Dppm Ligands Research Articles

Crystal structure of (μ-N-allyl-thio-urea-κ(2) S:S)bis-[μ-bis-(di-phenyl-phosphanyl)methane-κ(2) P:P']bis-[bromido-copper(I)] aceto-nitrile disolvate.

The reaction of cuprous bromide with a mixture of 1,1-bis-(di-phenyl-phosphan-yl)methane (dppm: C25H22P2) and N-allyl-thio-urea (ATU: C4H8N2S) in aceto-nitrile yielded the title solvated dinuclear complex, [Cu2Br2(C4H8N2S)(C25H22P2)2]·2C2H3N or [Cu2Br2(ATU)(dppm)2]·2CH3CN. Both Cu(+) ions adopt distorted tetra-hedral geometries, being coordinated by one terminal Br atom, one μ(2)-S atom of the bridging ATU ligand and two P atoms of the bridging dppm ligands. Within the complex, intra-molecular C-H⋯S, C-H⋯π, N-H⋯Br and π-π stacking inter-actions are observed. In the crystal, the components are linked by N-H⋯Br and C-H⋯N hydrogen bonds and weak π-π stacking inter-actions, generating chains propagating in the [100] direction.

Crystal structure of bis-[μ-bis-(di-phenyl-phosphan-yl)methane-κ(2) P:P']-μ-chlorido-chlorido-1κCl-(1-phenyl-thio-urea-2κS)disilver aceto-nitrile hemisolvate.

In the dinuclear title complex, [Ag2Cl2(C7H8N2S)(C25H22P2)2]·0.5CH3CN, each AgI ion displays a distorted tetra­hedral coordination geometry with two P atoms from two bis­(di­phenyl­phosphan­yl)methane (dppm) ligands, one bridging chloride ion, one terminal chloride ion and one terminal S atom from the N,N′-phenyl­thio­urea (ptu) ligand. The dppm ligands and the bridging chloride ion force the two Ag atoms into close proximity, with a short Ag⋯Ag separation of 3.2064 (2) Å. In the crystal, complex mol­ecules are linked by N—H⋯Cl hydrogen bonds forming a dimer. The dimers are linked via weak C— H⋯Cl hydrogen bonds forming a two-dimensional supra­molecular architecture in the yz plane. In addition, an intra­molecular N—H⋯Cl hydrogen bond is observed.

Crystal structure of tris-[μ2-bis-(di-phenyl-phosphan-yl)methane-κ(2) P:P']di-μ3-bromido-tris-ilver(I) bromide-N,N'-phenyl-thio-urea (1/1).

The title complex, [Ag3Br2(C25H22P2)3]Br·C7H8N2S, comprises a trinuclear [Ag3Br2(C25H22P2)3]+ unit, a Br− anion and one N,N′-di­methyl­thio­urea mol­ecule (ptu). Three AgI ions are linked via two μ3-bridging Br atoms, leading to a distorted triangular bipyramid with an Ag⋯Ag separation range of 3.1046 (6)–3.3556 (6) Å. The triangular Ag3 arrangement is stabilized by six P atoms from three chelating bis­(di­phenyl­phosphan­yl)methane (dppm) ligands. The AgI ion presents a distorted tetra­hedral coordination geometry. In the crystal, the bromide anion is connected to the ptu mol­ecule through N—H⋯Br hydrogen bonds [graph-set motif R 2 1(6)]. Each bromide/ptu aggregate links the complex ion via C—H⋯S and C—H⋯Br hydrogen bonds, leading to the formation of a three-dimensional network. Two phenyl rings from two dppm ligands were modelled as disordered over two sites.

