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1.
By control of mixed ligands with particular coordination sites, heterometallic coordination polymers, [Ln2(H2O)2Ag(C2O4)2(ina)3]n (Ln = Eu (1), Dy (2), Hina = isonicotinic acid) and {[LnAg(C2O4)(na)2]·2H2O}n (Ln = La (3), Tb (4), Hna = nicotinic acid), have been synthesized under hydrothermal conditions and characterized by elemental analysis, IR, thermogravimetric analysis (TGA), and single-crystal X-ray diffraction. These coordination polymers feature 3D pillar-layered coordination frameworks constructed from two-dimensional (2D) lanthanide–carboxylate layers and Ag(ina) or Ag(na) pillars. It is interesting that the in situ decarboxylation of pyridine-2,3-dicarboxylic acid into nicotinic acid was observed. The luminescent properties of 1 and 4 were also studied. 相似文献
2.
《Journal of organometallic chemistry》2005,690(24-25):5856-5862
The RuC bond of the bis(iminophosphorano)methandiide-based ruthenium(II) carbene complexes [Ru(η6-p-cymene)(κ2-C,N-C[P{NP(O)(OR)2}Ph2]2)] (R = Et (1), Ph (2)) undergoes a C–C coupling process with isocyanides to afford ketenimine derivatives [Ru(η6-p-cymene)(κ3-C,C,N-C(CNR′)[P{NP(O)(OR)2}Ph2]2)] (R = Et, R′ = Bz (3a), 2,6-C6H3Me2 (3b), Cy (3c); R = Ph, R′ = Bz (4a), 2,6-C6H3Me2 (4b), Cy (4c)). Compounds 3–4a–c represent the first examples of ketenimine–ruthenium complexes reported to date. Protonation of 3–4a with HBF4 · Et2O takes place selectively at the ketenimine nitrogen atom yielding the cationic derivatives [Ru(η6-p-cymene)(κ3-C,C,N-C(CNHBz)[P{NP(O)(OR)2}Ph2]2)][BF4] (R = Et (5a), Ph (6a)). 相似文献
3.
Eliandro Faoro Gelson Manzoni de Oliveira Ernesto Schulz Lang 《Journal of organometallic chemistry》2009,694(9-10):1557-1561
(DmephTe)2 (dmeph = 2,6-dimethylphenyl) reacts with resublimed iodine or with pyridinium iodide under Ar atmosphere to yield [{RTeI}{RTeI3}]n (1), [R2Te?TeIR] (2), (PyH)[RTeI2] (3) and (PyH)n[RTeI(μ-I)TeIR]n (4) (R = dmeph; Py = pyridine). While mesityl species analogue to 2 and 3 have been already described, the compounds 1 and 4 represent the first organotellurium iodides of their classes reported. In compound 4 a symmetrical, covalent iodine bridge links two RTeI groups, attaining single [RTeI(μ-I)TeIR] anions connected by Te?I secondary bonds and stabilized by pyridinium cations. 相似文献
4.
C.K. Modi D.H. Jani H.S. Patel H.M. Pandya 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2010,75(4):1321-1328
Fluorescence properties of five 4-acyl pyrazolone based hydrazides (H2SBn) and their Fe (III) heterochelates of the type [Fe(SBn)(L)(H2O)]·mH2O [H2SBn = nicotinic acid [1-(3-methyl-5-oxo-1-phenyl-4,5-di hydro-1H-pyrazol-4yl)-acylidene]-hydrazide; where acyl = –CH3, m = 4 (H2SB1); –C6H5, m = 2 (H2SB2); –CH2–CH3, m = 3 (H2SB3); –CH2–CH2–CH3, m = 1.5 (H2SB4); –CH2–C6H5, m = 1.5 (H2SB5) and HL = 1-cyclopropyl-6-fluoro-4-oxo-7-(piperazin-1-yl)-1,4-dihydroquinoline-3-carboxylic acid] were studied at room temperature. The fluorescence spectra of heterochelates show red shift, which may be due to the chelation by the ligands to the metal ion. It enhances ligand ability to accept electrons and decreases the electron transition energy. The kinetic parameters such as order of reaction (n), energy of activation (Ea), entropy (S*), pre-exponential factor (A), enthalpy (H*) and Gibbs free energy (G*) have been reported. 相似文献
5.
