X-ray Crystal Structure Of Trans Research Articles

Palladium(II) saccharinate complexes trans-[Pd(sac)2(LH)2] with amino- and acetylamino-pyridine co-ligands: molecular structures of trans-[PdCl2(2-ampyH)2].2dmf (2-ampyH = 2-amino-3-methylpyridine) and trans-[Pd(κ2-2-acmpy)2] (2-acmpyH = 2-acetylamino-3-methylpyridine)

Reaction of Na2[PdCl4] with two equivalents of amino- or acetylamino-pyridines (LH) affords trans-[PdCl2-(LH)2] {LH = 2-amino-3-methylpyridine (2-ampyH), 3-aminopyridine (3-apyH), 2-acetylamino-3-methylpyridine (2-acmpyH), 3-acetylamino-pyridine (3-acpyH)}. An X-ray crystal structure of trans-[PdCl2(2-ampyH)2] shows that the 2-ampy-H ligands are coordinated in a monodentate fashion via the nitrogen atoms of the pyridine rings. Treatment of trans-[PdCl2(2-acmpyH)2] with NEt3 affords the cyclometalated complex, trans-[Pd(κ2-2-acmpy)2], the X-ray structure of which shows that the 2-acmpy ligand is coordinated to palladium in a bidentate fashion via the nitrogen atom of the pyridine ring and oxygen. Reaction of trans-[PdCl2(LH)2] with two equivalents of sodium saccharinate affords the bis(saccharinate) complexes, trans-[Pd(sac)2(LH)2], in which the saccharinate anions are coordinated via the amide nitrogen atom.

Palladium(II) saccharinate (sac) and thiosaccharinate (tsac) complexes with supporting amino- and acetylamino-thiazole ligands: Crystal structures of trans-[PdCl2(abzt)2]·dmf (abzt = 2-aminobenzothiazole), trans-[PdCl2(bzta)2].dmf (bzta = 2-acetylaminobenzothiazole) and trans-[Pd(sac)2(abzt)2]·2dmf

Treatment of Na2PdCl4 with two equivalents of amino- or acetylamino-thiazoles [L=2-aminobenzothiazole (abzt), 2-aminothiazole (atz), 2-acetylaminobenzothiazole (bzta) and 2-acetylaminothiazole (tza)] or 2-aminobenzimidazole (abzim)] affords trans-[PdCl2L2] complexes in which the introduced ligands are coordinated to palladium through the endocyclic nitrogen as shown by X-ray crystal structures of trans-[PdCl2(abzt)2]·dmf and trans-[PdCl2(bzta)2]·dmf. Addition of two equivalents of sodium saccharinate (Nasac) yields trans-[Pd(sac)2L2] complexes whereby the saccharinate anions are coordinated through nitrogen as shown by the X-ray crystal structure of trans-[Pd(sac)2(abtz)2]·2dmf. With thiosaccharin (Htsac) trans-[Pd(tsac)2L2] result but now the thiosaccharinate ligands coordinate through the sulfur of the thiolate group as evidenced by spectroscopic studies.

Modulation of properties in analogues of Zeise's anion on changing the ligand trans to ethene. X-Ray crystal structures of trans-[PtCl2(OH)(η2-C2H4)]− and trans-[PtCl2(η1-CH2NO2)(η2-C2H4)

To get further insight in the reaction of nucleophilic substitution upon changing the ligand trans to a η(2)-olefin, the reactivity of some monoanionic platinum(II) complexes (trans-[PtCl(2)X(η(2)-C(2)H(4))](-), X = Cl(-), 1, OH(-), 2, and CH(2)NO(2)(-), 3) towards pyridines with different steric hindrance (py, 4-Mepy, and 2,6-Me(2)py) has been tested. All crystallographic (2 and 3 reported for the first time) and spectroscopic data are in accord with a platinum-olefin interaction decreasing in the order 2 > 1 > 3, paralleling the decreasing electronegativity of the donor atom (O > Cl > C). Not only the platinum-olefin bond but also the bond between platinum and the ligand trans to the olefin appear to be strongest in 2 (Pt-O distance at the lower limit for this type of bond). In the reaction with py, the ligand trans to the olefin is displaced in 1 and 2. Moreover the reaction is in equilibrium in the case of sterically hindered 2,6-Me(2)py, the equilibrium being shifted moderately or prevalently toward the reagents in the case of 1 and 2, respectively. In the case of 3, the reaction with pyridines leads to substitution of the olefin instead of the carbanion. This is in accord with the observation that carbanions strongly weaken the trans Pt-olefin bond.

