Interfragment transmission of electronic effects of π-acceptor ligands in heterometallic triad complexes with trans-[Ru(Py)4(CN)2] as a central unit

The complex trans-[RuPy₄(CN)₂] cleaves chloride bridges in the binuclear rhodium(i) and palladium(ii) complexes [Rh(CO)₂Cl]₂, [Rh(η⁴-C₈H₁₂)Cl]₂, [(η⁴-C₈H₁₂)Rh(μ-Cl)₂Rh(CO)₂], [Pd(η³-C₃H₅)Cl]₂, and [(η₃-C₃H₅)Pd(μ-Cl)₂Rh(CO)₂] to form heterometallic triad complexes [(CO)₂ClRh(NC)RuPy₄(CN)RhCl(CO)₂] (1), [(η⁴-C₈H₁₂)ClRh(NC)RuPy₄(CN)RhCl-(η⁴-C₈H₁₂)] (2), [(CO)₂ClRh(NC)RuPy₄(CN)RhCl(η⁴-C₈H₁₂)] (3), [(η³-C₃H₅)ClPd(NC)-Ru(Py)₄(CN)PdCl(η³-C₃H₅)] (4), and [(CO)₂ClRh(NC)Ru(Py)₄(CN)PdCl(η₃-C₃H₅)] (5), respectively. In solutions, complex 3 coexists with equilibrium amounts of compounds 1 and 2; complex 5 is in the equilibrium with compounds 4 and 1. In both cases, the ratio of concentrations is close to binomial. Complexes 2 and 5 treated with [Rh(CO)₂Cl]₂ are converted into 1 with the simultaneous formation of [Rh(η⁴-C₈H₁₂)Cl]₂ and [Pd(η³-C₃H₅)Cl]₂, respectively. The δ_H and δ_C values for the ligands η⁴-C₈H₁₂, η³-C₃H₅, and CO are sensitive to the nature of the remote triad unit. The ligand effects are shown to be transmitted along the chain L′-M′-(NC)-Ru-(CN)-M″-L″.     

Effect of anions on supramolecular architecture of benzimidazole-based ionic salts

The reaction of N,N,N′,N′-tetrakis-(1H,benzimidazol-2ylmethyl) propane-1,3-diamine (L) with different inorganic acids affords salts viz., LH₄ ⁴⁺·4ClO₄ ^?·H₂O (1), LH₄ ⁴⁺·4Cl^?·2H₂O (2), LH₄ ⁴⁺·2H₂PO₄ ^?·H₇P₃O₁₂ ^2?·3H₃PO₄ (3), LH₄ ⁴⁺·4NO₃ ^? (4), and 2LH⁺·2CF₃COO^?·5H₂O (5). The X-ray crystallographic studies revealed that the proton transfer occurred from acid to the ligand. It also demonstrated that different type of hydrogen bond between protonated ligand and anions is responsible for the supramolecular framework. The colorimetric test showed color change upon the addition of acids in the solution of the ligand. The photo-physical experiments suggested the fluorescence properties of ligand in the presence of acids.     

Synthesis and properties of ZnII and CdII complexes with chiral N-derivatives of aminoacetic acid based on natural monoterpenes (+)-3-carene and (?)-��-pinene. Crystal structure of coordination polymer [Zn(HL)Cl��2H2O] n

Chiral sodium salts of N-derivatives of aminoacetic acid based on (+)-3-carene (HLNa) and (?)-??-pinene (HLNa) were synthesized. Complexes Zn(HL)Cl (1), Cd(HL)Cl·0.5H₂O (3), Zn(HL??)Cl·0.5H₂O (4), and Cd(HL??)Cl·0.5H₂O (5) were obtained. The single crystals of the coordination polymer [Zn(HL)Cl·2H₂O] _n (2) were grown. According to the X-ray diffraction analysis, the crystal structure of 2 consists of 1D chains built of Zn(HL)Cl and water molecules. The coordination polyhedron ClN₂O₂ is a distorted square pyramid. The HL^? ligand performs the chelating tetradentate-bridging function, and the COO^? group binds two adjacent Zn atoms. The IR spectroscopy data for compounds 1 and 3?C5 indicate the coordination of the COO^?, NOH, and NH functional groups. The excitation and photoluminescence (PLM) spectra of the solid samples of compounds HLNa, HL??Na, 1, and 3?C5 were recorded at room temperature. The compounds exhibit blue PLM. The intensity of PLM of the CdII complexes is higher than that of the ZnII complexes, which is a characteristic feature of PLM of the studied compounds.     