Triphenylguanidine‐Promoted ortho‐Metalation Reaction in a Triply Bonded Dirhenium System – Spectroscopic, Structural, and Computational Studies

AbstractTriphenylguanidine‐promoted ortho‐metalation reactions have been observed in reactions between the triply bonded dirhenium(II) complex Re2Cl4(μ‐Ph2PCH2PPh2)2 (1) and different para‐substituted triphenylguanidine ligands (HTPGR) in ethanol under reflux. The products are of the type Re2Cl2(μ‐dppm)(μ‐dppm°)(TPGR) [2(R), dppm = Ph2PCH2PPh2, μ‐dppm° represents the ortho‐metalated dppm ligand and R = H, 2(H); Me, 2(Me), and OMe, 2(OMe)]. These are the first examples of ortho‐metalated dirhenium complexes with bridging dppm ligands. These complexes have very similar spectral (UV/Vis, IR, and NMR) and electrochemical properties, which are also reported. The solid‐state structure of 2(H) has been established by single‐crystal X‐ray diffraction [Re–Re distance 2.2741(6) Å]. In the solid state, the molecules are linked by π···π and C–H···π intermolecular interactions and form infinite supramolecular chains. Anion···π interactions have also been revealed in the solid state. The electronic structures of the complexes are also scrutinized by density functional theory (DFT) calculations.

Crystal structure of [1,3-bis-(di-phenyl-phosphan-yl)propane-κ(2) P,P'](N,N'-di-methyl-thio-urea-κS)(thio-cyanato-κN)copper(I).

The asymmetric unit of the title compound, [Cu(NCS)(C3H8N2S)(C27H26P2)], contains two independent mononuclear complex mol­ecules. In each, the CuI ion exhibits a distorted tetra­hedral geometry by coordination with two P atoms from one 1,3-bis(diphenylphosphino)propane (dppm) ligand, one terminal S atom of one N,N′-di­methyl­thio­urea (dmtu) ligand and one terminal N atom of the thio­cyanato ligand. The dppp ligand is involved in a bidentate coordination mode with the CuI ion, forming a six-membered CuP2C3 ring. In both mol­ecules, the coordination of the dmtu ligand is further stabilized by an intra­molecular N—H⋯N hydrogen bond with an S(6) graph-set motif. In the crystal, mol­ecules are linked by N—H⋯S hydrogen bonds forming a zigzag chain along the a-axis direction. In one independent mol­ecule, one of the phenyl rings of the dppp ligand is disordered over two sites with refined occupancies 0.639 (11):0.361 (11) and this corresponds with a mutual disorder of the dmtu ligand in the other independent mol­ecule giving the same ratio of refined occupancies. The structure was refined as a two-component inversion twin.

Synthesis, structure and spectral properties of dithiocarbamato bridged dirhenium(III,II) complexes: A combined experimental and theoretical study

Sodium salts of dimethyldithiocarbamate, diethyldithiocarbamate and pyrrolidinedithiocarbamate react with the multiply bonded paramagnetic dirhenium(III,II) complex Re2(μ-O2CCH3)Cl4(μ-dppm)2, 1 (dppm=Ph2PCH2PPh2) in refluxing ethanol to afford the paramagnetic substitution products of the type Re2(η2-S,S)2(μ-S,S)(μ-Cl)2(μ-dppm), where S,S represents the dithiocarbamato ligands [S,S=S2CNMe2, 4(LMe); S2CNEt2, 4(LEt) and S2CN(CH2)4, 4(LPyr)]. These are the first examples of dirhenium complexes that contain bridging dithiocarbamato ligand along with the dppm ligand. These complexes have very similar spectral (UV–Vis, IR, EPR) and electrochemical properties which are also reported. The identity of 4(LEt) has been established by single-crystal X-ray structure determination (Re–Re distance 2.6385 (9)Å) and is shown to have edge-shared bioctahedral structure. The electronic structure and the absorption spectra of the complexes are scrutinized by the density functional theory (DFT) and time-dependent density functional theory (TD-DFT) analyses.

