 g; 0.89 mmol) and py2 ( 0.109 afforded an air stable solid in 92% yield, re~z=415, g; 0.89 mmol) an off white, air stable solid i, quantitative M + =415 (for CsHH79Br2NO2SI°SPd). Anal. Found: C, yield was isolated. Colorless crystals were obtained by slow 15.10; H, 2.80; N, 3.53. Calc. for CsHt IBr2NO2SPd: C, 15.04; diffusion of Et20 into a concentrated solution of 2d in H, 2.78; N, 3.51%. IR (KBr, cm- ~): 1742 (C=O). CH3CN. Anal. Found: C, 34.41; H, 4.68; N, 10.10. Calc. for Complexes lb, le and ld were synthesized in a similar CsH~3CIN2Pd: C, 34.43; H, 4.70; N, 10.04%. IR (KBr, way. lb: reacting HmetMe (0.757 g; 2.88 mmoi) in 2IC2HC cm-t): 1605 (C=N). taCIIH} NMR (90% CD3CN+ 10% (10 mi) with PdBr2 (0.771 g; 2.88 mmol) afforded the DMSO-d ,6 343 K, 8): -9.9 (Pd-CH3); 37.8 (C2); 39.7 yellow air stable product in quantitative yield, re~z=429, (CI); 122.2 (CS); 124.4 (Ca); 138.0 (C6); 151.0 (C 7) 159.7 M + =429 (for C6Ht379Br2NO2SI°SPd). Anal. Found: C, (C3). H.A, Ankersmit et al. / Inorganica Chimica Acta 252 (1996) 203-219 702 elbaT 2 laniF setanidrooc dna tnelaviuqe ciportosi lamreht sretemarap of eht negordyh-non smota for ,a2 ,b2 2d dna b'b motA x y z qeU motA x y z U~ 2a Pd(1) 0.25611(4) 0.13564(3) 0.43268(4) 0.0171(I) Pd(2) 0,47651(4) 0.12321(3) 0.73870(4) 0.0214(I) Cl(1) 0.33454(13) 0.00288(13) 0.40155(12) 0.0242(4) CI(2) 0,36674(14) 0.1008(13) 0.76348(13) 0.0271(5) S(1) 0.19175(13) 0.26246(12) 0.47803(14) 0.0219(5) S(2) 0,58786(15) 0.22970(13) 0.71950(14) 0.0265(5) O(II) 0.0215(5) 0.0068(5) 0.5890(5) 0,046(2) O(21) 0.6646(5) -0.0535(4) 0.5670(5) 0.0365(19) O(12) 0.0498(4) 0.1307(4) 0.6933(4) 0.0393(17) 0(22) 0.6713(4) 0.0689(4) 0.4727(4) 0.0310(17) N( 11 ) 0.1781(5) 0.0619(4) 0.5186(5) 0.0250(17) N(2) 0.5319(5) 0.0335(4) 0.6464(4) 0.0212(17) C( I I ) 0.3170(6) 0.2096(5) 0,3450(6) 0.029(2) C(21 ) 0.4259(7) 1512.0 (6) 0.8196(7) 0.034(3) C(12) 0.1002(6) 0.3211(5) 0.3595(6) 0.034(2) C(22) 0.5009(6) 0.3026(5) 0.6116(6) 0.034(2) C(13) 0.0929(5) 0.2101(5) 0.5203(5) 0.0233(17) C(23) 0.6525(5) 0.1608(5) 0.6523(5) 0.0233(19) C(14) 0.1454(5) 0.1243(5) 0.5846(5) 0.0220(17) C(24) 0.5784(5) 0.0865(5) 0.5836(5) 0.0196(17) C(15) 0.0647(6) 0.0789(5) 0.6217(6) 0.027(2) C(25) 0.6429(5) 0.0236(5) 0.5413(5) 0.0191(17) C(16) -0.0240(8) 0.0958(8) 0.7350(8) 0.056(4) C(26) 0.7376(7) 0.0173(6) 0.4298(6) 0.036(3) Pd(3) 0.23559(4) 0.50162(4) !.05440(4) 0.0211(I) Pd(4) -0.03356(5) 0.99703(4) 0.22491(5) 0.0302(2) C1(3) 0.15338(15) 0.6315(2) 1.08653(13) 0.0352(6) C1(4) -0.1157(2) I.I143(2) 0.28117(15) 0.0344(6) S(3) 0.2980(2) 0.37587(13) !.00335(15) 0.0264(5 *S(4) 0.0194(2~ 0.8846(2) 0.1401(2) 0.0265(4) O(31) 0.4212(5) 0.6499(4) 0.8533(5) 0.046(2) *S(4B) 0.0851(6) 0.8987(6) 0.2152(6) 0.0265(4) 0(32) 0.5016(5) 0.5152(5) 0.8554(5) 0.0473(19) O(41) 0.1538(6) 1.1903(4) 0.0581(5) 0.045(2) N(3) 0.3112(5) 0.5794(5) 0.9678(5) 0.0249(17) 0(42) 0.2101(5) 1.0620(4) 0.0098(5) 0.0405(17) C(31) 0.1803(7) 0.4210(7) 1.1431(6) 0.037(3) N(4) 0.9390(5) 1.0921(5) 0.1530(5) 0.0271(19) C(32) 