《Journal of organometallic chemistry》2005,690(24-25):5562-5569
Dinuclear ruthenium(I,I) carboxylate complexes [Ru2(CO)4(μ-OOCR)2]n (R = CH3 (1a), C3H7 (1b), H (1c), CF3 (1d)) and 2-pyridonate complex [Ru2(CO)4(μ-2-pyridonate)2]n (3) catalyze efficiently the cyclopropanation of alkenes with methyl diazoacetate. High yields are obtained with terminal nucleophilic alkenes (styrene, ethyl vinyl ether, α-methylstyrene), medium yields with 1-hexene, cyclohexene, 4,5-dihydrofuran and 2-methyl-2-butene. The E-selectivity of the cyclopropanes obtained from the monosubstituted alkenes and the cycloalkenes decreases in the order 1b > 1a > 1d > 1c. The cyclopropanation of 2-methyl-2-butene is highly syn-selective. Several complexes of the type [Ru2(CO)4(μ-L1)2]2 (4) and (5), [Ru2(CO)4(μ-L1)2L2] (L2 = CH3OH, PPh3) (6)–(9) and [Ru2(CO)4(CH3CN)2(μ-L1)2] (10) and (11), where L1 is a 6-chloro- or 6-bromo-2-pyridonate ligand, are also efficient catalysts. Compared with catalyst 3, a halogen substituent at the pyridonate ligand affects the diastereoselectivity of cyclopropanation only slightly. 相似文献
6.
Adina Rotar Richard A. Varga Klaus Jurkschat Cristian Silvestru 《Journal of organometallic chemistry》2009,694(9-10):1385-1392
Hypercoordinated diorganotin(IV) dichloride, [2-(Et2NCH2)C6H4]2SnCl2 (1), was prepared by reacting [2-(Et2NCH2)C6H4]Li with SnCl4. Halide-exchange reactions between 1 and the appropriate potassium halides gave [2-(Et2NCH2)C6H4]2SnX2 [X = F (2), Br (3), I (4)]. Reaction of 1 with excess of Na2S gave the cyclo-[{2-(Et2NCH2)C6H4}2SnS]2 (5). The solution behavior of the title compounds in solution was investigated by multinuclear (1H, 13C, 19F and 119Sn) NMR spectroscopy, including variable temperature studies. Single-crystal X-ray diffraction analysis revealed for all compounds intramolecular N → Sn coordination thus resulting in distorted octahedral (C,N)2SnX2 configurations. Planar chirality is observed as result of the non-planarity of the SnC3N rings; all compounds, however, crystallizing as racemates. The isomers are linked by extensive hydrogen bonds to give different supramolecular architectures in the crystals of compounds 1, 3 and 4. 相似文献
7.
