Influence of the steric properties of pyridine ligands on the structure of complexes containing the {LnCd2(bzo)7} fragment

The reaction of Cd(NO₃)₂ · 4H₂O and Eu(NO₃)₃ · 6H₂O or Tb(NO₃)₃ · 6H₂O with potassium 3,5-di-tert-butylbenzoate (Kbzo) and N-donor ligands (1,10-phenanthroline (phen), 2,4-lutidine (2,4-lut), 3,4-lutidine (3,4-lut), phenanthridine (phtd), 2,3-cyclododecenopyridine (cdpy), acridine (acr)) afforded heterometallic LnCd₂ complexes: [EuCd₂(bzo)₇(EtOH)₂(phen)] (2), [LnCd₂(bzo)₇(2,4-lut)₄] (Ln = Eu (3), Tb (4)), [EuCd₂(bzo)₇(H₂O)₂(2,4-lut)₂] · MeCN (5), [EuCd₂(NO₃)(bzo)₆(EtOH)₂(2,4-lut)₂] (6), [EuCd₂(bzo)₇(H₂O)(EtOH)(3,4-lut)₂] · 5EtOH (7), 3[EuCd₂(bzo)₇(H₂O)₂(phtd)₂] · 4phtd (8), [EuCd₂(bzo)₇(EtOH)₃(cdpy)] (9), 2[EuCd₂-(bzo)₂(EtOH)₄] · acr (10). The structures of complexes 2, 3, and 5–10 were determined by single-crystal X-ray diffraction. The isostructurality of complexes 3 and 4 was confirmed by powder X-ray diffraction. The structure of the trinuclear {Ln₂Cd} metal core is stable and independent of the type of peripheral ligands coordinated to cadmium atoms. Photoluminescent properties of compounds 3 and 4 were studied.

     

Organoselenido Complexes of Tungsten

Organometallic tungsten selenido complexes of the type [cpW(CO)₃]₂Se_m; m = 2 (1), 3 (2), 4 (3), can be easily synthesized via insertion of selenium into the alkali-metal tungsten bond of LiWcp(CO)₃ in appropriate ratios and subsequent oxidation of the produced W-selenolates with O₂/SiO₂. In contrast, reactions of K₂Se₆ with [cpW(CO)₃Cl] and 18-crown-6 in DMF lead to a mixture óf [cpW(CO)₃]₂Se₄ (3), the η¹ Se-bonded selenocarbamato complex [cpW(CO)₃SeC(O)NMe₂] (4) and the ionic complex [(18-crown-6)K]⁺[cpW(Se₄)₂]^? (5). The crystal structures of 3 and 4 together with their ⁷⁷Se NMR data are presented.     

Polymerizations of methyl methacrylate and rac-lactide by zinc(II) precatalyst containing N-substituted 2-iminomethylpyridine and 2-iminomethylquinoline

The reaction of [ZnCl₂] with N-cyclopentyl-1-(quinolin-2-yl)methanimine (L_A), N-cyclohexyl-1-(quinolin-2-yl)methanimine (L_B), N-cyclohexyl-1-(pyridin-2-yl)methanimine (L_C), 2,6-diethyl-N-(pyridin-2-ylmethylene)aniline (L_D), N-cyclopentyl-1-(pyridin-2-yl)methanimine (L_E), and N-phenyl-(pyridin-2-yl)methanimine (L_F) in ethanol produced the bidentate [(NN′)ZnCl₂] complexes, [L_AZnCl₂], [L_BZnCl₂], [L_CZnCl₂], [L_DZnCl₂], [L_EZnCl₂] and [L_FZnCl₂], respectively. The molecular structures revealed that the zinc in [L_nZnCl₂] (L_n = L_A ? L_D) showed a distorted tetrahedral geometry involving two nitrogens of N,N’-bidentate ligands and two chloride ligands. Most of these initiators were effective for polymerization of methyl methacrylate (MMA) and polymerization of rac-lactide (rac-LA). [L_CZnCl₂] (with N-cyclohexyl substituted at imine-pyridine moiety) exhibited the highest catalytic activity for MMA polymerization in the presence of modified methylaluminoxane (MMAO) with an activity of 3.33 × 10⁴ g PMMA/mol·Zn·h at 60 °C, giving moderate syndiotactic poly methyl methacrylate (PMMA) with high molecular weight (9.62 × 10⁵ g/mol). The dimethyl derivatives [L_nZnMe₂] (L_n = L_A ? L_F), generated in situ, polymerized rac-LA with moderate activity and yielded a polylactide (PLA) with good number-average molecular weights and narrower polydispersity indices (PDIs). [L_AZnMe₂] effectively initiates the ring-opening polymerization (ROP) of rac-LA to attain heterotactic PLA (P_r = 0.91).     