Synthesis and Structural Characterization of Six Pentanuclear and Tetranuclear Mo/W‐Cu‐S Clusters with Bis(diphenylphosphanyl) Methane

AbstractSix heterothiometalic clusters, namely, [WS4Cu4(dppm)4](ClO4)2·2DMF·MeCN (1), [MoS4Cu4(dppm)4](NO3)2·MeCN (2) [MoS4Cu3(dppm)3](ClO4)·4H2O (3), [WS4Cu3(dppm)3](NO3)·4H2O (4), [WS4Cu3(dppm)3]SCN·CH2Cl2 (5), and [WS4Cu3(dppm)3]I·CH2Cl2 (6) [dppm = bis (diphenylphosphanyl)methane] were synthesized. Compounds 1–4 were obtained by the reactions of (NH4)2MS4 (M = Mo, W) with [Cu2(μ2‐dppm)2(MeCN)2(ClO4)2] {or [Cu(dppm)(NO3)]2} in the presence of 1,10‐phen in mixed solvent (CH3CN/CH2Cl2/DMF for 1 and 2, CH2Cl2/CH3OH/DMF for 3 and 4. Compounds 5 and 6 were obtained by one‐pot reactions of (NH4)2WS4 with dppm and CuSCN (or CuI) in CH2Cl2/CH3OH. These clusters were characterized by single‐crystal X‐ray diffraction as well as IR, 1H NMR, and 31P NMR spectroscopy. Structure analysis showed that compounds 1 and 2 are “saddle‐shaped” pentanuclear cationic clusters, whereas compounds 3–6 are “flywheel‐shaped” tetranuclear cationic clusters. In 1 and 2, the MS42– unit (M = W, Mo) is coordinated by four copper atoms, which are further bridged by four dppm molecules. In compounds 3–6, the MS42– unit is coordinated by three copper atoms and each copper atom is bridged by three dppm ligands.

Syntheses, characterization, and structures of three ruthenium complexes containing two monodentate dppm ligands

Three cis-Ru(dppm)2XY complexes (XY = C2O4, 1; X = Cl, Y = N3, 2; X = Y = N3, 3) were prepared by reactions of cis-Ru(dppm)2Cl2 with (NH4)2C2O4, a mixture of NaN3 and NaPF6, and only NaN3, respectively, while 3 could also be obtained from further reaction of 2 with NaN3 undergoing a facile chloride abstraction. All complexes have been characterized by IR, NMR, UV–vis, and luminescence spectroscopic analyses as well as X-ray diffraction studies. Of these structures, 1 shows oxalate coordinates to Ru as a chelating ligand, while 2 displays Ru and azide linear, and 3 gives two azide groups cis to each other, which are different from two substituting ligands commonly lying in trans positions in Ru(P–P)2 complexes by using cis-Ru(dppm)2Cl2 as a precursor.

Synthesis, structure and terahertz spectra of six Ag(I) complexes of bis(diphenylphosphino)methane with 4,4′-bipyridine and its derivations

The reactions of silver salts AgX [X=OTf (OTf=CF3SO3), ClO4 and BF4] and bis(diphenylphosphino)methane (dppm) with 4,4′-bipyridine (bipy) and its derivations [1,2-di(4-pyridyl)ethane (dpa), 1,2-di(4-pyridyl)ethylene (dpe), 1,3-bis(4-pyridyl)propane (bpp)] lead to six silver(I) complexes: {[Ag2(dppm)2(OTf)]2(μ-bipy)}(OTf)2·2CH3OH (1), {[Ag2(dppm)2(μ-bpp)(OTf)](OTf)·CH3OH}n (2), {[Ag2(dppm)2(CH3CN)]2(μ-dpa)}(ClO4)4·2CH3CN (3), [Ag2(dppm)3](ClO4)2 (4), {[Ag2(dppm)2(μ-bipy)(CH3CN)](BF4)2}n (5) and {[Ag2(dppm)2(μ-dpe)(CH3CN)](BF4)2}n (6). Complexes 1 and 3 are tetranuclear complexes with two eight-membered Ag2P4C2 rings bridged by bipy and dpa respectively. 2, 5 and 6 are of infinite chain structures formed by [Ag2(dppm)2] units linked by bpp, bipy and dpe respectively. 4 is a binuclear compound with two silver atoms bridged by three dppm ligands. All complexes are characterized by X-ray diffraction, fluorescence, 1H and 31P NMR spectroscopy and terahertz time-domain spectroscopy (THz-TDS).