0.4175(6) 0.3364(6) 1.1163(6) 0.040(2) C(41) -0.0864(8) 0.9003(7) 0.2998(9) 0.050(3) C(33) 0.3586(6) 0.4298(5) 0.9229(6) 0.032(2) *C(42A) 0.1411(7) 0.8338(6) 0.2386(7) 0.0265(4) C(34) 0.3987(5) 0.5269(5) 0.9589(5) 0.0223(17) *C(42B) -0.005(2) )2(018.0 0.139(2) 0.0265(4) C(35) 0.4416(6) 0.5724(6) 0.8843(6) 0.0286(19) *C(43A) 0.0764(8) 0.9555(7) 0.0668(8) 0.0265(4) C(36) 0.5463(8) 0.5525(8) 0.7840(7) 0.051(3) *C(43B) 0.110(3) )2(459.0 0.112(3) 0.0265(4) C(44) 0.1239(6) 1.0471(5) 0.1289(6) 0.028(2) C(45) 0.1634(6) i.1095(6) 0.0617(6) 0.0294(19) C(46) 0.2531(7) I.il47(8) -0.0524(6) 0.046(3) 2b 2d Pd(1) 0.40214(2) 0.28392(6) -0,01951 (3) 0.0235(I) ,tdP )I 0.14775(2) 0,20504(I) 0.27468(2) 0.0229(I) CI(I) 0.58222(11) 0.2995(3) -0.18376(10) 0.0334(3) CI(1) 0.17067(7) 0.02218(5) 0.35592(9) 0.0328(2) S(I) 0.22377(10) 0.25379(15) 0.13466(12) 0.0297(4) N(I) 0.1105(2) 0.3620(2) 0.1847(3) 0.0280(6) (O I ) 0.8561(3) 0.2502(7) 0.3372(4) 0.0500(16) N(I) 0.3525(2) 0.2475(2) 0.4873(3) 0.0253(5) O(2) 0.7524(3) 0.3955(6) 0.5127(3) 0.0412(10) C(I) 0.2183(3) 0.4442(2) 0.2800(3) 0.0301(7) N(I) 0.5947(3) 0.2676(10) 0.1477(4) 0.0299(13) C(2) 0.2647(3) 0.4338(2) 0.4731(3) 0.0298(7) C(I) 0.2305(4) 0.2919(14) -0.1886(5) 0.0389(12) C(3) 0.3774(2) 0.3486(2) 0.5546(3) 0.0269(7) C(2) 0.0798(5) 0.4350(9) 0.0982(6) 0.0497(16) C(4) 0.5047(3) 0.3739(2) 0.6924(4) 0.0363(8) C(3) 0.3059(4) 0.3383(8) 0.3144(5) 0.0358(14) C(5) 0.6105(3) 0.2969(2) 0.7616(4) 0.0420(10) C(4) 0.4629(4) 0.2572(7) 0.3686(5) 0.0316(14) C(6) 0.5872(3) 0.1948(2) 0.6903(4) 0.0390(10) C(5) 0.5910(4) 0.3450(6) 0.2941(4) 0.0250(12) C(7) 0.4566(3) 0.1732(2) 0.5545(3) 0.305(7) C(6) 0.7478(4) 0.3201(6) 0.3822(4) 0.0262(11) C(8) -0.0420(3) 0.1727(2) 0.0779(4) 0.0368(8) C(7) 0.8957(5) 0.3779(9) 0.6074(5) 0.0407(14) 5b Pd(l) 1.05138(5) 0.61951(3) 0.99810(4) 0.0427(3) CI( I ) 0.8554(2) 0,5829( I ) 1.1345(2) 0.063( I ) S(I) 1.2374(2) 0.6713(I) 0.8715(2) 0.0533(9) O(I) 0.6232(8) 0.6465(5) 0.6291 iT) 0.078(4) 0(2) 0.7323(7) 0.5623(4) 0.4840(5) 0.063(3) 0(3) 1.2948(8) 0.5677(4) 1.1933(6) 0.071(4) N( I ) 0.8632(7) 0.6085(4) 0.8296(6) 0,047(3) C(1) 1,198(2) 0.7038(7) 1.245(I) 0,086(7) C(2) (424.1 i ) 0.6187(8) 0.914( I ) 0.084(7) C(3) 1.187(I) 0.6255(5) 0.7071(8) 0.057(4) C(4) (710.1 1 ) 0.6492(5) 0.6446(8) 0.056(4) C(5) 0.8871(8) 0.5909(4) 0.6924(7) 0.044(3) C(6) 0.7322(9) 0.6040(5) 0.5991(7) 0.049(3) C(7) 0.589(1) 0.5744(7) 0.3868(8) 0.070(5) C(8) 1.204(!) 0.6254(5) !.1612(8) 0.055(4) 802 .A.H timsreknA te .la / acinagronl acimihC atcA 252 )6991( 912-302 2.5.3. lPdBr(Me){ HlMe lcysMe-N,S} (3a ) 2.5.6. PdX(COMe)(L)I (L= HMecysMe-N,S: X=CI(5a), A solution of a,2 (0.191 g; 0.62 mmol) in 21C2HC (20 ml) Br (6a), ! (7a); HmetMe-N,S: X= Cl (5b), Br (6b), I (Tb); was reacted with Ag(O3SCF 3) (0.159 g; 0.62 mmol) for PyI-N,N' : X= CI (5c), Br (6c); PyZ-N,N' : X= Cl (5d), Br 30 rain at room temperature after which the resulting suspen- (#d)) sion was filtered in order to remove the AgCi, after which Through a yellow solution of 2a (0.03 g; 0.10 