Polycondensation of Tris(Trimethylsilylseleno)Phosphane

Abstract

Tris-(trimethylsilyl)phosphane and their organo substituted derivatives (Me₃Si)_3?nP(Me₃C)_n (n: 0, 1, 2) (la-c) had been found suitable for the insertion of selenium into the phosphorus-silicon bond. At deep temperatures all silylselenophosphanes of the series (Me₃SiSe)_3?nP(Me₃C_n) (2a-c) are formed in a nearly quantitative reaction, if no excess selenium is present. (Me₃C)(Me₃SiSe)₂P=Se (3b) and (Me₃C)₂(Me₃SiSe)P=Se (3c) are detectable in small quantities as the only by-products of the reaction of (Ib-c), whereas (la) end in the formation of (2a) and traces of the dimer (Me₃SiSe)₂P-P(SeSiMe₃)₂ (4). On exposure to light or at elevated temperatures (2a) undergoes a disproportionation, forming Se=P(SeSiMe₃)₃ (3a), and the heterocycles P₃Se₄(SeSiMe₃) (5) and α-P₄Se₃(SeSiMe₃)₂ (6). (Me₃Si)₂Se is spUt off as a condensation product. After further irradiation or prolonged standing at room temperature, an insoluble oligomer is formed. The constitutions of (2-6) were determined by the analysis of their ³¹P- and ⁷⁷Se-nmr spectra.     

Syntheses and crystal structures of cobalt and nickel complexes of 2,6-bis(hydroxymethyl)pyridine

2?:?1 (L?:?M) Complexes of 2,6-bis(hydroxymethyl)pyridine (dhmp) with different Co(II) salts [CoCl₂·6H₂O, Co(SCN)₂, Co(NO₃)₂·6H₂O, CoSO₄·7H₂O and Co(OTos)₂·6H₂O] and Ni(II) salts [NiCl₂·6H₂O, Ni(NO₃)₂·6H₂O, NiSO₄·7H₂O and Ni(OTos)₂·6H₂O] have been prepared (1–9) and studied by infrared spectroscopy and X-ray crystallography. Influences on the distortion of the coordination polyhedron, the arrangement of the donor atoms and the packing structure of the complexes were investigated in terms of the different kinds of anions and cations. In the metal chloride Complexes 1 and 2, water of hydration was found, while in Complex 3 the counterion (SCN^–) acts as a ligand. The crystal structures of all complexes, except 3, show N₂O₄ hexacoordinated metal ions; in 3 the coordination environment is N₄O₂. Complex 1 is another exception in containing cobalt(III) instead of cobalt(II) as for the other complexes with cobalt salts. Logically, in Complex 1, one of the dhmp ligands is mono-deprotonated. In the neutral Complexes 2 and 4–9, the basal planes of the octahedra are made up of O donors and N atoms occupy the axial positions. In 1 as well as in 3, two N and two O atoms form the base, but in 1 O, and in 3 N atoms are on the axis of the coordination sphere. Moreover, the nickel Complexes 2, 5, 7 and 9 are more symmetrical in structure than the cobalt Complexes 1, 4, 6 and 8, in accordance with the Jahn–Teller effect. Packing structures of the complexes show specific interactions based on strong and weak H-bonds that involve the counterions, hydroxy groups and aromatic units, leading to extended network structures.     