Novel trans-platinum complexes of the histone deacetylase inhibitor valproic acid; synthesis, in vitro cytotoxicity and mutagenicity

The first examples of Pt complexes of the well known anti-epilepsy drug and histone deacetylase inhibitor, valproic acid (VPA), are reported. Reaction of the Pt(II) am(m)ine precursors trans-[PtCl 2(NH 3)(py)] and trans-[PtCl 2(py) 2] with silver nitrate and subsequently sodium valproate gave trans-[Pt(VPA −1H) 2(NH 3)(py)] and trans-[Pt(VPA −1H) 2(py) 2], respectively. The valproato ligands in both complexes are bound to the Pt(II) centres via the carboxylato functionality and in a monodentate manner. The X-ray crystal structure of trans-[Pt(VPA −1H) 2(NH 3)(py)] is described. Replacement of the dichlorido ligands in trans-[PtCl 2(py) 2] and trans-[PtCl 2(NH 3)(py)] by valproato ligands (VPA −1H) to yield trans-[Pt(VPA −1H) 2(py) 2] and trans-[Pt(VPA −1H) 2(NH 3)(py)] respectively, significantly enhanced cytotoxicity against A2780 (parental) and A2780 cisR (cisplatin resistant) ovarian cancer cells. The mutagenicity of trans-[Pt(VPA −1H) 2(NH 3)(py)] and trans-[Pt(VPA −1H) 2(py) 2] was determined using the Ames test and is also reported.

Tetradentate bis-phosphine ligands (P2N2 and P2S2) and their Rh(III), Ni(II) and 105Rh Complexes: X-ray crystal structures of trans-[RhCl2(L2)]PF6, [Ni(L2)](PF6)2 and μ-O2SO2-[Ni(L5)]2(PF6)2

Tetradentate acyclic and macrocyclic diphosphine ligands (P(2)N(2) and P(2)S(2)) have been synthesized and characterized as potential chelates for Rh(III). The coordination complexes [RhCl(2)(L1)]Cl, trans-[RhCl(2)(L2)]PF(6), [Ni(L2)](PF(6))(2), [Ni(L3)](PF(6))(2), [RhCl(2)(L4)]PF(6) and [RhCl(2)(L5)]PF(6) have been synthesized and characterized. In addition, radiochemistry studies of the (105)Rh complexes with the ligands N,N'-bis[2-(diphenylphosphino)phenyl]-1,3-diaminopropane (L1), 4,8-diphenyl-1,11-diaza-4,8-diphosphaundecane (L2), 5,9-diphenyl-5,9-diphospha-2,12-dithiatridecane (L3) and 1,4,8,11-tetraphenyl-4,8-diphospha-1,11-dithiaundecane (L4) are reported, including normal mouse biodistributions of (105)Rh-L2. trans-[RhCl(2)(L2)]PF(6) crystallized in the monoclinic space group P2(1)/c with a = 9.9353(5) Å, b = 9.0929(5) Å, c = 28.689(1) Å, β = 93.1400(10) deg, Z = 4, R = 0.037 and R(w) = 0.053. [Ni(L2)](PF(6))(2) crystallized in the monoclinic space group P2(1)/c with a = 11.9665(6) Å, b = 14.8903(7) Å, c = 31.148(1) Å, β = 91.587(1) deg, Z = 8, R = 0.056 and R(w) = 0.083. μ-O(2)SO(2)-[Ni(L5)](2)(PF(6))(2), an unusual sulfate-bridged Ni(II) dimer, crystallized in the triclinic space group P1 bar with a = 15.179(2) Å, b = 15.514(2) Å, c = 16.128(2) Å, α = 105.280(7) deg, β = 113.074(6) deg, γ = 101.657(8) deg, Z = 2, R = 0.050 and R(w) = 0.072. Phosphine-containing ligands allowed for lower temperatures and lower ethanol concentrations in the formulations for (105)Rh(L) complexation, but at the expense of higher ligand concentrations.