Utilisation des données d’information médicale pour effectuer un benchmarking des centres de lutte contre le cancer : une perspective internationale

The reactions of silver salts AgX [X = OTf (OTf = CF3SO3), ClO4 and BF4] and bis(diphenylphosphino)methane (dppm) with 4,4′-bipyridine (bipy) and its derivations [1,2-di(4-pyridyl)ethane (dpa), 1,2-di(4-pyridyl)ethylene (dpe), 1,3-bis(4-pyridyl)propane (bpp)] lead to six silver(I) complexes: {[Ag2(dppm)2(OTf)]2(μ-bipy)}(OTf)2·2CH3OH (1), {[Ag2(dppm)2(μ-bpp)(OTf)](OTf)·CH3OH}n (2), {[Ag2(dppm)2(CH3CN)]2(μ-dpa)}(ClO4)4·2CH3CN (3), [Ag2(dppm)3](ClO4)2 (4), {[Ag2(dppm)2(μ-bipy)(CH3CN)](BF4)2}n (5) and {[Ag2(dppm)2(μ-dpe)(CH3CN)](BF4)2}n (6). Complexes 1 and 3 are tetranuclear complexes with two eight-membered Ag2P4C2 rings bridged by bipy and dpa respectively. 2, 5 and 6 are of infinite chain structures formed by [Ag2(dppm)2] units linked by bpp, bipy and dpe respectively. 4 is a binuclear compound with two silver atoms bridged by three dppm ligands. All complexes are characterized by X-ray diffraction, fluorescence, 1H and 31P NMR spectroscopy and terahertz time-domain spectroscopy (THz-TDS).

Bimetallic osmium-tin complexes: Stannylene and hydrostannylene clusters upon addition of Ph3SnH to unsaturated triosmium clusters [(μ-H)2Os3(CO)8(μ-diphosphine)] (diphosphine = dppm, dppf)

Products of the addition of Ph3SnH to the unsaturated triosmium clusters [(μ-H)2Os3(CO)8(μ-dppm)] (1) and [(μ-H)2Os3(CO)8(μ-dppf)] (2) are highly dependent on the nature of the diphosphine. With the rigid bis(diphenylphosphino)methane (dppm), the stannylene complex [H2Os3(CO)7(μ-SnPh2)2(μ-dppm)] (3) is the major cluster product (35% yield), resulting from both Sn–H and Sn–C bond activation, while two previously reported triphenyltin complexes, [(μ-H)2Os3(CO)8(SnPh3)2(μ-dppm)] (4) (10% yield) and [(μ-H)2Os3(CO)8(SnPh3){μ-Ph2PCH2P(Ph)C6H4}] (5) (11% yield) also result. Biphenyl is also a co-product of this reaction and it is postulated to be formed concomitantly with 3. A similar reaction with the highly flexible 1,1′-bis(diphenylphosphino)ferrocene (dppf) complex leads to the formation of four tin-containing complexes: two previously reported compounds [HOs(CO)4(SnPh3)] (6) (8% yield) and [Os2(CO)6(SnPh3)2(μ-SnPh2)2] (8) (5% yield), and the new triphenyltin and hydrostannylene clusters [H(μ-H)2Os3(CO)8(SnPh3)(μ-dppf)] (10) (22% yield) and [(μ-H)Os2(CO)4(SnPh3)2(μ-HSnPh2)(μ-dppf)] (9) (12% yield) respectively, together with the dihydroxy cluster [Os3(CO)8(μ-OH)2(μ-dppf)] (7). Two of these new clusters have been characterized by X-ray crystallography. Cluster 3 consists of a central Os3 triangle with two stannylene groups, each bridging one Os–Os edge, a dppm ligand that bridges the third Os-Os edge, and two terminal hydride ligands. Cluster 10 consists of an Os3 triangle with a terminal SnPh3 group, one terminal and two bridging hydride ligands, and a bridging dppf ligand. The new compounds 3, 7, 9, and 10 have been investigated by electronic structure calculations, and the computed ground-state structures are discussed relative to the X-ray crystallographic structures.