Structural,Theoretical, and Spectroscopic Study of Mercury(II) Complexes of two New Unsymmetric Phosphorus Ylides

Abstract

The reaction of Ph₂PCH₂PPh₂ (dppm) with 4-methylphenacyl bromide and 2-(bromoacetyl)naphthalene in chloroform produce the new phosphonium salts [Ph₂PCH₂PPh₂CH₂C(O)C₆H₄Me]Br (1) and [Ph₂PCH₂PPh₂CH₂C(O)C₁₀H₇]Br (2). Further, by reaction of the monophosphonium salts of dppm with the strong base Et₃N the corresponding bidentate phosphorus ylides, Ph₂PCH₂P(Ph)₂ = C(H)C(O)C₆H₄Me (3) and Ph₂PCH₂P(Ph)₂ = C(H)C(O)C₁₀H₇ (4) were obtained. The reaction of these ligands with mercury(II) halides in dry methanol led to the formation of the mononuclear complexes {HgX ₂[(Ph₂PCH₂PPh₂C(H)C(O)C₆H₄Me)]} [X = Cl (5), Br (6), and I (7)] and {HgX ₂[(Ph₂PCH₂PPh₂C(H)C(O)C₁₀H₇)]} [X = Cl (8), Br (9), and I (10)]. Characterization of the obtained compounds was performed by elemental analysis, IR, ¹H, ³¹P, and ¹³C NMR spectra. The structure of compounds 3 and 10 are unequivocally determined by single crystal X-ray diffraction techniques. X-ray analysis of 10 reveals the presence of mononuclear complex containing Hg atom in a distorted tetrahedral environment. In all complexes, the title ylides are coordinated through the ylidic carbon and the phosphine phosphorus. Computational studies on ligand 4 and complexes 8, 9, and 10 at DFT (B3LYP) level of theory are also reported. It was shown that the formation of P,C-coordinated 1+1 complex 10 is energetically more favored than corresponding P,P-coordinated 1+2 product.

[Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the following free supplemental files: Additional figures]     

Syntheses,structures, and luminescence of three anion-dependent cadmium coordination polymers

Self-assembly of the flexible ligand 1,3,5-tri(1,2,4-triazol-1-ylmethyl)-2,4,6-trimethylbenzene (ttmb) with Cd(II) salts gave three coordination polymers {[Cd(ttmb)₂](SO₄)(H₂O)₁₆} _n (1), {[Cd(ttmb)₂(H₂O)₂](NO₃)₂(H₂O)₆} _n (2), and {[Cd(ttmb)₂(H₂O)₂](ClO₄)₂(H₂O)₇} _n (3). Complex 1 has a (3,6)-connected CdCl₂-type 2-D network. However, 2 and 3 show the 2-D (4,4) network and 1-D double chain, respectively. Complexes 1, 2, and 3 exhibit luminescent emission maxima at 306, 339, and 298?nm, respectively, in the solid state at room temperature.     

X-ray structures of cobalt(III) complexes with bio-relevant pyrazolyl thiosemicarbazone: Indication of structural changes on the increasing bulkiness of the alkyl substituents on thiosemicarbazone moiety