ChemInform Abstract: Involvement of Iron Alkyl Complexes and Alkyl Radicals in the Kharasch Reactions: Probing the Catalysis Using Iron Phosphine Complexes.

The X-ray crystal structure of trans-[FeBr2(depe)2](depe = Et2PCH2CH2PEt2) has been determined, and its catalysis of the reactions between MgBrEt and RBr (R = Et, Prn, Bun, PhCH2 or H2CCHCH2) to give alkanes and alkenes investigated. Detailed analysis of the products and the time courses of the reactions demonstrate that the hydrido-species trans-[FeH(Br)(depe)2]n+(n= 0 or 1) are not intermediates in the reaction, but are products formed in the termination steps. It is shown that the catalysis can proceed by one of two pathways, depending on the alkyl halide. One pathway is proposed to involve the intermediacy of iron(I) species, and the other of iron(III) complexes. Both catalytic cycles contain the same fundamental reaction: the abstraction of a β-hydrogen atom from a [FeEt(Br)(depe)2]n+ species by alkyl radicals to give the alkane and ethylene. The X-ray crystal structure of trans-[FeH(Br)(depe)2]BPh4 is reported.

Preparation and characterisation of mononuclear Pd(II) complexes with 1,8-bis(3,5-dimethyl-1-pyrazolyl)-3,6-dithiaoctane (bddo) ligand: Spectroscopy studies and crystal structure of trans-[Pd(SCN) 2(bddo)

Mononuclear palladium(II) complexes containing a pyrazole-thioether ligand, with general formula trans-[Pd(X) 2(bddo)] (X = CN − ( 1), SCN − ( 2) or N 3 − ( 3); bddo = 1,8-bis(3,5-dimethyl-1-pyrazolyl)-3,6-dithiaoctane), have been prepared. Similar reactivity carried out with pyridine or triphenylphosphine has been assayed. When pyridine is used, a mixture of [Pd(bddo)(py) 2](BF 4) 2 ([ 4](BF 4) 2) and [Pd(bddo)](BF 4) 2 is obtained. When triphenylphosphine is used, only [Pd(bddo)](BF 4) 2 is obtained. The complexes have been characterised by elemental analyses, conductivity measurements, IR and NMR spectroscopies. X-ray crystal structure of trans-[Pd(SCN) 2(bddo)] ( 2) is presented. In this complex the metal atom is coordinated by the two azine nitrogen atoms of the pyrazole rings and two SCN − anions in trans disposition.

Benzylamidine complexes of platinum(II) derived by nucleophilic addition of primary and secondary amines. X-ray crystal structure of trans-[PtCl 2{ Z-N(H) [dbnd]C(NHMe)CH 2Ph} 2

The reaction of cis- and trans-[PtCl 2(NCCH 2Ph) 2] with a 5-fold excess of MeNH 2 and Me 2NH in CH 2Cl 2 at −10 °C affords in high yield the bis-amidine derivatives cis- and trans-[PtCl 2{ Z-N(H) C(NHMe)CH 2Ph} 2] ( 1a, 2a) and cis- and trans-[PtCl 2{ E-N(H) C(NMe 2)CH 2Ph} 2] ( 3a, 4a), respectively. The complexes were characterized by means of elemental analysis, multinuclear NMR and FT-IR techniques. The X-ray diffraction analysis was carried out for trans-[PtCl 2{ Z-N(H) C(NHMe)CH 2Ph} 2] ( 2a). Moreover, the in vitro cytotoxicity for the new derivatives was evaluated in a wide panel of human tumor cell lines.