《Journal of organometallic chemistry》2011,696(26):4207-4214
The reaction of [Cp1IrCl2]2 (Cp* = η5 − C5Me5) with the tridentate 3-thiapentane-1,5-dithiolate ligand, S(CH2CH2S−)2 (tpdt), led to the formation of [Cp1Ir(η3 − tpdt)] (1) in 81% isolated yield. Subsequent reactions of 1 with [Cp1IrCl2]2 in 2:1 and 1:1 molar equiv ratios resulted in the formation of [Cp1Ir(μ − η2:η3 − tpdt)Cp1IrCl][PF6] (2) and [Cp1Irμ − η2:η3 − tpdt)Cp1IrCl][Cp1IrCl3] (3) in 86 and 79% yields, respectively, based on 1, whereas the reactions of 1 with [(COD)IrCl]2 (COD = 1,5-cyclooctadiene) in 2:1 and 1:1 molar equiv ratios resulted in the formation of the homo-bimetallic derivatives Cp1Ir(μ − η1:η3 − tpdt)(COD)IrCl (4) (92% yield) and [Cp1Ir(μ − η2:η3 − tpdt)(COD)Ir] [(COD)IrCl2] (5) (82% yield). Reactions between 1 and [(COD)RhCl]2, yielded the hetero-bimetallic derivatives Cp1Ir(μ − η1:η3 − tpdt)(COD)RhCl (6) and [Cp1Ir(μ − η2:η3 − tpdt)(COD)Rh][(COD)RhCl2] (7), in 92 and 93% yields, respectively. The reaction of 1 with methyl iodide gave mono-methylated derivative [Cp1Ir(η3-C4H8S3Me)]I (8) (93% yield). All these compounds have been comprehensively characterized. 相似文献
8.
Chang Xu Yongxin Li Lai Yoong Goh Sumod A. Pullarkat 《Journal of organometallic chemistry》2012,696(26):4207-4214
The reaction of [Cp1IrCl2]2 (Cp* = η5 ? C5Me5) with the tridentate 3-thiapentane-1,5-dithiolate ligand, S(CH2CH2S?)2 (tpdt), led to the formation of [Cp1Ir(η3 ? tpdt)] (1) in 81% isolated yield. Subsequent reactions of 1 with [Cp1IrCl2]2 in 2:1 and 1:1 molar equiv ratios resulted in the formation of [Cp1Ir(μ ? η2:η3 ? tpdt)Cp1IrCl][PF6] (2) and [Cp1Irμ ? η2:η3 ? tpdt)Cp1IrCl][Cp1IrCl3] (3) in 86 and 79% yields, respectively, based on 1, whereas the reactions of 1 with [(COD)IrCl]2 (COD = 1,5-cyclooctadiene) in 2:1 and 1:1 molar equiv ratios resulted in the formation of the homo-bimetallic derivatives Cp1Ir(μ ? η1:η3 ? tpdt)(COD)IrCl (4) (92% yield) and [Cp1Ir(μ ? η2:η3 ? tpdt)(COD)Ir] [(COD)IrCl2] (5) (82% yield). Reactions between 1 and [(COD)RhCl]2, yielded the hetero-bimetallic derivatives Cp1Ir(μ ? η1:η3 ? tpdt)(COD)RhCl (6) and [Cp1Ir(μ ? η2:η3 ? tpdt)(COD)Rh][(COD)RhCl2] (7), in 92 and 93% yields, respectively. The reaction of 1 with methyl iodide gave mono-methylated derivative [Cp1Ir(η3-C4H8S3Me)]I (8) (93% yield). All these compounds have been comprehensively characterized. 相似文献
9.
Gemma Aragay Josefina Pons Jordi García-Antón Xavier Solans Mercè Font-Bardia Josep Ros 《Journal of organometallic chemistry》2008,693(21-22):3396-3404
The synthesis of two N-alkylaminopyrazole ligands, 1-[2-(diethylamino)ethyl]-3,5-diphenylpyrazole (L1) and 1-[2-(dioctylamino)ethyl]-3,5-diphenylpyrazole (L2), is reported. These ligands present, a priori, one pyrazole nitrogen and one amine nitrogen as potential donor atoms. However, in the reaction of the ligands (L1 and L2) with [PdCl2(CH3CN)2] one of the Cphenyl atoms can also behave as a donor atom. As a result, we have obtained the formation of three different compounds for each one of the ligands: chelated ([PdCl2(L)] L = L1 (1a), L2 (2a)), zwitterionic ([PdCl3(LH)] LH = LH1 (1b), LH2 (2b)), and cyclopalladated compounds ([PdCl(LC)] (LC = LC1 (1c), LC2 (2c)). The solid-state structures for 1a, 1b and 1c were determined by single crystal X-ray diffraction methods. The potentially [C,N,N′]? ligand is coordinated through the Npz and the Namino to the metal atom for 1a, through the Npz for 1b, and through the Npz, the Namino and a Cphenyl for 1c. 相似文献
10.