X-ray crystallographic studies of cobalt(III) complexes of 5-methyl-3-formylpyrazole-N(4)-diethylthiosemicarbazone (HMP_zNEt₂), [Co(MP _z NEt ₂ ) ₂ ]Br·2H ₂ O, 5-methyl-3-formylpyrazole-N(4)-dipropylthiosemicarbazone (HMP_zNPr ₂ ), [Co(MP _z NPr ₂ ) ₂ ]Br·2H ₂ O and 5-methyl-3formylpyrazole-N(4)-dibutylthiosemicarbazone (HMP_zNBu ₂ ), [Co(MP _z NBu ₂ ) ₂ ]Br·H ₂ O, have been reported. In all the three complex species, X-ray crystallography has authenticated a CoN₄S₂ octahedral coordination with the pair of orthogonally coordinated NNS tridentate ligands in the monodeprotonated form of the ligand. The two azomethine nitrogen atoms are trans to each other, while the pyrazolyl ring nitrogens and the thiolato sulfurs are in cis positions. A gradual decrease in the dihedral angle between the coordinating ligands has been observed with increase in the bulkiness of the aliphatic side chains of the substituent on the thiosemicarbazone moieties. In all the three complexes, intraligand C–H···S contacts appear to arrest the free rotation of the side chains about the C(6)–N(5) single bond. ^†Deceased     

Coordination architectures and luminescent properties of 5-(pyrimidyl)tetrazolate (Hpmtz) with group 2 metal ions

Four alkaline earth metal-organic frameworks, [Mg(H₂O)₆]?·?(pmtz)₂ (1), [Ca(pmtz) ₂(H₂O)₃]?·?H₂O (2), [Sr(pmtz)₂(H₂O)₄] (3), and [Ba(pmtz)₂(H₂O)₂]?·?4H₂O (4) [pmtz?=?5-(pyrimidyl)tetrazole anion], were synthesized and characterized by elemental analysis, IR spectroscopy, and X-ray crystallography. The crystal structures reveal that 1–3 are mononuclear while 4 displays a 2-D layer structure by bis(bidentate) bridging pmtz^?. The luminescence properties of 1–4 were investigated in the solid state at room temperature.     

Reactions of aqueous copper acetate with triethylamine and 3,5-dimethylpyrazole

The dissolution of aqueous copper acetate in tetrahydrofuran gives the Cu₂(μ-OOCMe)₄(thf)₂ complex (1), and its reaction with triethylamine in the presence of acetic acid yields “[Cu₂(μ-OOCMe)₄[μ-OOCMe(HNEt₃)]” _n polymer (2). Complexes 1 and 2 react with 3,5-dimethylpyrazole to form Cu(Hdmpz)₂(OOCMe)₂ (3) and Cu₂(μ-OOCMe)₄(Hdmpz)₂ (4), respectively. The structures of complexes 1–4 and that of solvate 4 × 0.5C₆H₆ (5) are determined by X-ray diffraction.     

Synthesis,structure, and reactivity of siloxides and germyloxides of iron(ii) and cobalt(ii)

Iron and cobalt siloxides and germyloxides [(Me₃Si)₃SiO]₂M (M = Fe (1), Co (2)), (Me₅Si₂O)₂Fe (3), (Prⁱ ₃SiO)₂M (M = Fe (4), Co (5)), (Prⁱ ₃GeO)₂Fe (6), (Ph₃SiO)₂Fe (7), (Me₃SiO)₂Fe (8), (Prⁱ ₃GeO)₂Fe(bpy) (9), and [(Me₃Si)₂NFe(-OSi₂Me₅)₂]₂Fe·C₆H₆ (10) were synthesized by the reactions of metal silylamides [(Me₃Si)₂N]₂M (M = Fe, Co) with the corresponding silanols or triisopropylgermanol. The reaction of pentamethyldisilanol with iron(ii) silylamide affords either polymeric complex 3 or coordination oligomer 10, depending on the ratio of the reactants. The structures of complexes 9 and 10 were established by X-ray diffraction analysis. The interaction of the prepared compounds with carbon oxides was studied. Low-coordination cobalt siloxide is the only among all prepared compounds that absorbs CO (2 mol) at room temperature and under 1 atm to form an unstable cluster. Compounds 1, 2, and 4—8 react with CO₂ to form carbonate complexes, and their reactivity decreases with a decrease in the electron-donating ability of the substituents at the central atom: (Me₃Si)₃SiO > Prⁱ ₃GeO Prⁱ ₃SiO > Me₃SiO Ph₃SiO.     