mmol) in NaBr (excess) was added. The mixture was stirre6 for 81 h CDCI3 (0.5 ml) CO was bubbled for 1 min. A small amount after which the suspension was filtered and the resulting yel- of colloidal palladium was formed and complex 5a was not low solution was evaporated. An air stable yellow solid was isolated. IR ,21C2HC( cm - i ): 1746 ( C (O) OMe ); 1700 (Pd- obtained in 80%. Anal. Found: C, 20.52; H, 4.00; N, 3.98. C(O)Me). Calc. for C6H~,:BrNO2SPd: C, 20.56; H, 4.03; N, 4.00%. IR A pressurizing flask was charged with 2b (0.06 g; 0.2 (KBr, cm-t): 1748 (C=O). mmol) in CH2CI2 (5 ml). The yellow solution was pressur- ized with CO (5 bar), and the uptake of CO was measured at room temperature. Isolation of 5b was achieved by filtra- 2.5.4. PdBr(Me)(L) (L=HmetMe-N,S (3b); PyI-N,N' tion over celite and subsequent evaporation of tile solvent. (3c); Py2-N,N' (3d)) Yellow crystals were obtained by slow diffusion of Et20 into Reacting lb (0.724 g; 1.77 mmoi) with Me4Sn (0.473 g; a concentrated solution of 5b. The crystals were kept in par- 2.65 mmol) in 21C2HC ( 51 ml) and NC~.HC ( 01 ml) for 81 a|fin oil. Elemental analysis could not be carried out owing h at room temperature resulted in a brownish solution. Evap- to slow degradation of the complex. IR (CH2C12, cm-~): oration of the solvent afforded a brown solid which was 1748 (C(O)OMe); 1701 (Pd--C(O)Me). 13C{IH} NMR purified by column chromatography (silica). Using 21C2HC (CDCI3, 293 K, 8): 21.2 (C2); 30.2 (C4); 35.2 (C3); 38.2 as the eluent a yellow fraction was isolated. After evaporation (Pd--C(O)CH3); 53.4 (C7); 54.6 (C5); 173.6 (C6); 228.3 of the solvent and drying of the product, the yellow--orange (Pd-C(O)CH3). complex 3b was collected in 60% yield. Anal. Found: C, Compounds 5c, 5d, 6a, 6b, 6c, 6d, 7a, 7b were synthesized 23.06; H, 4.44; N, 3.78. Calc. for :dPS2ONrB6~HTC C, 23.15; as described for 5b. The complexes were not isolated because H, 4.43; N, 3.84%. IR (CH2C12, cm-I): 1746 (C=O). of the gradual degradation, i.e. small amounts of colloidal }HI{C31 NMR (CDCI3, 213 K, 8): -5.0 (Pd---CH3) 21.1, palladium were formed on attempted isolation. 5e: IR 21.8 (C 2 ); 28.8, 30.5 (C a ); 33.8, 35.7 (C 3); 54.0 (C 7 ); 54.5, ,21C2HC( cm-I): 1618 (C=N); 1697 (Pd-C(O)Me). 5d: 55.0 (C5); 173.8 (C6). (CDCI3, 233 K, 8): -4.8 (Pd---CH3) IR (CH2CI ,2 cm-I): 1619 (C=N); 1701 (Pd-C(O)Me). 21.5 (C 2); not observed (C a) ; not observed (C 3); 53.8 (C 7); 6a: IR (CH2CI ,2 cm-I): 1748 (C(O)OMe); 1701 (Pd- 54.5 (C5); 174.0 (C6). (CDCI3, 293 K, 8): -4.5 (Pd--CH3) C(O)Me). 6b: IR (CH2CI2, cm-I): 1743 (C(O)OMe); 21.4 (C2); 29.9 (Ca); 34.8 (C3);53.5 (C7); 54.4 (C 5) 174.1 1700 (Pd-C(O)Me).6e: IR (CH2CI2,cm- i): 1617 (C=N); (C6). 3c and 3d were synthesized in a similar way using lc 1700 (Pd--C(O)Me). 6d: IR (CH2C12, cm-t): 1618 and ld, respectively. 3e: IR ( KBr, em - l ): 1614 (C=N). :d3 (C=N); 1702 (Pd-C(O)Me). 7a: IR (CH2C12, cm-I): IR (KBr, cm-I): 1619 (C----N). 13C{IH} NMR (CD3CN, 1747 (C(O)OMe); 1701 (Pd-C(O)Me). 