Probing delocalisation across highly ethynylated mono and dinuclear Pt(II) tethers containing nitrogroups and organic models as redox active probes: X-ray crystal structure of trans-[Pt(C [tbnd]C–C 6H 4NO 2) 2(PPh 3) 2

The electrochemical study on Pt(II) organometallic and organic ethynylated compounds bearing nitro substituents in the phenyl groups has been performed, demonstrating that the presence of severe chemical irreversibility accompanying the electron transfer, preclude an evaluation of the electronic communication between redox active centres. The X-ray structure of the complex trans-[Pt(C C–C 6H 4NO 2) 2(PPh 3) 2] is showed.

Trans --> cis isomerization of trans-[(dppm)2Ru(H)(L)][BF4] (L = P(OR)3) complexes: preparation of cis-[(dppm)2Ru(eta2-H2)(L)][BF4]2.

A series of new dicationic dihydrogen complexes of ruthenium of the type cis-[(dppm)(2)Ru(eta(2)-H(2))(L)][BF(4)](2) (dppm = Ph(2)PCH(2)PPh(2); L = P(OMe)(3), P(OEt)(3), PF(O(i)Pr)(2)) have been prepared by protonating the precursor hydride complexes cis-[(dppm)(2)Ru(H)(L)][BF(4)] (L = P(OMe)(3), P(OEt)(3), P(O(i)Pr)(3)) using HBF(4).Et(2)O. The cis-[(dppm)(2)Ru(H)(L)][BF(4)] complexes were obtained from the trans hydrides via an isomerization reaction that is acid-accelerated. This isomerization reaction gives mixtures of cis and trans hydride complexes, the ratios of which depend on the cone angles of the phosphite ligands: the greater the cone angle, the greater is the amount of the cis isomer. The eta(2)-H(2) ligand in the dihydrogen complexes is labile, and the loss of H(2) was found to be reversible. The protonation reactions of the starting hydrides with trans PMe(3) or PMe(2)Ph yield mixtures of the cis and the trans hydride complexes; further addition of the acid, however, give trans-[(dppm)(2)Ru(BF(4))Cl]. The roles of the bite angles of the dppm ligand as well as the steric and the electronic properties of the monodentate phosphorus ligands in this series of complexes are discussed. X-ray crystal structures of trans-[(dppm)(2)Ru(H)(P(OMe)(3))][BF(4)], cis-[(dppm)(2)Ru(H)(P(OMe)(3))][BF(4)], and cis-[(dppm)(2)Ru(H)(P(O(i)Pr)(3))][BF(4)] complexes have been determined.

Complexes of rhenium(V) with aminoacetophenones and their reactions with some bidentate ligands

Complexes of rhenium(V) with 2-, 3- and 4-aminoacetophenone (H2aap) have been synthesized. The reaction of trans-ReOCl3(PPh3)2 with 2-H2aap in benzene yielded the imido complex [Re(2-aap)Cl3(PPh3)], in which the oxo oxygen and one of the PPh3 groups were substituted by the dianionic imido nitrogen and the neutral ketonic oxygen, respectively. With 3- and 4-H2aap the imido complexes trans-[Re(aap)Cl3(PPh3)2] were isolated. The monodentate coordination mode of these latter two ligands was authenticated by the X-ray crystal structure of trans-[Re(3-aap)Cl3(PPh3)2]; crystals are triclinic, P1, with a = 10.567(5), b = 11.989(6), c = 18.739(8) A, α= 74.82(4)o, β= 75.27(4)o, γ= 73.15(4)o, U = 2152(2) A3, Z = 2, R = 0.0469. The further reaction of [Re(3-aap)Cl3(PPh3)2] with the bidentate ligands 2-aminophenol and 8-hydroxyquinoline (HL) led to the isolation of complexes of the type [Re(3-aap)Cl2(PPh3)(L)]. However, with 1,2-diaminobenzene (H2dab), the 3-aap imido moiety was displaced by the imido group {N(C6H4)NH2}, to give the complex trans-[Re(dab)Cl3(PPh3)2]. (Bulletin of The Chemical Society of Ethiopia: 2002 16 (2): 149-156)