The Thermolysis of [Ru3(CO)12] in Cyclohexene: Synthesis and Charaterisation of the New Clusters [Ru3H2(CO)9(μ3-η1:η2:η1-C6H8)] and [Ru5(CO)12(μ4-η2-C6H8)(η4-C6H8)]

Thermolysis of [Ru₃(CO)₁₂] in cyclohexene for 24 h affords the complexes [Ru(CO)₃(η⁴-C₆H₈)] (1), [Ru₃H₂(CO)₉(μ₂-η¹:η²:η¹-C₆H₈)] (2), [Ru₄(CO)₁₂(μ₄-C₆H₈)] (3) [Ru₄(CO)₉(μ₄-C₆H₈)(η⁶-C₆H₆)] (4a and 4b, two isomers) and [Ru₅(CO)₁₂(μ₄-η²-C₆H₈)(η⁴-C₆H₈)] (5), where 1, 3, 4a and 4b have been previously characterised as products of the thermolysis of [Ru₃(CO)₁₂] with cyclohexa-1,3-diene. The molecular structures of the new clusters 2 and 5 were determined by single-crystal X-ray crystallography, showing that two conformational polymorphs of 5 exist in the solid state, differing in the orientation of the cyclohexa-1,3-diene ligand on a ruthenium vertex.     

Multi-component hydrogen-bonding salts formed between imidazole and aromatic acids: Synthons cooperation and crystal structures

Imidazole base was crystallized with different aromatic carboxylic acids 2,4-dihydroxybenzoic acid, 5-chlorosalicylic acid, and 1,8-naphthalic acid, affording three new binary molecular organic salts of [(C 3 H 5 N 2 + )·(C 7 H 5 O 4 )] (1), [(C 3 H 5 N 2 + )·(C 7 H 4 O 3 Cl )] C 7 H 5 O 3 Cl (2), and [(C 3 H 5 N 2 + ) (C 12 H 7 O 4 )] (3). Proton transfer occurs from the COOH of carboxylic acid to nitrogen of imidazole in all complexes (1-3), leading to the hydrogen bond N-H…O in all structures. To our knowledge, the recognition pattern between the carboxylic acid group and imidazole (acid-imidazole synthon) is less well-studied so far. The cooperation among COOH, COO and imidazolium cation functional groups for the observed hydrogen bond synthons is examined in the three structures. Generally, the strong N-H…O and O-H…O hydrogen bonds define supramolecular architecture and connectivity within chains, while weaker C-H…O hydrogen bonds play the dominant role in controlling the interactions between layers in these novel organic salts. Thermal stability of these compounds has been investigated by thermogravimetric analysis (TGA) of mass loss.     

Synthesis and some properties of anionic chloranilate complexes of iron(iii). Crystal and molecular structure of rubidium and cesium chloranilatoferrates

New anionic chloranilate complexes of iron(iii) Cs[Fe(C₆O₄Cl₂)₂(H₂O)₂]·4H₂O (1), Rb[Fe(C₆O₄Cl₂)₂(H₂O)₂]·4H₂O (2), Rb₂[Fe(C₆O₄Cl₂)₂(H₂O)₂]₂·5H₂O (3), Cs₃Fe(C₆O₄Cl₂)₃ (4), (Bu₄N)Fe(C₆O₄Cl₂)₂ (5), (Bu₄N)₄Fe₂(C₆O₄Cl₂)₅ (6), and (R₄N)₃Fe(C₆O₄Cl₂)₃ (R = Pr (7), Bu (8), C₅H₁₁ (9)) were synthesized in an aqueous medium. The Mössbauer spectra of the synthesized chloranilatoferrates are characteristic of the high-spin state of Fe^III in an octahedral oxygen coordination. The crystal and molecular structures of compounds 1–3 were determined by X-ray diffraction. The complex anions [Fe(C₆O₄Cl₂)₂(H₂O)₂]^2? involved in these compounds are composed of two chelate chloranilate ions and two water molecules trans-(1,2) or cis-coordinated (3) to the iron atom. Since tetraalkylammonium tris(chloranilato)ferrates 7–9 and binuclear complex 6 are soluble in many organic solvents, they are promising precursors for the synthesis of metal-organic coordination polymers. Tetrabutylammonium bis(chloranilato)ferrate (Bu₄N)Fe(C₆O₄Cl₂)₂ (5) is the first example of the preparation of an anionic chloranilate complex of iron(iii) with a plausible chain structure in an aqueous medium.     