Anca Beleaga Monika Kulcsar Calin Deleanu Alina Nicolescu Cristian Silvestru Anca Silvestru 《Journal of organometallic chemistry》2009,694(9-10):1308-1316
Arylselenium(II) derivatives of dithiophosphorus ligands of type ArSeSP(S)R2 [Ar = Ph, R = Ph (1), OPri (2); 2-[MeN(CH2CH2)2NCH2]C6H4, R = Ph (3), OPri (4); 2-[O(CH2CH2)2NCH2]C6H4, R = OPri (6)] were prepared by redistribution reactions between Ar2Se2 and [R2P(S)S]2. The derivative [2-{O(CH2CH2)2NCH2}C6H4]SeSP(S)Ph2 (5) was obtained by the salt metathesis reaction between [2-{O(CH2CH2)2NCH2}C6H4]SeCl and NH4S2PPh2. The compounds were investigated by multinuclear (1H, 13C, 31P, 77Se) NMR and infrared spectroscopy. The crystal and molecular structures of 1, 3, 4 and 6 were determined by single-crystal X-ray diffraction. In compounds 3, 4 and 6 the N(1) atom is intramolecularly coordinated to the selenium center, resulting in a T-shaped geometry (hypervalent 10-Se-3 species). The dithiophosphorus ligands act as anisobidentate in 1 and monodentate in 3, 4 and 6. Supramolecular architectures based on intermolecular S?H and N?H contacts between molecular units are formed in the hypervalent derivatives 3 and 4, while in the compounds 1 and 6 the molecules are associated into polymeric chains through either Se?S or O?H contacts, with no further inter-chain interactions. 相似文献
11.
《Journal of organometallic chemistry》2007,692(1-3):208-216
The reaction of [Cp1CoI2]2 (1b) with 2 equiv of NaNCNH affords the 16-membered macrocyclic NCNH-bridged tetracobalt(III) complex [Cp1CoI(μ2-NCNH-N,N′)]4 (2b), while that with 2 equiv of Na2NCN yields the C3-elongated cubane-like NCN-bridged tetracobalt(III) complex [Cp1Co(μ3-NCN-N,N,N′)3(CoCp1)3(μ3-NCN-N,N,N)] (4b). Treatment of [Cp1RhCl2]2 (1c) with 2 equiv of NaNCNH gives the C3-elongated cubane-like tetrarhodium(III) complex [Cp1Rh(μ3-NCN-N,N,N′)3(RhCp1)3(μ3-NCN-N,N,N)] (4c) via the macrocyclic complex [Cp1RhCl(μ2-NCNH-N,N′)]4 (2c). On the other hand, the reaction of [Cp1CoCl]2 (7) with Na2NCN affords the anionic bis(NCN)-capped tricobalt(II) complex Na[(Cp1Co)3(μ3-NCN-N,N,N)2] (6). The molecular structures of complexes 2b · CH2Cl2 and 4c · 2C6H6 have been confirmed by X-ray analyses. The electrochemical properties of these types of NCN-bridged group 9 metal complexes have also been examined. 相似文献
12.