New tetrazole-based Cu(i) homo- and heteroleptic complexes with various P^P ligands: synthesis, characterization, redox and photophysical properties

Four Cu(I) complexes with general formulas [Cu(N^N)(2)][BF(4)] and [(P^P)Cu(N^N)][BF(4)] were prepared, where N^N stands for 2-(2-tert-butyl-2H-tetrazol-5-yl)pyridine and P^P is a chelating diphosphine, namely bis-(diphenylphosphino)methane (dppm), bis-(diphenylphosphino)ethane (dppe) or bis[2-(diphenylphosphino)phenyl]ether (POP). In an acetonitrile medium, the Electro-Spray Ionization Mass Spectrometry (ESI-MS) determination provided the preliminary evidence for the occurrence of the dppm-containing complex as a mixture of a cationic mononuclear [Cu(N^N)(dppm)](+) species and a bis-cationic dinuclear [Cu(2)(N^N)(2)(dppm)(2)](2+)-type compound. Definitive evidence of peculiar structural features came from X-ray crystallography, which showed both the dppm- and, unexpectedly, the dppe-based heteroleptic compounds to crystallize as diphosphine-bridged Cu(I) dimers, unlike [Cu(N^N)(2)](+) and [(POP)Cu(N^N)](+) which are mononuclear species. In solutions of non-coordinating solvents, (31)P NMR studies at variable temperatures and dilution titrations confirmed that the dppm-based complex undergoes a monomer-dimer dynamic equilibrium, while the dppe-containing complex occurs as the bis-cationic dinuclear species, [Cu(2)(N^N)(2)(dppe)(2)](2+), within a concentration range comprised between 10(-2) and 10(-4) M. Differences among heteroleptic complexes might be related to the smaller natural bite angle displayed by dppm and dppe phosphine ligands (72° and 85°, respectively), with respect to that reported for POP (102°). The electrochemical features of the new species have been investigated by cyclic voltammetry. Despite the irreversible and complicated redox behaviour, which is typical for copper complexes, the reductions have been attributed to the tetrazole ligand whereas the oxidations are characterized as Cu(I/II) processes with a substantial contribution from the P^P-based ligands in the case of the heteroleptic species. All the four complexes are weakly or not luminescent in CH(2)Cl(2) solution, but heteroleptic complexes are bright green luminophores in a solid matrix, with quantum yields as high as 45% (dppm complex) even at room temperature. This makes them potential candidates as cheap emitting materials for electroluminescent devices.

Bis[μ-bis(diphenylphosphanyl)methane-κ2P:P′](μ-1-ethylthiourea-κ2S:S)bis[iodidocopper(I)] acetonitrile sesquisolvate

In the dinuclear title compound, [Cu2I2(C3H8N2S)(C25H22P2)2]·1.5CH3CN, each CuI atom exhibits a distorted tetra­hedral coordination with two P atoms from two bis­(diphenyl­phosphan­yl)methane (dppm) ligands, one metal-bridging S atom from the 1-ethyl­thio­urea (ettu) ligand and one iodide ion. The dppm ligand and the bridging S atom of the ettu ligand force the two copper atoms into close proximity, leading to the formation of a close intra­molecular Cu⋯Cu contact [3.3747 (17) Å]. The conformation of the dimeric complex is such that the two dppm ligands are located on one side of the dinuclear metal complex, while the two iodine atoms are pointed towards the other side of the complex, a conformation that is stabilized by two intra­molecular N—H⋯I hydrogen bonds between the ettu NH2 and NHEt moieties and the I atoms. Another pair of symmetry-equivalent N—H⋯I hydrogen bonds is established between neighboring mol­ecules across an inversion center, linking mol­ecules into dimers. The dimers are connected with each other and with the inter­stitial acetonitrile solvent mol­ecules via a range of weaker C—H⋯I and C—H⋯S inter­actions and through weak C—H⋯π inter­actions, leading to the formation of a three-dimensional network. One of the acetonitrile solvent mol­ecules is disordered in a 1:1 ratio across a crystallographic inversion center.