Benzoylacetonate and its fluorinated derivatives as ligands for Co(II) complexes: the effect of the presence of fluorine atoms on the crystal packing

The influence of the introduced fluorine atoms to diketonato backbone exerted on the crystal packing was studied on cobalt(II) bis(4,4,4-trifluoro-1-phenylbutane-1,3-dionato-κ ² O,O′) compounds with pyridine (1), 2,2′-bipyridine (2) and 1,10-phenanthroline (4), and cobalt(II) bis(benzoylacetonato-κ ² O,O′) compound with 2,2′-bipyridine (3). The solid-state structures of 1–4 were determined by single crystal X-ray analysis. The coordination of Co(II) is octahedral in all four compounds. The differences in crystal packing of 1 with regard to the known complexes with non-fluorinated analogue and 4,4,4-trifluoro-1-(4-fluorophenyl)butane-1,3-dionate were observed. Unit cell parameters of 2·½C₇H₈ and 3·½C₇H₈ slightly differ, but they have similar crystal packing dominated by the π–π interactions. Strong π–π interactions and weak C–H···π(arene) and C–F···π(arene) interactions are present in 2–4, while no significant intermolecular interactions are present in 1.     

Water-induced reversible dissolution/reorganization transformations of Cu(Ⅱ)-K(I) heterometallic coordination polymers

Three new heterometallic coordination compounds, namely, [KCu(I3)(L)2(H2O)2]n(1), [KCu(I3)(L)2(H2O)]n(2) and [CuK4(I3)2(L′)4]n(3), were prepared and characterized(HL=5-methylpyrazine-2-carboxylic acid, HL′=p-tolylacetic acid). Structural studies revealed that 1 and 2 exhibit 3D frameworks with rectangular channels occupied by triiodide ions. Both compounds can be symbolized as a 5-connected net with pcu topology. In compound 3, a one-dimensional polyhedral chain is connected by hexanuclear mask like clusters [Cu2K4O8]. These chains are further linked each other via rare(1,1,3,3)-triiodide ion-bridging units to generate a 3D(4,5,6)-connected net with the point symbol of {12}2{4·122}4{46}{48·62}4{49·66}4. It is noteworthy that water-induced reversible dissolution/reorganization processes occur between 1/2 and [Cu(L)2(H2O)]n·3nH2O. The thermal and photoluminescence properties of compounds 1, 2, and 3 were investigated as well.     

Synthesis and crystal structures of 2,4,6-pyridine-tricarboxylic anions/guanidinium and tetraalkylammonium inclusion compounds

Two different hydrogen-bonded inclusion compounds, [2,4,6-C₅H₂N(COO^?)₃]_0.5·[C(NH₂) ₃ ⁺ ]_0.5·[(C₂H₅)₄N⁺]·2H₂O (1) and [2,4,6-C₅H₂N(COO^?)₃]·[C(NH₂) ₃ ⁺ ]·[(C₂H₅)₄N⁺]·[(C₃H₇)₄N⁺]·6H₂O (2) are reported in this paper, in which 2,4,6-pyridine-tricarboxylic anions, guanidiniums and water molecules jointly construct host lattices while tetraalkylammonium cations are accommodated as guest species. Both two compounds formed sandwich-like hydrogen-bond inclusion compounds. In compound 1, the dimers composed of 2,4,6-pyridine-tricarboxylic anions and guanidiniums form 2D hydrogen-bonded layers by connecting with water molecules. In compound 2, 2,4,6-pyridine-tricarboxylic anions, guanidiniums and water molecules contribute to generate an undulate rosette hydrogen-bonded architecture. Interestingly, in compound 2, there are two species of guest molecules, tetraethylammonium and tetrapropylammonium, which are alternately arranged between the neighboring layers. Mixed guest cations accommodated in hydrogen-bonded inclusion compounds are seldom seen.     