Tian-Pin Shu Jun-Long Wen Hai-Mei Feng Ke-Wei Lei Hong-Ze Liang 《Solid State Sciences》2009,11(12):2180-2183
The novel 18-metallacrown-6 metallamacrocycle, with the formula of [Fe6(amshz)6(C3H7NO)6]·6CH3OH (1), has been synthesized by the self-assembly reaction of iron ions with N-substituted salicylhydrazide ligands. Six Fe(III) ions and six deprotonated N-acetyl-3-methylsalicylhydrazide (amshz3?) ligands construct a planar 18-membered ring based on Fe–N–N–Fe linkage. Due to the coordination, the ligand enforces the stereochemistry of the Fe3+ ions as a propeller shape with alternating …ΔΛΔΛ… configurations. There exists a strong antiferromagnetic exchange interaction with μeff = 12.54 μB at 300 K between the Fe(III) spin 5/2 centers. 相似文献
13.
A novel Fe(III) spin-crossover complex, [Fe(qsal)2][Ni(dmise)2] · 2CH3CN 1 [qsalH = N-(8-quinolyl)-salicylaldimine, dmise = 4,5-dithiolato-1,3-dithiole-2-selone] was prepared. The magnetic susceptibility measurements revealed 1 exhibited a cooperative spin transition with a thermal hysteresis loop of 15 K. The high and the low temperature structures of 1 indicated three-dimensional intermolecular π?π interactions play a key role in the cooperative spin transition, accompanying a reversible molecular slipping of π-dimer of Ni(dmise)2 along the molecular long axis. The transfer integral calculation for 1 suggested the π-dimer of Ni(dmise)2 is in the spin singlet state. 相似文献
14.
《Journal of organometallic chemistry》2007,692(1-3):26-35
A series of heterodinuclear acylpalladium–cobalt complexes having a bidentate nitrogen ligand, L2(RCO)Pd–Co(CO)4 (L2 = bpy, R = Me (5), Ph (6); L2 = tmeda, R = Me (7), Ph (8); L2 = phen, R = Me (9), Ph (10)) are prepared by metathetical reactions of PdRIL2 with Na+[Co(CO)4]− followed by treatment with CO. These complexes are characterized by NMR and IR spectroscopies and elemental analyses, and the molecular structures of 6, 8, and 9 are determined by X-ray structure analysis. Geometry at Pd is essentially square planar and the Co atom is considered to have d10 tetrahedral structure, where cobalt(-I) anion coordinates to palladium(II) cation. Heterodinuclear organopalladium–cobalt complexes are shown to catalyze copolymerization of aziridines and CO under mild conditions. Reaction of (dppe)MePd–Co(CO)4 (1) with aziridine gives a cationic (aziridine)palladium(II) complex with [Co(CO)4]− anion, [PdMe(aziridine)(dppe)]+[Co(CO)4]− (13). 相似文献
15.
Xianzhu Xu Peng Wang Rong Hao Meina Gan Fuxing Sun Guang-shan Zhu 《Solid State Sciences》2009,11(1):68-71
A novel zinc diphosphonate, Zn[HO3PCH2(C6H4)CH2PO3H] (1) was synthesized from tetraethyl para-xylylenediphosphonate, Et2O3PCH2C6H4CH2PO3Et2, and Zn (AcO)2·2H2O under solvothermal conditions. The structure of compound 1 was determined by single-crystal X-ray diffraction, which reveals that the structure crystallizes in the monoclinic space group C2/c (No. 15), with a = 22.4844(19) Å, b = 6.4361(5) Å, c = 8.1194(7) Å, β = 102.595(2)°, V = 1146.70(16) Å3, T = 298(2) K, Z = 8. The novel three-dimensional (3D) construction is simply built up from linear inorganic chains of corner-sharing four-rings of tetrahedral [ZnO4] and [PO3C] which connected adjacent chains by the organophosphorus ligand para-xylylenediphosphonate. The framework has 10 Å × 4 Å (containing the van der Waals radii of atoms) channels running along the b-axis. 相似文献
16.