Phosphine-bridged dinuclear gold(I) alkynyl complexes: Thioredoxin reductase inhibition and cytotoxicity

The study of the biological properties of four dinuclear gold(I) alkynyl complexes with general formulae [(μ2-diphos)(AuCCC5H4N)2] (diphos=dcypm, dcypb, dppm and dppb) is reported in this work. The biological evaluation included enzymatic inhibition and tumor cell proliferation studies. Inhibition of the enzyme thioredoxin reductase (TrxR) was confirmed for the gold derivatives containing dppm and dppb bridging ligands and indicated a preference for the shorter bridging ligand. Strong cytotoxic activities against two different cultured tumor cell lines (MCF-7 and HT-29) were noted for most of the compounds but were not correlated with an activity against TrxR.

Regio- and Stereocontrolled Reaction of Arenes with Ethyl Propiolate Catalyzed by Palladium or Platinum Complexes with a Bidentate Phosphine Ligand. An Efficient and Straightforward Synthesis of (1Z,3E)-1-Aryl-1,3-butadienes

Abstract The reaction of mesitylene with ethyl propiolate in the presence of [Pd(dppe)(OAc)2] in TFA at 30 °C for 5 h gave diethyl (2E,4Z)-4-[(2,4,6-trimethylphenyl)methylene]-2-pentenedioate selectively. Screening several bidentate phosphines ligands showed that dppe and dppm ligands are good for the arylbutadiene formation. This reaction was applied to other electron-rich arenes and found to be effective for synthesis of arylbutadienes and extended π-conjugated molecules. The regio- and stereoselective addition of an arene to propiolate was confirmed by NMR and single-crystal X-ray structural analyses of the products, suggesting that the arylbutadiene formation consisted of anti addition of an arene and a metal to the triple bond of ethyl propiolate, followed by syn addition to another molecule of ethyl propiolate. Similarly, the reaction of various arenes with ethyl propiolate in the presence of [Pt(dppe)(OTf)2] catalyst gave arylbutadienes selectively. In the Pd- or Pt-catalyzed reaction of arenes with ethyl propiolate, it was found that a bidentate ligand controlled the reaction to lead the formation of arylbutadienes.

Formation of (Alkenylphosphonio)phenylruthenium Complexes from Diphenylacetylene and a [CpRu(dppm)] Cation: Experimental Evidence for the Equilibrium between η1-Disubstituted Vinylidene and η2-Internal Alkyne

The reaction of diphenylacetylene at a cationic ruthenium complex with a dppm (Ph2PCH2PPh2) ligand, [CpRu(dppm)]+, has been studied to reveal essentially for the first time the existence of an equilibrium between an η2-internal alkyne and η1-disubstituted vinylidene at a transition metal center. The reaction mixture at 70 °C for 69 h unexpectedly afforded a coupling product of diphenylacetylene and the dppm ligand, an (alkenylphosphonio)phenyl complex [CpRu{Ph2PCH2P(C6H4)Ph(η2-C(Ph)═CHPh)}]+ with the extremely rare coordination mode of κ1P,η1C,η2C,C′. The (alkenylphosphonio)phenyl complex further undergoes inversion of the coordination face of the alkene moiety at p-xylene reflux temperature. Both isomers of (alkenylphosphonio)phenyl complexes as well as the intermediary η2-internal alkyne and η1-disubstituted vinylidene complexes were fully characterized spectroscopically and crystallographically. By considering the structure of the (alkenylphosphonio)phenyl complexes obtained, the coupling reaction has been proposed to involve the attack of a phosphorus atom on the coordinated diphenylacetylene, which is in equilibrium with an η1-diphenylvinylidene ligand, and the C–H bond activation of a phenyl group on the cationic phosphorus atom leading to the products. Theoretical calculations support the proposed mechanism.

Palladium and platinum pyrimidine-2-thionate complexes with diphosphines

[MCl2(P–P)] (M=Pd and Pt; P–P=dppe and dppm) reacts with NaC4H3SN2, in a 1:2 molar ratio at room temperature, to give [M(S-C4H3SN2)2(dppe)] [M=Pd (1); M=Pt, (2)], [Pd(S-C4H3SN2)2(dppm)2] (3) and trans-[Pt(S-C4H3SN2)2(dppm)] (5), as well as other by-products such as [Pd2(S,N-C4H3SN2)4] (4) and trans-[Pt(S-C4H3SN2)2(PPh2Me)2] (6). A possible mechanism for the formation of 6, which requires cleavage of P–C bonds of the dppm ligands, is proposed.