Syntheses and structures of three disulfoxide uranyl complexes

Three disulfoxide uranyl complexes [UO₂(DBSOB)(NO₃)₂] _n (1), [UO₂(DBM)₂]₂(DBSOB) (2), and [UO₂(PMBP)₂]₂(DBSOB) (3) (DBSOB = 1,4-di(butylsulfinyl)butane, HDBM = dibenzoylmethane, HPMBP = 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone) were synthesized and characterized. The [UO₂(NO₃)₂] groups are connected by bridging disulfoxide ligands DBSOB to form a 1-D zigzag chain in 1. Two [UO₂(DBM)₂] or [UO₂(PMBP)₂] groups are connected by a bridging DBSOB to form the dimeric structures of 2 or 3, respectively. Complexes 1, 2, and 3 are the first structurally characterized disulfoxide–actinide compounds. Thermal stabilities of 1, 2, and 3 were investigated.     

Metal–Heterocyclic thione interactions-15 – reactivity of coordinated thiones of bis(pyridine- 2-thiolato- or 1-oxopyridine- 2-thiones)palladium(II)/platinum(II) towards divalent metal halides: synthesis of polynuclear complexes

Reactions of dinuclear tetrakis(pyridine-2-thiolato)dipalladium(II) or platinum(II), M₂(C₅H₄NS)₄, with divalent metal halides in organic solvents formed compounds of stoichiometry: [M₂(C₅H₄NS)₄·(M′X₂)₂] {M = Pd, M′X₂ = HgCl₂ (1), PtCl₂ (2), CdCl₂ (3); M = Pt, M′X₂ = HgCl₂ (4)}. Similarly, bis(1-oxopyridine-2-thione)-palladium(II)/platinum(II) formed compounds: [M(C₅H₄NOS)₂·M′X₂] {M = Pd, M′X₂ = HgCl₂ (5), HgBr₂ (6), HgI₂ (7), CdCl₂ (8), PtCl₂ (9); M = Pt, M′X₂ = HgBr₂ (10), HgI₂, (11)}. Compounds 1–11 have been characterized using elemental analysis, IR, far-IR, and NMR (¹H, ¹³C) spectroscopy. Coordination to metal centers of M′X₂ occurs via coordinated sulfur. Possible structures are suggested. The crystallization of (5) in dimethyl sulfoxide formed crystals of Pd(C₅H₄NOS)₂ as revealed by X-ray crystallography.     

An Examination of the Coordination Chemistry of L2Pt(1,2-DITHIOLENES) Using Atmospheric Pressure Chemical Ionization Mass Spectrometry

Abstract

Atmospheric pressure chemical ionization mass spectrometry (APCI–MS) has been utilized in the characterization of two series of platinum dithiolene complexes, (COD)Pt(dt) 1, (COD)–Pt(edt) 2, (COD)Pt(dmid) 3, (COD)Pt(mnt) 4, (COD)Pt(eddo) 5, (COD)Pt(dddt) 6 and (Ph₃P)₂Pt(dt) 7, (Ph₃P)₂Pt(edt) 8, (Ph₃P)₂Pt(dmid) 9, (Ph₃P)₂Pt(dmit) 10, (Ph₃P)₂Pt(mnt) 11 (where COD = 1,5–cyclooctadiene, dt = ethane–1,2–dithiolate, edt = ethylene–1,2–dithiolate, dmid = 1,3–dithiole–2–oxo–4,5–dithiolate, dmit = 1,3–dithiole–2–thione–4,5–dithiolate, mnt = maleonitrile–1,2–dithiolate, eddo = 4–(ethylene–1′,2′–dithiolate)–1,3-dithiole–2–one, and dddt = 5,6–dihydro–1,4–dithiin–2,3–dithiolate). The series that contains triphenylphosphine is labile toward the loss of HPPh₃ ⁺. In addition, an orthometallated species involving the platinum and triphenylphosphine is identified. A dimer is identified for 2, which is shown to be a product of the experiment and not present in the parent material. In addition, a 1:1 adduct with NH₄ ⁺ is identified for 4 and 11 where the NH₄ ⁺ originates from the acid hydrolysis of acetonitrile. Finally, a highly unique ion, Pt⁺, a bare platinum ion, is observed in all COD complexes indicating that a radical mechanism must accompany the decomposition of the COD complexes during the fragmentation process.     