Masaki Kakeya Makoto Tanabe Yoshiyuki Nakamura Kohtaro Osakada 《Journal of organometallic chemistry》2009,694(14):2270-2278
Alkyl and arylplatinum complexes with 1,5-cyclooctadiene ligand, [PtR2(cod)] (R = Me, Ph, C6H4-p-CF3, C6F5), react with secondary phosphines, PHR′2 (R′ = i-Bu, t-Bu, Ph), to afford the mononuclear platinum complexes, cis-[PtR2(PHR′2)2] (1a: R = Me, R′ = i-Bu; 1b: R = Me, R′ = t-Bu; 1c: R = Me, R′ = Ph; 2a: R = Ph, R′ = i-Bu; 2b: R = Ph, R′ = t-Bu; 2c: R = R′ = Ph; 3a: R = C6H4-p-CF3, R′ = i-Bu; 3b: R = C6H4-p-CF3, R′ = t-Bu; 3c: R = C6H4-p-CF3, R′ = Ph; 4a: R = C6F5, R′ = i-Bu; 4c: R = C6F5, R′ = Ph) in 81–98% yields. Molecular structures of the complexes except for 1a, 1c and 2a were determined by X-ray crystallography. Complex 1b has a square-planar structure with Pt–C(methyl) bonds of 2.083(8) and 2.109(8) Å, while the Pt–C(aryl) bonds of 2b–c, 3a–c, 4a and 4c (2.055(1)–2.073(8) Å) are shorter than them. Thermal decomposition of 1b, 2a–c, and 3a–c releases methane, biphenyl or 4,4′-bis(trifluoromethyl)biphenyl as the organic products, which are characterized by NMR spectroscopy. The solid product of the thermal reactions of 2b and 2c were characterized as the metallopolymers formulated as [Pt(PR′2)2]n (5b: R′ = tBu; 5c: R′ = Ph), based on the solid-state NMR and elemental analyses. 相似文献
17.
Christos Lampropoulos Theocharis C. Stamatatos Khalil A. Abboud George Christou 《Polyhedron》2009,28(9-10):1958-1964
The use of a convenient source of MnIII ions, namely the [Mn(OR)(O2CR′)2]n (R = H, Me, and R′ = Me, But) family of 1-D coordination polymers, afforded two new enneanuclear and decanuclear molecular clusters, homometallic [Mn9O7(O2CBut)13(MeCN)2] (3) and heterometallic [Mn10?xFex(OMe)20(O2CMe)10] (x < 10) (4), respectively. Compound 3 was synthesized by a solvent-induced structural transformation, whereas complex 4 resulted from the reaction of [Mn(OH)(O2CMe)2]n with an FeIII source. The core of 3 comprises two [Mn4O2]8+ butterfly units and a [Mn3O]7+ triangular unit fused together by sharing one Mn atom. Magnetic susceptibility measurements of 3 revealed dominant antiferromagnetic interactions within the molecule, and a ground state of S = 1 with many low-lying excited states. Complex 4 is a mixed FeIII/MnIII single-strand molecular wheel, which forms 3D nanotubular stacks arranged in a zig–zag fashion. The described work suggests that the [Mn(OR)(O2CR′)2]n compounds represent excellent starting materials for MnIII carboxylate cluster chemistry. 相似文献
18.
《Journal of organometallic chemistry》2007,692(1-3):499-504
A new water-soluble sulfur-containing palladacyclic diaqua complex [(SC)PdII(H2O)2]2(SO4) {[1]2(SO4), SC = C6H4-2-(CH2StBu)} was synthesized from a reaction of Ag2SO4 with a water-insoluble palladacyclic dichloro complex [(SC)PdII(μ-Cl)]2 (2) in water. Water-solubility of [1]2(SO4) at pH 7 at 25 °C is 9.4 mg/mL. NH4PF6 was added to the solution of [1]2(SO4) in water to give [1](PF6). The structures of [1](PF6) and 2 were unequivocally determined by X-ray analysis. 相似文献
19.