P–C bond cleavage in dppm derivatives: X-ray structure of [Pd2(μ2-P,C-PPh2CHPOPh2)(μ2-dppm)Cl(PPh2Me)

cis -[PdCl 2 (dppm)] [dppm = 1,2-bis(diphenylphosphino)methane] reacts with NaOH in ethanol to afford [Pd 2 (μ 2 - P , C -PPh 2 CHPOPh 2 )(μ 2 -dppm)Cl(PPh 2 Me)], which clearly shows different aspects of the formation of PPh 2 Me from the starting dppm ligand, especially the μ 2 - P , C methanide coordination. The Pd–Pd bond length of 2.6754(4) Å is in the usual range for dipalladium(I) compounds. cis -[PdCl 2 (dppm)] reacts with NaOH in ethanol to afford [Pd 2 (μ 2 - P , C -PPh 2 CHPOPh 2 )(μ 2 -dppm)Cl(PPh 2 Me)], which clearly shows different aspects of the formation of PPh 2 Me by P–C cleavage from the starting dppm ligand, especially the μ 2 - P , C methanide coordination. ► P–C bond cleavage of dppm complex with formation of PPh 2 Me complex. ► X‐ray structure of one of the few examples of μ 2 - P , C - coordination of a dppm-H derivative. ► Coexistence of both PPh 2 Me and μ 2 - P , C -PPh 2 CHPOPh 2 , showing that the former should precede the latter.

Bis[μ2-bis(diphenylphosphanyl)methane-κ2P:P′]bis(μ4-diphenylphosphinato-κ4O:O:O′:O′)bis(μ2-trifluoroacetato-κ2O:O′)tetrasilver(I) acetonitrile disolvate

In the cation of the title compound, [Ag4(C2F3O2)2(C12H10O2P)2(C25H22P2)2]·2CH3CN, the two independent Ag+ cations are four-coordinated in a distorted tetra­hedral geometry by one P atom from a bis­(diphenyl­phosphan­yl)methane (dppm) ligand, one O atom from a trifluoro­acetate anion and two O atoms from two diphenyl­phosphinate (dpp) ligands. Two dppm ligands, two dpp ligands and two trifluoro­acetate anions bridge four metal atoms, forming a centrosymmetric tetra­nuclear complex. Intra­molecular C—H⋯O hydrogen bonds and a weak π–π inter­action [centroid–centroid distance = 3.9804 (13) Å] are also observed.

Synthesis, Structures, and Photophysics of Polynuclear Silver(I) Thiolate and Silver(I) Thiocarboxylate Complexes with Dppm Ligands

AbstractTrinuclear silver(I) thiolate and silver(I) thiocarboxylate complexes [Ag3(μ‐dppm)3(μn‐SR)2](ClO4) [n = 2, R = C6H4Cl‐4 (1) and C{O}Ph (2); n = 3, R = tBu (3)], pentanuclear silver(I) thiolate complex [Ag5(μ‐dppm)4(μ3‐SC6H4NO2‐4)4](PF6) (4), and hexanuclear silver(I) thiolate complexes [Ag6(μ‐dppm)4(μ3‐SR)4]Y2 [Y = ClO4, R =C6H4CH3‐4 (5) and C10H7 (2‐naphthyl) (7); Y = PF6, R = C6H4OCH3‐4(6)], were synthesized [dppm = bis(diphenylphosphanyl)methane] and their crystal structures as well as photophysical properties were studied. In the solid state at 77 K, trinuclear silver(I) thiolate and silver(I) thiocarboxylate complexes 1 and 2 exhibit luminescence at 470–523 nm, tentatively attributed to originate from the 3IL (intraligand) of thiolate or thiocarboxylate ligands, whereas hexanuclaer silver(I) thiolate complexes 5 and 7 produce dual emission, in which high‐energy emission is tentatively attributed to come from the 3IL of thiolate ligands and low‐energy emission is tentatively assigned to come from the admixture of metal···metal bond‐to‐ligand charge‐transfer (MMLCT) and metal‐centered (MC) excited states.