Synthesis and structural characterization of new multiferrocenyl diyne ligands and their cobalt carbonyl complexes

New multiferrocenyl diyne ligands FcC(CH₃)₂Fc′–C≡C–C≡C–Fc [L ₁ ; Fc?=?C₅H₅FeC₅H₄; Fc′?=?C₅H₅Fe(1,3-disubstituted)C₅H₃], FcC(CH₃)₂Fc′–C≡C–C≡C–Fc′C(CH₃)₂Fc (L ₂ ) and their complexes [FcC(CH₃)₂Fc′–C≡C–C≡C–Fc][Co₂(CO)₆] _n [n?=?1, (1); n?=?2, (2)], [FcC(CH₃)₂Fc′–C≡C–C≡C–Fc′C(CH₃)₂Fc][Co₂(CO)₆] _n [n?=?1, (3); n?=?2, (4)] have been synthesized by the coupling reaction of terminal ferrocenylacetylene and the reaction of ligands L₁ and L₂ with Co₂(CO)₈. The composition and molecular structure of the ligands L₁ , L₂ and their cobalt complexes were characterized by element analysis, IR, ¹H(¹³C)NMR and MS. The electrochemical properties of compounds L₁ , L₂ , 1, 2, 3, 4 were studied by cyclic voltammetry(CV). The results of the electrochemical research reveal that all three ferrocenyl groups in L₁ become redox active centers, but there are only two (not four) ferrocenyl redox active centers in L₂ .     

Influence of intermolecular hydrogen bonding on magnetic properties of mononuclear cobalt and nickel pivalates with amidine ligands

The magnetic properties of the mononuclear cobalt(ii) amidine complex Co(Me₃CCOO)₂{H₂N(C₅H₃N)NH(MeC=NH} (1) having a tetrahedral structure and its solvate 1·HOOCCMe₃·0.5C₆H₆ (1a) are substantially different. Complex 1 possesses ferromagnetic properties and exhibits residual magnetization at liquid-helium temperatures, whereas solvate 1a and the octahedral amidine complex Ni(Me₃CCOO)₂{H₂N(C₅H₃N)NH(MeC=NH}·MeCN (3·MeCN) show antiferromagnetic properties. Apparently, this is associated with the difference in the type of intermolecular nonbonded interactions in the crystals of 1, 1a, and 3·MeCN, which form channels for spin-spin exchange. The tetrahedral isostructural mononuclear complexes ML₂ (M = Co (5), Ni (6), L is N-tosyl-2,5-dimethyl-8-aminoquinoline) were synthesized. These complexes exhibit antiferromagnetic properties.     

Syntheses and structures of three new coordination polymers with the flexible 1,4- bis (imidazol-1-yl)butane ligand

Three new coordination polymers [Co(bimb)₂(NCS)₂] _n (1), {[Co(bimb)₂(dca)₂]?·?CH₃CN} _n (2) and [Cu(bimb)₂(NO₃)₂] _n (3) (bimb?=?1,4-bis(imidazol-1-yl)butane, dca?=?dicyanamide) were synthesized and characterized. In 1, each Co(II) links two Co(II)'s by double bimb ligands and extends to form a one-dimensional chain containing the Co₂(bimb)₂ 22-membered metallocycle. 2 and 3 are two-dimensional (4, 4) networks linked by bimb bridges. The conformations of the bimb ligands in 1, 2 and 3 are analyzed.     