Nickel(II) promoted P–N bond cleavage of (Ph 2PNH) 2CS. X-ray crystal structure of trans-[Ni{Ph 2PNHC(S)NH 2– P,S} 2]Cl 2

The reaction of (Ph 2PNH) 2CS with nickel(II) chloride hexahydrate in methanol proceeds with methanolysis of a P–N bond to give trans-[Ni{Ph 2PNHC(S)NH 2–P,S} 2]Cl 2, whose structure has been confirmed by X-ray crystallography.

Cobalt(III) complexes of monobenzyl-cyclam macrocycle derivatives

Two dichlorocobalt(III) complexes of ligands L1 and L3 in which 4-R-benzyl moieties (R = NO2, NH2) are either N-bonded (1-position) or C-bonded (6-position) to the 1,4,8,11-tetraazacyclotetradecane (cyclam) macrocycle have been prepared and characterized: L1 = 1-(4-nitrobenzyl)cyclam; L3 = 6-(4-aminobenzyl)cyclam. The X-ray crystal structure of trans-[Co(L1)Cl2]ClO4 {M 564.73, monoclinic P21/c (No. 14); a 13.1987(14), b 11.7701(11), c 14.9305(14) Å, β 97.692(9)˚; V 2298.6(4) Å3. Z 4. Dc 1.632 g cm–3; final R1 0.0282, wR2 0.0671 (3438 refls Fo > 4σFo), [for all 4022 unique data R1 0.0366, wR2 0.0717]} shows a distorted octahedral stereochemistry at Co, with a Cl–Co–Cl angle of 174˚. The X-ray crystal structure of trans-[Co(L3)Cl2]Cl·H2O {M 488.77; monoclinic P21/n (No. 14); a 10.5781(12), b 13.536(2), c 15.065(3) Å, β 101.027(13)˚; V 2117.3(6) Å3. Z 4. Dc 1.207 g cm–3; final R1 0.0284, wR2 0.0727 (5296 refls Fo > 4σFo), [for all 7928 data R1 0.0345, wR2 0.0762]} shows a less distorted octahedral stereochemistry. The Cl–Co–Cl angle is essentially linear, 179.80(14)˚. The cyclam moieties in both structures display the trans-III conformation. Manuscript received: 11 April 2001.

Peripherally-metallated porphyrins: synthesis and spectra of meso-η 1-palladio- and platinioporphyrins and the crystal structures of cis-{PtBr[10,20-diphenylporphyrinatonickel(II)-5-yl](PPh 3) 2} and trans-{PtBr[10,20-diphenylporphyrin-5-yl](PPh 3) 2}·0.25CH 2Cl 2

A series of meso-η 1-palladio(II)- and platinio(II)porphyrins containing either monodentate Group 15 ligands (PPh 3, AsPh 3) or chelating diphosphines (dppe, dppp, dppf) has been prepared by oxidative addition of mono- and dibromo derivatives of 5,15-diphenylporphyrin (H 2DPP) to Pd(0) and Pt(0) precursors. The products were characterized by their 1H- and 31P-NMR, visible absorption, and mass spectra and the X-ray crystal structures of trans-[PtBr(H 2DPP)(PPh 3) 2] ( 14) (as a 0.25CH 2Cl 2 solvate) and cis-[PtBr(NiDPP)(PPh 3) 2] ( 15) were determined. The structures show approximately square planar geometry about the Pt atoms, although there are distortions due to crowding of the PPh 3 ligands in 15. The NiDPP ring in 15 suffers ruffling typical of peripherally-crowded Ni(II) porphyrins, the pairs of opposite meso carbons being displaced alternately >±0.4 Å out of the C 20N 4 mean plane The conformations of the phenyl groups of the PPh 3 ligands indicate the presence of non-covalent phenyl–porphyrin π–π interactions. These derivatives are the first isolated examples of peripheral organometallic porphyrins with direct transition metal to porphyrin σ-bonds, and they represent a new class of superstructured porphyrins with one or both faces of the macrocycle heavily shielded by the phenyl groups on the auxiliary ligands.