Keggin-Type Polyoxometalate Cluster Functionalized with Dinuclear M-H2biim (M = Cu, Ag) Metal–Organic Segments

Three inorganic–organic hybrid complexes, [Cu₂(H₂biim)₂(OH)₂]₂(SiW₁₂O₄₀)·2H₂O (1), [Cu₂(H₂biim)₂]₂(SiW₁₂O₄₀)·2H₂O (2) and [Ag₂(H₂biim)₂]₂(SiW₁₂O₄₀)·2H₂O (3) (H₂biim = 2, 2′-biimidazole), have been synthesized under hydrothermal conditions, and characterized by elemental analysis, IR, PXRD, TG and single-crystal X-ray diffraction. The crystallographic analysis reveals that in compounds 1–3, the Keggin polyanions [α-SiW₁₂O₄₀]^4? act as inorganic building blocks, which are linked with the dinuclear metal–organic units via Cu–O bonds in compound 1, or through supramolecular interactions in compounds 2 and 3. Compound 1 shows a 3D supramolecular structure constructed by net-like layers. Compounds 2 and 3 display 2D layer structures which were composed of wave-like chains. In addition, these compounds show electrochemical activities, and photoluminescence properties are measured in the solid state.     

One-dimensional metal phosphonates based on 6-phosphononicotinic acid: A structural and magnetic study

The reactions of 6-phosphononicotinic acid (pnaH₃) and metal salts result in three new compounds, namely, M(pnaH)-(H₂O)₃·H₂O [M = Co(II) (1), Ni(II) (2), Zn(II) (3)]. These compounds are isostructural and contain 2₁ helical chains made up of corner-sharing {MO₅N} octahedra and {PO₃C} tetrahedra. The chains are further connected by extensive hydrogen bonds to form a three-dimensional supramolecular structure. Magnetic studies reveal that dominant antiferromagnetic interactions are mediated in both 1 and 2. Interestingly the dehydrated compound 1 shows metamagnetic behavior at low temperature.     

Synthesis, structure, solid-state thermolysis, and catalytic properties of binuclear Ce, Nd, Eu, and Gd cymantrenecarboxylate complexes with DMSO

New rare-earth cymantrenecarboxylate complexes [Ln₂(μ,η²-O₂CCym)₂(μ²-O₂CCym)₂-(η²-O₂CCym)₂(DMSO)₄] (Cym = (η⁵-C₅H₄)Mn(CO)₃, Ln = Ce (1), Nd (2), Eu (3), Gd (4)) were synthesized and characterized by X-ray diffraction. In dimeric structures 1–4, two of four bridging carboxylates are chelating-bridging, and Ln atoms have coordination number 9. The catalytic activity of complex 2 in the polymerization of 2,3-dimethyl-1,3-butadiene was investigated. The thermal decomposition of the synthesized compounds was studied by DSC and TGA. According to the X-ray powder diffraction data, the final thermal decomposition product of 1 in air consists of CeO₂ and Mn₃O₄. Under the same conditions, complexes 2–4 afford mixtures of LnMn₂O₅ and Mn₂O₃.     

Supramolecular compounds constructed from Keggin anions and metal–organic complex cations of 3-aminopyrazine-2-carboxylic acid

Three new supramolecular compounds based on Keggin-type polyoxometalate (POM) and transition metal complexes, [M(Hapca)₂(H₂O)₂]₂[SiW₁₂O₄₀]·nH₂O, (M = Ni^II(1), Zn^II(2), n = 12; Co^II (3), n = 15; Hapca = 3-aminopyrazine-2-carboxylic acid), have been synthesized in aqueous solution and characterized by single-crystal X-ray diffraction, elemental analysis, TG analyses, IR and fluorescence spectroscopy. The X-ray structrual analysis reveals that three compounds are isostructural with a P21/c space group. [M(Hapca)₂(H₂O)₂] ₂ ⁴⁺ are linked together via O···N hydrogen-bonding interaction to give birth to 2D layer with rectangle grids. Anions [SiW₁₂O₄₀]^4? are located in the cavities and link the 2D layers into 3D supramolecular architecture via hydrogen bonds. The compounds represent the first examples of self-assembly of 2D metal–Hapca complex supramolecular “host” networks formed by hydrogen bonding interactions and “guest” polyoxoanion species. In addition, solid-state luminescence properties of compounds 2 and 3 have been studied at room temperature.     

One ligand different metal complexes: Biological studies of titanium(IV), tin(IV) and gallium(III) derivatives with the 2,6-dimethoxypyridine-3-carboxylato ligand