Jinpeng Li Linke Li Hongwei Hou Yaoting Fan 《Journal of organometallic chemistry》2009,694(9-10):1359-1368
Seven Cd(II)–ferrocenesuccinate coordination complexes with the formulas [Cd(η2-FcCOC2H4COO)2(pbbbm)]2 (1), [Cd(η2-FcCOC2H4COO)(pbbbm)Cl]2 (2), [Cd(η2-FcCOC2H4COO)(pbbbm)I]2 (3), {[Cd(η2-FcCOC2H4COO)2(btx)2]2(CH3OH)0.5} (4), [Cd(η2-FcCOC2H4COO)2(bix)]2(H2O) (5), {[Cd(η2-FcCOC2H4COO)(bbbm)1.5Cl] · (CH3OH)0.5}n (6), and {[Cd(η2-FcCOC2H4COO)(mbbbm)Cl] · (H2O)2.75}n (7) [pbbbm = 1,4-Bis(benzimidazole-1-ylmethyl)benzene), btx = 1,4-bis(triazol-1-ylmethyl)benzene), mbbbm = 1,3-bis(benzimidazole-1-ylmethyl)benzene), bix = 1,4-bis(imidazol-1-ylmethyl)benzene, bbbm = 1,1-(1,4-Butanediyl)bis-1H-benzimidazole)] have been synthesized and characterized. Single-crystal X-ray analysis reveals that complexes 1–5 are all dimers and bridged by pbbbm, btx and bix, respectively. But the five complexes present some differences in their dimeric conformations, which can be ascribed to the impacts of adjuvant ligands and counter anions. In contrast to complexes 1–5, both 6 and 7 are of 1-D structures (with the same counter anions), and the former is double ladder-like structure only bridged by bbbm, while the latter is chain-like structure bridged by chlorine anions and adjuvant ligand mbbbm. Notably, various π–π interactions are found in complexes 1–7, and they have significant contributions to molecular self-assembly processes. The electrochemical studies of complexes 1–7 in DMF solution display irreversible redox waves and indicate that the half-wave potentials of the ferrocenyl moieties in these complexes are all shifted to positive potential compared with that of ferrocenesuccinate. 相似文献
20.
《Comptes Rendus Chimie》2015,18(8):816-822
The treatment of [PdL3(NH3)]OTf (L3 = (PEt3)2(Ph) (1), (2,6-(Cy2PCH2)2C6H3) (3)) with NaNH2 in THF afforded dimeric and monomeric parent-amido palladium(II) complexes with bridging and terminal NH2, respectively, anti-[Pd(PEt3)(Ph)(μ-NH2)]2 (2) and Pd(2,6-(Cy2PCH2)2C6H3)(NH2) (4). The dimeric complex 2 crystallizes in the space group P21/n with a = 13.228(2) Å, b = 18.132(2) Å, c = 24.745(2) Å, β = 101.41(1)°, and Z = 4. It has been found that there are two crystallographically independent molecules with Pd(1)–Pd(2) and Pd(3)–Pd(4) distances of 2.9594 (10) and 2.9401(9) Å, respectively. The monomeric amido complex 4 protonates from trace amounts of water to give the cationic ammine species [Pd(2,6-(Cy2PCH2)2C6H3)(NH3)]+. Complex 4 reacts with diphenyliodonium triflate ([Ph2I]OTf) to give aniline complex [Pd(2,6-(Cy2PCH2)2C6H3)(NH2Ph)]OTf (5). Reaction of 4 with dialkyl acetylenedicarboxylate (DMAD, DEAD) yields diastereospecific palladium(II) vinyl derivative (Z)–(Pd(Cy2PCH2)2C6H3)(CR = CR(NH2)) (R = CO2Me (6a), CO2Et (6b)). Reacting complexes 6a and 6b with p-nitrophenol produces (Pd(Cy2PCH2)2C6H3)(OC6H4–p-NO2) (8) and cis-CHR = CR(NH2), exclusively. 相似文献