7b: IR (CH2CI2, 293 K, 8): not observed (Pd-CH3); 39.0 (CI); 40.4 (C2); cm-I): 1744 (C(O)OMe); 1699 (Pd-C(O)Me). 125.0 (C5); 138.0 (C4); 139.8 (C6); 154.4 (C7); 158.7 (C3). Elemental analysis of 3e and 3d failed, probably due 2.5.7. IPdCl{ 2112HC)eM(C2HC-3~ (8) to traces of lc. PdCI(Me)(COD) (0.387 g; 1.528 mmol) was dis- solved in CH2CI2 ( 10 ml). Allene was bubbled through (2 2.5.5. PdI(Me)(L)I (L=HMeIcysMe-N,S (4a): HmetMe- ml/min) this solution at room temperature which resulted in N,S (4b)) an almost instant ( < 1 min) color change from colorless to To a solution of 2a (0.191 g; 0.62 mmol) in CH2C!2 (10 yellow. Evaporation of the solvent and subsequent drying of ml) Nal (excess) was added. An immediate color change the residue in vacuo afforded a yellow solid in 72% yield. was observed. After 1 h the suspension was filtered and the Anal. Found: C, 24.40; H, 3.58. Calc. for CsHI4CI2Pd2: C, residue was washed with H20 ( 10 ml). The organic layer 24.39; H, 3.59%. 13C{IH} NMR (CDCI3, " . x,,, 8): 23.3 was separated and dried on CaCI2. After filtration and sub- (C2'-CH3); 62.4 (-CH2); 127.5 (C2'). sequent evaporation of the solvent a hygroscopic red solid was obtained in 55% yield. IR (CH2Ci2, cm-~): 1745 2.5.8. PdCl{ ,ILCH2C(Me)C(Me)e} 2 (9) (C=O). 4b was prepared as described for 4a, starting with To a solution of PdCI(Me)(COD) (0.183 g; 0.72 2b (0.21 g; 0.65 mmol). IR ,21C2HC( cm-' ): 1742 (C=O). mmol) in CH2Cl2 ( I0 ml), DMA (0.051 g; 0.72 mmol) was '3C{~H} NMR (CDCI3, 293 K, 8): 8.56 (Pd-CH3) 20.5 added. The solution was stirred for 01 min at room temper- (C2); 27.7 (C4); 30.7 (C3); 52.7 (C7); 53.6 (C5); 172.7 ature, after which the solvent was evaporated, resulting in an (C6). Elemental analysis of 4a and 4b could not be carried air stable yellow solid in 84% yield. Anal. Found: C, 31.99; out due to the presence of traces of CH2CI2, which could not H, 4.93. Cale. for :2dP2IC22H2IC C, 32,03; H, 4.93%. {C31 IH} be removed by either washing with Et20 or drying in vacuo. NMR (CDCI3, 293 K, 8): 20.9 (C2'-CH3); 24.1 (a"aCH3); .A.H timsreknA te La acin/ agronl acimihC atcA 252 )6991( 912-302 902 24.7 ("CH3); 58.6 (-CH2); 89.5 (-C(CH3)2); 119.7 Complex 12c PdI~C-CH2C(Me)C(Me)2}(PyI-N,N')I - (c2'). CI was synthesized as described for 12a, using a 35 mM solution of 2c in CDCI3. Upon the addition of DMA (1 .9.5.2 PdCl{ lz)eM(C)eM(C2)eM(C-3I~ 2 ( )OI equiv.) a small amount of colloidal palladium was formed Synthesized as described for 9. Reacting the compounds immediately. IH (CDCI3, 293 K, 6): 8.04 (broad s, IH, for 01 h at room temperature afforded a yellow solid in 85% CtH); 7.47 (broad s, IH, CSH); 6.55 (broad s, IH, Call); yield. 13C{IH} NMR (CDCI3, 293 K, 8): 19.3 (C2'-CH3); 6.44 (broad s, IH, Call); 3.62 (broad s, IH, H°'~); 3.12 26.7 (°~aCH3); 28.6 ;)3HC"Y~( 85.7 (-C(CH3)2); 114.4 (broad s, IH, H~'~); 2.84 (broad s, 3H, C2'H3); 2.05 (broad (C 2'). Elemental analysis was not carried out, since the sim- s, 3H, a"aCH3); 1.27 (broad s, 3H, .)3HCnYs The product ilar complexes 8, 9 and 11 are analyzed properly. showed a specific conductivity ofA = 3010 l- i cm 2 tool- 1 (CH2CI ,2 293 K). .01.5.2 PdCl{ zI2)eM(C)eMOC(C2HC-3I~ (11) .21.5.2 Pd{ ~-CH2C(Me)C(Me)2 lC)S,N-eMtemH(} A solution of PdCI (Me) (COD) (0.154 g; 0.608 mmol) (12b) in 21C2HC (10 ml) was cooled to 223 K and subsequently Route B. To a solution of PdCi{~-CH2C(Me)- put under a CO atmosphere ( 1 bar) for5 min. l,l-Dimethyl- C(Me)z} 2 in 21C2HC (10 ml) a solution of HmetMe-N,S ailene (0.083 g; 1.216 mmol) was added which caused a (0.146 g; 0.897 mmol) in alC2HC (5 ml) was added. The color change from colorless to yellow. Evaporation of the mixture was stirred at room temperature for 81 h after which solvent and subsequent drying in vaeuo afforded a yellow the solvent was evaporated, resulting in yellow solid 12b in solid in 65% yield. Anal. Found: C, 33.21; H, 4.38. Calc. for 86% yield. '3CIIH } NMR (CDC13, 293 K, ,5): 20.7 (C 2'- :2dP2IC2022H41C C, 33.23; H, 4.39%. 13C{IH} NMR CH3); 22.1 (ca); 24.9 ('~'iCH3); 25.3 (~"CH3); 33.0 (ca); (CDCI ,3 293 K, 6): 24.6 (o"t~CH3); 25.6 (':'~CH3); 29.6 33.3 (C3); 54.3 (C7); 57.4 (C3'Ha); 59.3 (C5); 91.0 (-(CO)CH3); 56.9 (-CH2); 92.2 (-C(CH3)2); 117.8 (CI'(CH3)z); 121.7 (ca'); 174.4 (C7). Conductivity exper- (C2'); 199.4 (-(CO)CH3). iments performed during the reaction of 3-methyl-l,2-buta- The complexes having the general formula Pd{rl -3 diene and 2b in zIC2HC (1421 l -I cm z mol -t at 293 K) allyl} (L) X were synthesized as yellow hygroscopic sol- showed an increase of the conductivity; A = 2530 1~- ~ cmz ids via two routes, i.e. (A) reaction of PdCi(Me) (L) with tool- i (293 K). allene and (B) reaction of the ligand (L) with a PdCI('o -3 allyl) 2 complex (Scheme 1 ). 2.5.13. lPd{ 7f IC)L(}2)eM(C)eMOC(C2HC- Elemental analyses of the a-amino ester containing atlyl- (L = S,N-eMsyceMH (13a): HmetMe-N,S (13b)) palladium complexes 12a-14b could not be carried out as a A solution of 2b (0.092 g; 0.301 mmol) in 21C2HC ( I0 result of the presence of small amounts of allene (Route A) ml) was stirred at room temperature under a CO atmosphere or dimer (Route B) due to the high solubility of the products ( 1 bar) for 5 min. DMA (0.020 g; 0.301 mmol) was added and starting compounds in apolar solvents like Et20 and and after a color change to yellow, the solution was evapo- bexane. rated and subsequently dried in vacuo affording yellow com- plex 13b in 65% yield. Complex 13a was obtained as .11.5.2 Pd{ ~LCHzC(Me)C(Me)z}(HIMecysMe- described for 13b in 70% yield. {C31 IH} NMR (CI~13, 293 N,S)IICI1 (12a) K, 8): 20.1 (C2); 29.8 (C2'--C(O)CH3); 24.5 (~CH3); Route A. A mixture of 2a (0.137 g; 0.448 mmol) and l,l- 25.8 (sYnCH3); 40.2 (C3); 53.5 (ca), 56.2 (Ca); 66.3 dimethylallene (0.031 g; 0.448 mmol) in 21C2HC (10 ml) (C3'H2); not observed (C1'(CH3)2); not observed (C2'); was stirred for 30 min at room temperature. Evaporation and 171.7 (C5); 200.6 (C2'-C(O)CH3). subsequent drying in vacuo afforded compound 12a in 75% Complexes 14b, Pd{ (Me)2CC(Me)C(Me)2} (I-hnet- yield as a hygroscopic yellow solid. {C31 'H} NMR (CDCI3, Me-N,S)CI and 15b, Pd{H2CC(Me)CH(nBu)}- 293 K, 6): 18.1 (C2-CH3); 19.8 (°~'~CH3); 20.7 ('Y"CH3); (HmetMe-N,S) CI were synthesized via route A, using ?,b 23.8 (C2); 39.2 (C3); 52.4 (C6); 54.6 (C4); 65.5 (C3'H2); (0.114 g, 0.373 mmol ). Conductivity measurements of 14b 89.0 (Ct'(CH3)2); 123.0 (C2'); 172.1 (C(O)OCH3). (CH2C12) showed a specific conductivity ofA = 1879 at243 C3 { I H } NMR ( ,3ICDC 213 K, 3): 20.3 d~°~b ( 3HC---'2C ); 21.0 K, 2842 at 293 K and 3567 1~- ' cm 2 mol- 1 at 343 K, and (o"'/CH3); 22.0 ('Y"CH3); 24.9, 25.0 (C2); 39.9 d~°~ (C3); for 15b A = 1884 at 243 K, 2942 at 293 K and 3765 l~ -~ 54.2 (ca); 56.1 da°~b (C4); 66.9 (C3'H2); 95.1 (C"(CH3)2); cm 2 tool- ~ at 343 K. 125.6, 125.8 (C2'); 172.0, 172.2 (CS). Conductivity experiments performed during a reaction of 3-methyl-l,2-butadiene (DMA) and 2a in CH2C!2 (1283 3. Results ft- t cm 2 mol- ~ at 293 K) showed an increase of conductiv- ity; A = 2459 ~- i cm 2 mol - ' ( 293 K). The product showed Reaction of ligand L, i.e. racemic { (S-methyl)-DIL-cys- a specific conductivity (CH2C!2) of A = 2010 at 243 K, 3486 teine}methyl ester (HMecysMe (a)); racemic D/L- at293 K and 4102 l -t Zmc mol -~ at343 K. methionine methyl ester (HmetMe (b)); 2-amino- 2 !0 H.A. Ankersmit et aL/lnorganica Chirnica Acta 252 (1996) 203-219 O O LC I O J 3fi llo &l =n I .¢1 =n I l~n 2=n l=n 2=n .bl 2eh 2=n.dl ,a2 IC=X ,b2 ~C=X .e2 IC=X ,d2 IC=X ,43a, # ImX=X Br .~43b, -XX= ; Br ,.¢3 X= Br 3d, X= Br (~C12 Fig. .2 Numbering of the complexes, a = H eM ;S,N-eMsyc b = -eMtemH IC N.S; c = Py'-N,N" ; d = Py2-N,N'. 5C C4 methylpyridine (Fy' (c)); 2-2-aminoethylpyridine (Py 2 (d)), respectively with PdBr 2 afforded the I:I complexes SC ~ N I PdBr2(L) (I), see Fig. 2. The methyl-palladium com- plexes FdX(Me)(L) (X=CI (2), Br (3), I (4)) were synthesized via various routes. The chloride complex was prepared from PdCI(Me) (1,5-COD) and L, which could be converted with an excess of Nal to PdI(Me)(L). PdBr(Me)(L) was synthesized from PdBr2(L) and Me4Sn. The complexes dissolve in polar solvents such as .giF .3 latsyrC serutcurts of a2 )eM(lCdP I eMsyc)eM(H } l (top) dna d2 MeCN, CH2CI: and acetone and can be stored under air for )eM(ICdP )2yp( l .)mottob( pelrO sgniward era nward htiw a %05 -borp ytiliba ,level snegerdyh era dettimo rof .ytiralc sihT( is osla eurt rof .giF 6). a prolonged period. 2.149(3) (Pd-N), 2.2528(13) (Pd-S), 2.034(4) (Pd-C) 3.1. Crystal structures and 2.3246(13) (Pd-CI) ,~. The six-membered chelate ring has a chair conformation with both the methyl ester and the Single crystal X-ray determinations were carried out for thioether methyl group in equatorial position, as was also the complexes 2a (Fig. 3), )12 (Fig. 6) and 2d (Fig. 3). observed for dichlom- (D/L-methionine-N,S) palladium(II) The unit cell of 2a contains four independent molecules, 25. The NS bite angle is 95.02(10) °, which is slightly less which all consist of a cysteine ester ligand L which is biden- than the bite angle (96.88(37) °) observed in dichloro- tate bonded to the palladium center via the amine nitrogen ( D I L-methi onine-N,S ) palladium ( II ) 251. (Pd-N=2.163(7) A,) and the thioether sulfur donor (Pd- The 2- 2-aminoethyl pyridine (py2) containing complex S --- 2.2407 ( 19 ) A,). The square-planar coordinated geometry 2d again has a square planar surrounding. Relevant distances of the palladium atom is further completed by the chlorine are 2.189(2) (Pd-N(py)), 2.053(2) (Pd-NH2), 2.009(3) atom (Pd--C1--2.33i(2) A,) and the methyl group (Pd- (Pd-C) and 2.3358(7) (Pd-Cl) A. The methyl group is CI 1 =2.026(8) ,~). The latter ligand is located cis to the bonded to the palladium center cis to the amine moiety, which sulfur atom, as expected in analogy with corresponding PN might indicate that the NH2 unit has a larger trans influence palladium complexes where the methyl (or acyl) group is than the pyridine nitrogen donor. The dihedral angle of N2- always cis to the phosphorus donor atom, being the atom with PdI-N1-C1 (-0.6(2) °) shows that these atoms all lie in the highest trans influence 2b,22. The five-membered che- one plane. Since the pyridine group is twisted out of the late ring has a A conformation with an envelope geometry coordination plane by 26.9 ° the six-membered ring formed 23, with the methyl ester substituent in an equatorial posi- by the chelate bonding of the NN' ligand has a flattened tion and the thioether methyl group in an axial position, anal- twisted-boat geometry, with an N-Pd-N bite angle of ogous to the earlier reported dichloro-(S-methyi-L- 92.90(9) °. Hydrogen bonds between the NH2 unit and the cysteine-N,S)palladium(II) complex 24. The absolute chloride ion are observed; the distances (3.426(2) and configuration of the sulfur center is R, while the stereogenic 3.385(2)/~) and angles (141.1(2) and 153.9(3) °) between carbon atom C4H of the iigand has an S configuration in all the donor and acceptor fall within the normal range 26. four independent molecules in the unit ceil. Although four diastereomers, i.e. RR, SS, RS and SR, might be present in the solid state, since a racemic mixture of the ligand is used, only 3.2. Structures in solution one (SIC) is observed in the crystal lattice. The N-Pd-S bite angle of the NS coordinated cysteine ligand is 86.08(17) °, The IH and 13C{IH} NMR data for the complexes con- which is slightly less than the bite angle observed in the taining the racemic HMecysMe and the HmetMe ligands dichloro-( S-methyi-L-cysteine-N,S)palladium(II) complex confirm that, also in solution, these NS ligands are chelate (87.2(3) °) 24. bonded as evidenced by the downfield proton shifts of the S- Complex 2b, with one independent molecule in the unit Me group (A8=0.45-0.67 ppm) and of the proton on the cell, has an analogous square planar arrangement around the stereogenic carbon atom C4H (a), CSH (b) ( A 8-- 0.06-1.26 palladium center, as observed for 2a, with distances of ppm ) with respect to the values of the free l igands (Table 3). H.A. Ankersmit et al. / lnorganica Chimica Acta 252 (1996) 203-219 112 Table 3 Relevant H~ NMR data of the complexes la-Ta, lb-Tb, 1¢-6c and ld--6d, measured at room temperature .oN Solvent 3H6C (s) H4C (m) 3H2C (s) Pd-Me (s) Pal--COMe (s) H (Me) CysMe 86.3 3.6 i 2.06 la DMSO 17.3 4.19 46.2 2a 3ICDC 87.3 b88.3 b15.2 0.59 3a 3ICDC 18.3 * 45.2 0.67 4a 3ICDC 18.3 98.3 35.2 0.68 5a 3ICDC 97.3 28.3 54.2 2.60 6a 3ICDC 18.3 a 55.2 2.18 7a 3ICDC 77.3 87.3 24.2 2.10 .oN Solvent 3H7C (sO) HSC (m) 3H2C Pd-Me (s) Pd-COMe (s) HMetMe 26.3 35.3 !.97 lb DMSO 27.3 4.79 46.2 2b 3ICDC 57.3 56.3 54.2 0.58 3b 3ICDC 67.3 56.3 54.2 0.60 4b 3ICDC 47.3 95.3 04.2 0.56 5b 3ICDC 67.3 95.3 14.2 2.50 6b CDCI 3 + NC3DC (5:1 ) 06.3 4.20 2.56 2.59 7b 3ICDC 97.3 48.3 04.2 2.54 .oN Solvent H3C HSC CSH H~C 2H~C Pd-Me (s) Pd--COMe (s) pyl 6.55dt 6.34d td93.7 d50.8 2.89s lc DMSO-d 6 d75.7 7A6t t40.8 d5C.9 b15.3 2e CD3CN d66.6 6.64t td46.7 b05.8 b13.3 0.55s 3c DMSO-d 6 + 3ICDC ( :3 i ) 6.58b 6.58b b34.7 b30.8 b43.3 0.91b 5c NC3DC 6.60d 6.69t t36.7 oT2.8 2.89s 2.34s 6c NC3DC I 6.65d 6.74t t07.7 )143.8 3.0Is 2.35s .oN Solvent H*C HSC H~C HTC 2HtC Pd-Me (s) Pd-COMe (s) 2yp 7. I 0dt d60.7 td35.7 dTA8 2.85t ld DMSO-d 6 7.58d 7.46t t40.8 9.06d b92.3 2d DMSO-d 6 b83.7 7.35b td58.7 9.06d b50.3 0.30s 3d DMSO-d ~ 7.38b 7.38b b71.8 9.10b 3.38b 0.67s 5d DMSO-d 6 7.34 I(63.7 t10.8 d30.9 4.28b 2.05s 6d DMSO-d ~ 7.41t d53.7 t31.8 d21.9 3.20b 2.19 s, singlet; d, doublet; t, triplet; dt, double triplet; b, broad resonance signal; m, muitiplet. The coupling constants of H ,3 H ,4 H 5 and 61-! of the pyridine moiety are approximately ! J(H 3 -H 4 ) = 5.0 Hz, i J(H 4 -H 5 ) = 8.4 Hz, I J(H 5 -H 6 ) =4.7 Hz and of the ethylene-amine bridge | J(H-H) =6.6 ..rH a Obscured by the CO2Me resonance. Also the J3C{ IH} signals of the S-Me group show downfield shifts (A 8 = 5.1-6.5 ppm ) (2a, 2b, 31) and 4b; Section 2 ). Interestingly, the C4and C a ~3C{ ~H } resonances of 2a have S-Me eM-laP S-Ilk ~ IM-Me shifted downfield (A~=9.4 and 3.1 ppm, respectively), while the analogous signals of 2b, 3b and 4b did not shift to the same extent. In all NS complexes coordination of the earboxylic oxygen atom of the C(O)OMe unit does not occur, since the corresponding IR CO absorption (1735- 1748 cm-i) does not shift notably when compared to the values found for the free ligands ( 1739 cm- t). Both the five- and the six-membered NS complexes (2a- ,f~ 4b and 5b vide infra) show broad IH NMR signals at room j k..,,,.~ 7.X~K ~ tMeem perature. singlets split Upon (Fig. cooling 4) indicating to 213 K the the presencSe -Me and of twoth e dPida-- 5.2 mpp 0,2 0.1 mmtp 0.0 5.2 0I.2~ OL 0p.p0m stereoisomers in solution. The tH NMR spectra of 2a at 233 Fig. 4. HI NMR spe~taof Pdl(Me)(HmetMe) (,lib) in the S-Meregion K show a sharp triplet (3j(C4H-C3H2) = 1 ! Hz) and a mul- (2.5-2.0 ppm) and the Pd-Me region ( 1.0-0.0 ppm), ngasumt in .31CDC