The reaction of 2,6-dimethoxypyridine-3-carboxylic acid (DMPH) with different precursors [Ti(η⁵-C₅H₅)₂Cl₂], [Ti(η⁵-C₅H₄Me)₂Cl₂], [Ti(η⁵-C₅H₄SiMe₃)(η⁵-C₅H₅)Cl₂], [Ti(η⁵-C₅Me₅)Cl₃], SnMe₃Cl and Ga^tBu₃ yielded the complexes [Ti(η⁵-C₅H₅)₂(DMP-κO)₂] (1), [Ti(η⁵-C₅H₄Me)₂(DMP-κO)₂] (2), [Ti(η⁵-C₅H₄SiMe₃)(η⁵-C₅H₅)(DMP-κO)₂] (3), [Ti(η⁵-C₅Me₅)(DMP-κ²O,O′)₃] (4), [SnMe₃(μ-DMP-κO:κO′)]_∞ (5), and [Ga^tBu₂(μ-DMP-κO:κO′)]₂ (6). 1-6 have been characterized by spectroscopic methods and the molecular structure of the complexes 1, 2, 3, 5 and 6 have been determined by X-ray diffraction studies. The cytotoxic activity of 1-6 was tested against the tumour cell lines human adenocarcinoma HeLa, human myelogenous leukaemia K562, human malignant melanoma Fem-x and human breast carcinoma MDA-MB-361. The results of this study show a higher cytotoxicity of the tin(IV) and gallium(III) derivatives in comparison to their titanium(IV) counterparts. Furthermore, the different titanium compounds showed differences in their cytotoxicities with a higher activity of complex 4 (mono-(cyclopentadienyl) derivative) compared to that of 1-3 (bis-(cyclopentadienyl) complexes). A qualitative UV-vis study of the interactions of these complexes with DNA has also been carried out.     

Photochemical arene exchange in the iron dicarbollide complex [(η-9-SMe2-7,8-C2B9H10)Fe(η-C6H6)]+

Visible light irradiation of the dicarbollide complex [(η-9-SMe₂-7,8-C₂B₉H₁₀)Fe(η-C₆H₆)]⁺ (2a) in the presence of the benzene derivatives in CH₂Cl₂/MeNO₂ resulted in cations [(η-9-SMe₂-7,8-C₂B₉H₁₀)Fe(η-C₆R₆)]⁺ (2b-g; arene is anisole (b), toluene (c), m-xylene (d), mesitylene (e), durene (f), and hexamethylbenzene (g)) due to the arene exchange. The structures of [2g]PF₆ and related tricarbollide complex [(η-1-Bu^tNH-1,7,9-C₃B₈H₁₀)Fe-(η-C₆H₆)]PF₆ (1) were confirmed by X-ray diffraction analysis. The nature of bonding in cations 1, 2a, and [CpFe(η-C₆H₆)]⁺ was analyzed by an energy decomposition analysis.     

Synthesis,crystal structures,luminescence and catalytic properties of three silver(I) coordination polymers with bis(imidazole) and benzenedicarboxylic acid ligands

Three new silver coordination compounds with empirical formula [Ag₂(L1)₂·(ntp)·(H₂O)_3.25]_n (1), [Ag_1.5(L1)_1.5·(H_0.5bdc)·(H₂O)₄]_n (2) and [Ag(L2)(Hmip)]_n (3) (L1 = 1,4-bis(imidazol-1-ylmethyl)benzene, L2 = 1,1′-(1,4-butanediyl)bis-1H-benzimidazole, H₂ntp = 2-nitroterephthalic acid, H₂bdc = 1,3-benzenedicarboxylic acid, H₂mip = 5-methylisophthalic acid) were synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction and physico-chemical spectroscopic methods. The silver centers display different environments with a linear geometry in 1 and 2 and distorted T-shaped geometry in 3. In 1–3, the bidentate N-donor ligands (L1 and L2) bridge neighboring silver centers to form 1D infinite chain structures. Complexes 2 and 3 are extended into 2D layers, and 1 is packed into a 3D 3,4,4,6-connected supermolecular network via classical O–H···O hydrogen bonds, while 3 is further extended into 3D framework through π–π interactions. The luminescence properties of complexes 1, 2 and 3 were investigated in the solid state. These coordination polymers possess a remarkable activity for degradation of methyl orange by persulfate in a Fenton-like process.     

New aryl ethynylene substituted silicon-centered molecules

The reactions of substituted dichlorosilane monomers,Cl₂SiRR′, with two equivalents of lithium aryl acetylide(1), LiC ≡ C-4-C₆H₄-Ph, afford RR′Si(C ≡ C-4-C₆H₄-Ph)₂ (6: R,R′ =CH₃; 7: R = CH₃, R′ = CH=CH₂; 8: R,R′ = Ph). An isomeric mixture of meso, (R,R)- and (S,S)-Bis[2-(N,N-dimethylaminomethyl)ferrocenyl]dichlorosilane (5) was used as starting chlorosilyl compound for reaction with LiC ≡ C-4-C₆H₄-Ph to give (FcN)₂Si(C ≡ C-4-C₆H₄-Ph)₂ (9). A detailedcharacterization of 6, 7, 8 and 9 has been carried out by ¹H-NMR, ¹³C-NMR, ²⁹Si-NMR, IR and UV-VIS spectroscopy. The crystal structure of 9 has been determined by X-ray diffraction analysis.     

Honeycomb-like layers constructed by hydrogen bonds. Synthesis, structure, and property of two new supramolecular compounds based on polyoxotungstate

Two new compounds based on polyoxotungstate [Co₂(PCA)₄(H₂O)₆][SiW₁₂O₄₀]·8H₂O (1), [Cd₂(PCA)₄(H₂O)₆][SiW₁₂O₄₀]·8H₂O (2) (PCA = pyridine-4-carboxylic acid) are prepared and characterized by single crystal X-ray diffraction, elemental analysis, IR spectroscopy, and thermal analysis. The results of the single crystal X-ray diffraction analysis reveal that 1 and 2 are isomorphic and two water molecules in the compounds act as the bridging groups of two cobalt or cadmium atoms, forming dinuclear coordination cations. The ligand PCA adopts a monodentate coordination mode and its uncoordinated carboxyl oxygen atom and the protonized nitrogen atom form hydrogen bonds with other ligands, by which the cations are linked into a supramolecular 2D network with hexagonal grids. The polyoxotungstate anions are arranged above and below the cationic grids. A strong emission peak at 420 nm of 2 is attributed to a ligand-metal transition.     

Structural diversity of transition-metal coordination polymers derived from isophthalic acid and bent bis(imidazole) ligands

Four coordination polymers associated with bent bis(imidazole) 1,3-bis(imidazol-l-yl-methyl)benzene (mbix) and isophthalic acid (H₂ip) or 5-methylisophthalic acid (H₂mip) ligands, formulated as {[Cd(mbix)(mip)]·H₂O} _n (1), {[Co(mbix)(mip)]·0.4H₂O} _n (2) [Ni(mbix)(mip)H₂O] _n (3) and [Ni(mbix)(ip)] _n (4), were synthesized under hydrothermal conditions and characterized by physico-chemical and spectroscopic methods. Complexes 1 and 2 are isomorphous and exhibit a 1D loop-like chain. Complex 3 features a 2D (4,4) layer, which further extends into an unusual 2D (3,5)-connected 3,5L2 double-layered supramolecular network via classical O–H···O hydrogen bonding interactions. Complex 4 is a 3D network, which shows a rare binodal (3,5)-connected 3,5T1 framework. Moreover, the luminescence and catalytic properties of the complexes for the degradation of methyl orange by sodium persulfate in a Fenton-like process are reported.     

Synthesis and characterization of palladium(II) and platinum(II) metal complexes with iminophosphine ligands: X-ray crystal structures of platinum(II) complexes and use of palladium(II) complexes as pre-catalysts in Heck and Suzuki cross-coupling reactions

The reactions of N-(2(diphenylphosphino) benzylidene) (phenyl) methanamine, Ph₂PPhNHCH₂-C₅H₄N, 1 and N-(2-(diphenylphosphino) (benzylidene) (thiophen-2-yl) methanamine, Ph₂PPhNHCH₂-C₄H₃S, 2 with MCl₂(cod) and MCl(cod)Me (M = Pd, Pt; cod = 1,5-cyclooctadiene) yield the new complexes [M(Ph₂PPhNHCH₂-C₅H₄N)Cl₂], M = Pd1a, Pt1b, [M(Ph₂PPhNHCH₂-C₅H₄N)ClMe], M = Pd1c, Pt 1d, [M(Ph₂PPhNHCH₂-C₄H₃S)Cl₂], M = Pd2a, Pt 2b, and [M(Ph₂PPhNHCH₂-C₄H₃S)ClMe], M = Pd2c, Pt 2d, respectively. The new compounds were isolated as analytically pure crystalline solids and characterized by ³¹P-, ¹H-NMR, IR spectroscopy, electro spray ionization-mass spectrometry (ESI-MS) and elemental analysis. The representative solid-state molecular structures of the platinum complexes 1b and 2b were determined using single crystal X-ray diffraction analysis and revealed that the complexes exhibit a slightly distorted square-planar geometry. Furthermore, the palladium complexes were tested as potential catalysts in the Heck and Suzuki cross-coupling reactions.