Hydrogen-bond networks of 1,3-imidazolidine-2-thione: synthesis and structures of complexes of silver(I), copper(I), cadmium(II) and zinc(II)

Solution reactions of silver(I), copper(I), cadmium(II) and zinc(II) salts with 1,3-imidazolidine-2-thione (imdt) under diverse conditions yielded four complexes: [Cd(SC₃H₆N₂)₂(Ac)₂] (1), [Zn(SC₃H₆N₂)₂(Ac)₂] (2), [Cu₂(SC₃H₆N₂)₆]SO₄ (3) and [Ag₂(SC₃H₆N₂)₆]SO₄ (4). Complexes 1 and 2 are 1D and 2D hydrogen-bond aggregations. Complexes 3 and 4 are isostructural 3D hydrogen-bond networks. The diverse coordination modes of imdt and different anions are the major factors for three distinct hydrogen-bond structures.     

Electronic states of XC<Subscript>3</Subscript>H<Subscript>3</Subscript>Si five-membered rings (X = CH,N, P,and As)

Stable configurations of XC₃H₃Si five-membered rings, 1 _X and 2 _X (X = CH, N, P, and As) in the singlet and triplet states are found at B3LYP/6-311++G** level of theory. All the singlet states of 1 _X and 2 _X have lower potential energy than the triplet state. The ΔG _s−t differences between the singlet and triplet states of 1 _X and 2 _X changes at the B3LYP/6-311++G** level in the order (in kcal/mol): 1 _N (−17.56) > 1 _CH (−15.26) > 1 _P (−4.96) > 1 _As (−3.45) and 2 _CH (−15.26) > 2 _N (−9.21) > 2 _P (−7.39) > 2 _As (−6.15), respectively.     

Synthesis,X-ray structural and DFT studies of n-membered ring P,C-chelated complexes of Pd(II) and Pt(II) derived from unsymmetrical phosphorus ylides and application of Pd(II) complexes as catalyst in Suzuki reaction

The phosphonium salts [Ph₂P(CH₂)_nPPh₂CH₂C(O)C₆H₄-m-OMe]Br (n = 1 (S₁) and n = 2 (S₂)) were synthesized in the reaction of bis(diphenylphosphino)methane (dppm) and bis(diphenylphosphino)ethane (dppe) with 2-bromo-3?-methoxy acetophenone, respectively. Further treatment with NEt₃ gave the phosphorus ylides Ph₂P(CH₂)_nPPh₂C(H)C(O)C₆H₄-m-OMe (n = 1 (Y₁) and n = 2 (Y₂)). These ligands were treated with [MCl₂(cod)] (M = Pd or Pt; cod = 1,5-cyclooctadiene) to give the P, C-chelated complexes, [MCl₂(Ph₂P(CH₂)_nPPh₂C(H)C(O)C₆H₄-m-OMe)] (n = 1, M = Pd (3), Pt (4), and n = 2, M = Pd (5), Pt (6)). These compounds were characterized by elemental analysis, spectroscopic methods, UV–visible, and fluorescence emission spectra. Further, the structures of complexes 3 and 6 were characterized crystallographically. The palladium complexes 3 and 5 proved to be excellent catalysts for the Suzuki reactions of various aryl chlorides. Also, a theoretical study on the structure of complexes 3–6 has been investigated at the BP86/def2-SVP level of theory. The strength and nature of donor?acceptor bonds between the phosphorus ylides (L) and MCl₂ fragment in the [LMCl₂] (M = Pd, Pt, L = Y₁, Y₂) were studied by NBO and energy decomposition analysis (EDA), as well as their natural orbitals for chemical valence variation (EDA-NOCV).