Synthesis and characterization of chiral diimino- and diaminodiphosphine complexes of ruthenium. X-ray crystal structure of Trans- RuCl2( 1R,2R-cyclohexyl-P 2N 2)·C 6H 5CH 3

The interaction of RuCl 2(DMSO) 4 with I equivalent of 1 R,2 R-cyclohexyl-P 2N 2 and 1 R,2 R-cyclohexyl-P 2N 2H 4 in refluxing toluene gave trans-RuC 2(1 R,2 R-cyclohexyl-P 2N 2) ( I) and trans- RuCl 2(1 R,2 R-cyclohexyl-P 2N 2H 4) ( II) in 80% and 75% yields, respectively. Compounds I and II have been fully characterized by analytical and spectroscopic methods. The structure of II has been established by an X-ray diffraction study.

Methoxy-palladation of allylamines: a facile synthesis of chiral cyclopalladated compounds. X-ray crystal structure of trans-[Pd(CH 2CH(OMe)CH(Me)NMe 2)(Cl)(Py)

The reaction of racemic N,N-dimethylamino-3-but-l-ene (1) and N,N-dimethylamino-l-cyclohex-2-ene (2) with Li 2PdCl 4 in methanol at 0°C yielded [Pd(CH 2CH (OMe)CH(Me)NMe 2)(μ-Cl)] 2 (4) and [Pd(CHCH(OMe)CHNMe 2(CH 2) 3)(μ-Cl)] 2 (6), respectively, as single isomers. On the other hand, only the deallylation product trans-PdCl 2[NH-(R,R)-(MeCHPh) 2] 2 (8) was isolated from the reaction of (R,R)-α,α-dimethyldibenzylallylamine with palladium(II) salts.

Alkylation of cyanide at [NBu 4] trans-[Re(CN) 2(Ph 2PCH 2CH 2PPh 2) 2]. Syntheses and properties of derived isocyanide complexes and X-ray structure of trans-[Re(CNEt) 2(Ph 2PCH 2CH 2PPh 22][PF 6

The reaction of RI (R = Me, Et or Pr) or [Et 3O][PF 6] with [NBU 4] trans-[Re(CN) 2(dppe) 2] (dppe = Ph 2PCH 2CH 2PPh 2) affords the diisocyanide complexes trans-[Re(CNR) 2(dppe) 2]A (R = Me, A = I; R = Pr, A =I 3; R = Et, A = PF 6, whereas trans-[Re(CNH)(CNSiMe 3)(dppe) 2]CF 3SO 3 is obtained from the reaction with Me 3SiO 3SCF 3. The X-ray crystal structure of trans-[Re(CNEt) 2)(dppe) 2]CF 6 was determined. The redox properties of the compounds were studied by cyclic voltammetry and controlled potential electrolysis, and are discussed in terms of the electronic properties of the metal centres and ligands.

Reactions of the haloalcohols HO(CH 2) nCl ( n = 2, 3) with platinum(II) - alkynyl and -alkyne complexes. X-ray crystal structure of trans-[Pt(Me) {C(OCH 2CH 2Cl) (CH 2Ph)} (PPh 3) 2] [BF 4

The chloro complexes trans-[Pt(Me)(Cl)(PPh 3) 2], after treatment with AgBF 4, react with 1-alkynes HCCR in the presence of NEt 3 to afford the corresponding acetylide derivatives trans-[Pt(Me) (CCR) (PPh 3) 2] (R = p-tolyl ( 1), Ph ( 2), C(CH 3) 3 ( 3)). These complexes, with the exception of the t-butylacetylide complex, react with the chloroalcohols HO(CH 2) n Cl ( n = 2, 3) in the presence of 1 equiv. of HBF 4 to afford the alkyl(chloroalkoxy)carbene complexes trans-[Pt(Me) {C[O(CH 2) n Cl](CH 2R) } (PPh 3) 2][BF 4] ( R = p- tolyl, n = 2 ( 4), n = 3 ( 5); RPh, n = 2 ( 6) ). A similar reaction of the bis(acetylide) complex trans-[Pt(CCPh) 2(PMe 2Ph) 2] with 2 equiv. HBF 4 and 3-chloro-1-propanol affords trans-[Pt(CCPh) {C(OCH 2CH 2CH 2Cl)(CH 2Ph) } (PMe 2Ph) 2][BF 4] ( 7). T alkyl(chloroalkoxy)-carbene complex trans-[Pt(Me) {C(OCH 2CH 2Cl)(CH 2Ph) } (PPh 3) 2][BF 4] ( 8) is formed by reaction of trans-[Pt(Me)(Cl)(PPh 3) 2], after treatment with AgBF 4 in HOCH 2CH 2Cl, with phenylacetylene in the presence of 1 equiv. of n-BuLi. The reaction of the dimer [Pt(Cl)(μ-Cl)(PMe 2Ph)] 2 with p-tolylacetylene and 3-chloro-1-propanol yields cis-[ PtCl 2{ C(OCH 2 CH 2 CH 2 Cl)( CH 2 C 6 H 4-p- Me}( PMe 2 Ph)] ( 9) . The X-ray molecular structure of ( 8) has been determined. It crystallizes in the orthorhombic system, space group Pna2 1, with a = 11.785(2), b = 29.418(4), c = 15.409(3) A ̊ , V = 4889(1) A ̊ 3 and Z = 4 . The carbene ligand is perpendicular to the Pt(II) coordination plane; the PtC(carbene) bond distance is 2.01(1) Å and the short C(carbene)-O bond distance of 1.30(1) Å suggests extensive electronic delocalization within the PtC(carbene)O moietry.

N-cyanoacetylurethane complexes of palladium(II), and the x-ray crystal structure of trans-[PdCl{EtO 2C NC(O)CH 2CN}(PPh 3) 2

Reaction of [PdCl 2(DPPE)] (DPPE = Ph 2PCH 2CH 2PPh 2) with N-cyanoacetylurethane, NCCH 2NHCO 2Et, and silver(I) oxide gave the four-membered ring palladalactam complex [P d{CH(CN)C(O)N (CO 2Et)}(DPPE)] in high yield. In contrast, reaction of [PdCl 2(PPh 3) 2] with N-cyanoacetylurethane and silver(I) oxide gave the monodentate amide complex trans-[PdCl{EtO 2C NC(O)CH 2CN}(PPh 3) 2] in high yield. The amide complex was characterized by multinuclear NMR spectroscopy and by a single-crystal X-ray diffraction study. The plane of the N-bonded cyanoacetylurethane ligand is virtually perpendicular to the square-plane of the palladium coordination sphere.

Synthesis of trans-(.sigma.-allenyl)platinum(II) and -palladium(II) compounds. X-ray crystal structure of trans-[PtBr{C(H):C:CMe2}(PPh3)2] and highly diastereoselective trans-cis isomerization of (.sigma.-allenyl)palladium(II) bromides

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSynthesis of trans-(.sigma.-allenyl)platinum(II) and -palladium(II) compounds. X-ray crystal structure of trans-[PtBr{C(H):C:CMe2}(PPh3)2] and highly diastereoselective trans-cis isomerization of (.sigma.-allenyl)palladium(II) bromidesJacqueline M. A. Wouters, Rene A. Klein, Cornelis J. Elsevier, Ludger Haming, and Casper H. StamCite this: Organometallics 1994, 13, 11, 4586–4593Publication Date (Print):November 1, 1994Publication History Published online1 May 2002Published inissue 1 November 1994https://doi.org/10.1021/om00023a071RIGHTS & PERMISSIONSArticle Views178Altmetric-Citations44LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (872 KB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts