Three-coordinate Silver Research Articles

Electrodes composited by bisbenzimidazole silver(I) coordination polymers as electrocatalysts for hydrogen evolution and H2O2-sensing

Two new silver(Ⅰ) coordination polymers (CPs) {[Ag2(p-HMOPhIDC)(BBP)](H2O)}n (1), {[Ag2(m-HMOPhIDC)(BBP)](H2O)}n (2) (BBP = 1,3-[bis(2,2′-benzimidazole)] propane, p-H3MOPHIDC = 2-(4-methoxyphenyl)–2H-imidazole-4,5-dicarboxylic acid, m-H3MOPHIDC = 2-(3-methoxyphenyl)–2H-imidazole-4,5-dicarboxylic acid), were prepared under hydrothermal condition and structurally characterized. The CPs 1–2 both exhibit binuclear 1D “square waveform” chain structures. Structural analysis shows that the two silver ions in CP 1 are crystallographically independent but chemically identical; whereas the two silver ions in CP 2 are crystallographically independent and chemically different. Electrocatalytic hydrogen evolution reaction (HER) of carbon paste composite electrodes (CPCEs 1–2) prepared by mixing graphite powder with coordination polymers was investigated by variable temperature linear sweep voltammetry (VT-LSV), controlled potential electrolysis (CPE) and electrochemical impedance spectroscopy (EIS) in 0.5 M H2SO4 electrolyte. It was found that the overpotential η10293K of CPCEs 1–2 positively shifted 449 and 172 mV compared with sCPCE (−966 mV), and the Tafel slope of sCPCE and CPCE 1–2 were 276, 160 and 226 mV dec-1, respectively. The results proved that CPCEs 1–2 could effectively catalyze and accelerate the HER behavior. The higher HER activity of the CPCE 1 than CPCE 2 can be attributed to the fact that CP 1 contains more three-coordinated silver ions. Moreover, the recognition performance of CPCEs 1–2 for H2O2 was further studied by chronoamperometry in 0.2 M phosphate buffer solution (PBS, pH = 6). The two sensors can detect H2O2 in a linear range from 0.5 μM to 4 mM with a detection limit of 128 µM for CPCE 1 and 27.1 µM for CPCE 2 at a signal-to-noise ratio of 3, and also revealed long-term stability and good selectivity.

Utility of Three-Coordinate Silver Complexes Toward the Formation of Iodonium Ions.

The work herein describes the synthesis of five three-coordinate silver(I) complexes comprising a bidentate ligand L1, either bpy (2,2′-bipyridyl) or bpyMe2 (4,4′-dimethyl-2,2′-dipyridyl), and a monodentate ligand L2, either mtz (1-methyl-1H-1,2,3-triazole), 4-Etpy (4-ethylpyridine), or 4-DMAP (N,N-dimethylpyridin-4-amine). Upon reaction of the three-coordinate silver(I) complexes with 0.5 equiv of I2, the reactions quantitatively produce a 1:1 pair of complexes of a four-coordinate silver(I) complex [Ag(L1)2]PF6 and a two-coordinate iodonium complex [I(L2)2]PF6. The combination of [Ag(bpyMe2)2]PF6 and [I(4-DMAP)2]PF6 gave rise to an I+···Ag+ interaction where the I+ acts as a nucleophile, only the second example of which, that was observed in both the solution (NMR) and solid (X-ray) states.

Photoluminescence properties of TADF-emitting three-coordinate silver(i) halide complexes with diphosphine ligands: a comparison study with copper(i) complexes.

Synthesis and X-ray structures of silver(i) bromide complexes with diphosphine ligands LMe, LEt, and LiPr are described, where LMe = 1,2-bis[bis(2-methylphenyl)phosphino]benzene, LEt = 1,2-bis[bis(2-ethylphenyl)phosphino]benzene, and LiPr = 1,2-bis[bis(2-isopropylphenyl)phosphino]benzene. Crystals of complex [(LMe)AgBr]2 (1), prepared from LMe and AgBr, showed a tetrahedral bimetallic structure. LEt and LiPr, with bulkier substituents than those of LMe, reacted with AgBr to give crystalline three-coordinate complexes (LEt)AgBr (2) and (LiPr)AgBr (3). Nuclear magnetic resonance (NMR) studies demonstrated that 1 dissociates in solution to yield a monomeric three-coordinate complex (LMe)AgBr. Luminescence studies showed that complexes 1-3 exhibit efficient blue thermally activated delayed fluorescence (TADF) in both solid state and solution. Density functional theory (DFT)/Time-dependent (TD)-DFT calculations revealed that the electronic transition responsible for TADF corresponds to (σ + Br) → π*. The photophysical properties of silver complexes 1-3 are discussed in detail and compared to those of the copper complex (LMe)CuBr.

Mechanistic Understanding of a Silver Pyridylpyrrolide as a Catalyst for 3 + 2 Cyclization of a Nitrile with Diazo Ester

The trinuclear argentate complex Ag3(μ2-3,5-(CF3)2PyrPy)3 (PyrPy = 2,2′-pyridylpyrrolide) catalyzes the 3 + 2 cycloaddition of several NCR (R = Me, Ph, tBu) and N2CHCO2Et to disubstituted oxazoles, even in the presence of light and air. Structural and theoretical studies imply a three-coordinate silver carbene complex, (3,5-(CF3)2PyrPy)Ag(CHCO2Et), to be responsible in a stepwise nitrile addition and cyclization step to form the heterocycle.

Three-coordinate silver(I) ions and tridentate ligands as complementary tectons in coordination polymer construction: a new example of semiregular 4.82 nets

The structures of the reaction products of silver nitrate with monoheterotopic tridentate ligands derived from N-alkyl-3,5-bis(3-pyridylmethylene)piperidin-4-one were studied. The aliphatic nitrogen atoms are involved in the coordination, all three nitrogen atoms of the ligands being coordinated to three different silver atoms. In turn, each silver atom is coordinated by two nitrogen atoms of the pyridine ring and one nitrogen atom of the piperidine ring of different ligands. The crystal structures of the complexes are different. Infinite ladder-like chains consisting of 16-membered metallamacrocycles as monomeric building blocks are present in the structure of the N-methyl derivative, whereas two-dimensional 4.82 nets consisting of 16-and 40-membered metallamacrocycles are observed in the crystal structure of the N-benzyl analog.

Structural Variations of Silver Ethylene Complexes Supported by Boron-Protected Fluorinated Scorpionates and the Isolation of a Ligand-Directed Silver Helix

Silver(I) ethylene adducts [PhB(3-(CF3)Pz)3]Ag(C2H4) and [MeB(3-(CF3)Pz)3]Ag(C2H4) have been synthesized using the corresponding lithium salts, AgOTf, and ethylene. X-ray data show that [PhB(3-(CF3)Pz)3]Ag(C2H4) has a planar three-coordinate silver center whereas [MeB(3-(CF3)Pz)3]Ag(C2H4) features a tetrahedral silver site. The ethylene-free {[PhB(3-(CF3)Pz)3]Ag}n adopts a helical structure with a hexagonal pore.

Syntheses, IR spectra, thermal analyses, crystal structures, luminescence properties and DFT calculations of two silver–saccharinato complexes with 2-(dimethylaminomethyl)-3-hydroxypyridine and N-(2-aminoethyl)pyrrolidine

Two new silver(I)–saccharinato (sac) complexes, [Ag(sac)(dmamhpy)] ( 1), [Ag 2(sac) 2(aeprd) 2] ( 2), (dmamhpy=2-(dimethylaminomethyl)-3-hydroxypyridine and aeprd= N-(2-aminoethyl)pyrrolidine, have been prepared and characterized by elemental analysis, IR spectroscopy, thermal analysis and single crystal X-ray diffraction. X-ray diffraction analyses reveal that complexes 1 and 2 have a dimeric structure containing three-coordinate silver(I) ions with a distorted T-shaped coordination of AgN 3. The dimeric structure of complex 1 is achieved by aromatic π⋯π stacking interactions, while the dimeric structure of complex 2 was governed by ligand unsupported Ag⋯Ag interaction with Ag–Ag contact of 3.1444(3) Å. The dimeric units are further linked by hydrogen bonds and C–H⋯π interactions into a three-dimensional supramolecular network so that the structure of 1 has solvent accessible voids with a volume of 132.1 Å 3. IR spectra and thermal analysis data for 1 and 2 are in agreement with the crystal structures. Complex 2 displays intense luminescence with emission maximum at 373 nm upon excitation at 210 nm. On the basis of experiment, both complexes were calculated by DFT-B3LYP/3-21G in gaussian 03.

A Cyclic Hexamer of Silver Trifluoroacetate Supported by Four Triphenylphosphine Sulfide Template Molecules

Crystallization of silver trifluoroacetate from chloroform solutions containing triphenylphosphine sulfide affords a trigonal and a monoclinic form of a 6:4 complex {[CF3C(O)OAg]6(Ph3PS)4} of C2 symmetry with different amounts of chloroform in the crystals. With the Ph3PS components as template molecules, the CF3C(O)OAg units are assembled to form a 6-membered metallacycle codetermined by metallophilic bonding and enclosed by a 24-membered ring [AgOCO]6. A complex of the type [LAgOC(O)CF3]2, with L representing the isocyanide ligand pTolSO2CH2NC, has been shown to have a conventional bicyclic structure with three-coordinate silver atoms engaged in transannular metallophilic interactions.

Syntheses, Structures and Vibrational Spectroscopy of Some Adducts of Silver(I) Cyanide with (Oligo-)Pyridine Bases

Abstract Crystalline materials obtained by the crystallization of silver(I) cyanide from/with a variety of (oligo-)pyridine bases, L, of various bulk, have been characterized by room temperature single crystal X-ray structure determination. From L = quinoline (= ’quin’), AgCN : quin (1:2), is obtained, the structure being a single-stranded polymer, the successive silver atoms located on two-fold axes linked by linearly bridging cyanide groups and four-coordinate, the other two coordination sites being occupied by symmetry related quinoline nitrogen atoms. From L = 2,4,6-trimethylpyridine (‘collidine’ ≡ ‘coll’) AgCN : coll (1:1) is obtained; it is similarly a one-dimensional polymer with bridging cyanide linkages, but now with three-coordinate silver(I), the one ligand nitrogen being coordinated. The adduct for L = pyridine (= ‘py’), is of novel AgCN : py (10:9) stoichiometry; it also is a onedimensional polymer, with three-coordinate silver(I) atoms also coordinated by pyridine nitrogen, but with periodic ‘errors’ in a wave-like array (similar to that recently reported for ‘LT-CuCN’), here associated with the incorporation of occasional two-coordinate silver(I) lacking the pyridine - an unusual coordination complex example of a ’modulated’ structure? 1:1 adducts are obtained with L = 2,2’-bipyridine, ‘bpy’, 1,10-phenanthroline, ’phen’, and 2,9- dimethylphenanthroline, ‘dmp’, the latter two adducts being ’solvated’ with additional moles of phen and pyridine respectively. AgCN : bpy (1:1) is a single-stranded polymer with four-coordinate silver atoms linearly bridged by cyanides. The complex components of AgCN : phen (1:2) (≡ AgCN : phen (1:1). phen) and AgCN : dmp (: py) (1:1(:1)) are both mononuclear 1:1 species, [LAgCN], with threecoordinate metal atoms. With 2,2’:6’,2”-terpyridyl, ‘tpy’, a pyridine solvated adduct of AgCN : tpy : py (8:2:1) stoichiometry is found, the pyridine being incorporated in the one-dimensional polymer which comprises an . . .Ag’(NCAgCN)Ag’(NCAgCN)Ag’. . . spine, with (tpy)Ag(NCAgCN)Ag’ and Ag’(NCAg(py)CN)(tpy) units pendant to either side at alternate three-coordinate Ag’. In all of the oligodentate ligand complexes, the molecular packing is of interest, being dominated by the usual interleaving and perpendicular aromatic planar moieties. The IR spectra of the one-dimensional polymers show bands that are assigned to vibrations of the extended AgCN chains in these complexes: ν(CN), ν(AgC/N) (the AgC/AgN stretching mode, involving vibration of the CN group between its two neighbouring Ag atoms), δ (AgCN) (the restricted rotation of the CN group), and δ (NAgC) (the counter-vibration of the Ag substructure against the CN substructure). The ν(CN) and ν(AgC/N) bands in AgCN : py (10:9) occur in the ranges 2096 - 2154 and 360 - 460 cm−1 respectively, and show splittings that can be attributed to the unusual structure of this complex in the solid state. The Raman spectra of the py complex in the solid state and in solution are also discussed. In the other two unidentate ligand complexes, single bands are observed for the ν(CN) and ν(AgC/N) modes at 2140, 392 (AgCN : coll (1:1)) and 2140, 422 cm−1 (AgCN : quin (1:2)) respectively. The monomeric AgCN : bidentate ligand complexes AgCN : phen (1:1) and AgCN : dmp (1:1) show lower ν(CN) and ν(AgC/N) frequencies than the polymeric AgCN : bpy (1:1), despite the fact that the Ag-C/N distances in the former are shorter than that in the latter, in agreement with previously observed trends in AgCN/ER3 compounds.

Silver(I) Complexes of a Sterically Demanding Fluorinated Triazapentadienyl Ligand [N{(C3F7)C(Dipp)N}2]- (Dipp = 2,6-Diisopropylphenyl)

Sterically demanding triazapentadiene [N((C3F7)C(Dipp)N)2]H affords the isolation of thermally stable, two- and three-coordinate silver complexes. The free ligand [N((C3F7)C(Dipp)N)2]H has a W-shaped ligand backbone in the solid state.[N((C3F7)C(Dipp)N)2]H reacts with silver(I) oxide in acetonitrile leading to CH(3)CNAg [N((C3F7)C(Dipp)N)2]HIt features a two-coordinate silver center and a kappa(1)-coordinated triazapentadienyl ligand. This silver acetonitrile complex serves as an excellent precursor to obtain thermally stable, silver isocyanide t-BuNCAg [N((C3F7)C(Dipp)N)2]Hand silver phosphine [[N((C3F7)C(Dipp)N)2]HAgPPh(3) adducts. IR spectroscopic data for the silver(I) isocyanide t-BuNCAg [N((C3F7)C(Dipp)N)2]Hshows nu(CN) at 2219 cm(-)(1). The silver ion coordinates to the triazapentadienyl ligand via the central nitrogen atom. The silver PPh(3) adduct,[N((C3F7)C(Dipp)N)2]HAgPPh(3), was synthesized by treating CH3CNAg [N((C3F7)C(Dipp)N)2]Hwith PPh(3). It displays relatively large Ag-P coupling in the (31)P NMR spectrum. The triazapentadienyl ligand in[N((C3F7)C(Dipp)N)2]HAgPPh(3) acts as a chelating kappa(2)-donor. The Ag-P bond is relatively short (2.3487(10) A).

Liquid crystals of silver complexes derived from simple 1-alkylimidazoles.

A homologous series of silver complexes of 1-alkylimidazoles (R-im, R = CnH(2n+1), where n= 10, 12, 14, 16 and 18) was synthesized. All the CnH(2n+1)-im ligands are non-mesomorphic. Upon complexation, all the [Ag(CnH(2n+1)-im)2]-[NO3], except for n = 10, exhibit liquid crystalline properties. The crystal structure of [Ag(C12H25-im)2][NO3] shows that the silver center is two-coordinate and adopts a U-shaped conformation with bilayer packing. The non-mesomorphic [Ag(C16H33-bim)2][NO3](bim = benzimidazole) has a three-coordinate silver ion and has a chair conformation with monolayer stacking. Non-mesomorphic [Ag(C16H33-bim)2][BF4] has a linear geometry around the silver ion and also has a chair conformation. The mesophase for the Ag-(CnH(2n+1)-im) complexes has been identified as the smectic A (SmA) phase. [Ag(C16H33-im)2]+ with four different anions, NO3-, BF4-, PF6- and CF3SO3- were compared. Of the four Ag-im complexes, only that with the CF3SO3- anion does not show liquid-crystal behavior.

Structural diversity in the coordination of amidines and guanidines to monovalent metal halides.

A series of structurally characterised, monovalent metal-halide complexes incorporating neutral amidine and guanidine ligands is reported. N,N'-diphenylbenzamidine reacted with copper(I) chloride to afford the bis-ligand complex [CuCl(PhC[NPh][NHPh])2]2 (1), that exists as a chlorine bridged dimer in the solid state, with a non-symmetrical distribution of NH...Cl interactions within the 'Cu2Cl2' metallacycle. In contrast, only one equivalent of the guanidine, Me2NC[NiPr][NHiPr] (2), is coordinated in the copper(I) iodide complex [CuI(Me2NC[NiPr][NHiPr])]2 (3), which was also isolated as the dimer with bridging halide atoms. The molecular structure of the bicyclic guanidine, 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-alpha]pyrimidine (hppH), is reported, revealing a hydrogen bridged dimer with extensive delocalisation throughout the ligand framework. Coordination of hppH to lithium chloride afforded the dimeric bis-ligand complex [LiCl(hppH)2]2 (4) in which each hppH molecule interacts with a different chlorine atom of the central 'Li2Cl2' core of the molecule via NH...Cl hydrogen bonding. In contrast the 2:1 ligand to metal complex is formed with silver(I) chloride to afford AgCl(hppH)2 (5), a unique example of a monomeric, three-coordinate silver chloride supported by nitrogen-based ligands. The series of mixed ligand complexes [CuX(hppH)(PPh3)]n (6, X = Cl, n= 1; 7, X = Br, n= 2; 8 X = I, n= 2) have also been synthesised and structurally characterised, allowing comparisons of the relative coordinating behaviour of hppH and PPh3 as neutral donors at copper(I) centres to be made.

Synthesis and structure characterization of three-coordinate silver (I) and seven-coordinate cobalt (II) coordination polymers with 4-pyridylthioacetate

The synthesis and self-assembly of Silver (I) and Cobalt (II) with the 4-pyridylthioacetate (pyta) ligand leads to two new coordination polymers, Ag(pyta) ( 1) and [Co(pyta) 2H 2O] ( 2). 1 is a three-connected silver coordination polymer, which consists of a wave layer and regular rectangle cavities (5.54×8.16 Å). While 2 is constructed by fascinating assembly of pyta ligands with a new structure of seven-coordinate cobalt ions. The two-dimensional layers structure is based on four kinds of chiral helices viewed from a and b directions. The crystallographic parameters are as follows: for 1, monoclinic, space group P21/ c, with a=8.160(2) Å, b=10.109(2) Å, c=10.097(2) Å, β=104.93°, and Z=4; for 2, monoclinic, space group C2/ c, a=15.928(3) Å, b=6.3448(12) Å, c=15.582(3) Å, β=94.698(3)°, and Z=8.

Syntheses and structures of two photofluorescent infinite one-dimensional chains from assembly of tetradentate dipyridyl ligand with cadmium(II) and silver(I) salts

A new flexible tetradentate ligand 1,2-bis(3′-pyridylmethylamino)ethane (L) was synthesized and its coordination complexes with cadmium(II) and silver(I) salts were characterized by X-ray single crystal structure analysis. The structure of [Cd(L)](NO 3) 2·H 2O ( 1) is an infinite zigzag chain in which the Cd(II) atom is octahedrally coordinated with N 4O 2 donor set. The complex [Ag 3(L) 2](CF 3SO 3) 3 ( 2) has a different 1D chain structure, interestingly, containing two- and three-coordinated silver(I) atoms. The photofluorescence and electrospray mass spectrometry of complexes 1 and 2 were also investigated.

Novel Ag(I) complexes with propeller-like structure of tripodal ligand: syntheses and structures of two- and three-coordinate silver (I) complexes

Two mononuclear Ag(I) complexes, [Ag(tbsb)](NO 3)·DMF ( 1) and [Ag(tbsb)](NO 3)·4.5H 2O ( 2) {tbsb=1,3,5-tris(2-benzimidazol)sulfanylmethyl)-2,4,6-trimethylbenzene}, have been synthesized by self-assembly reaction of AgNO 3 with tbsb and characterized structurally. The silver atoms of both the complexes are coordinated by the imine nitrogen atoms from a tripodal ligand (tbsb) to form two- and three-coordinate structures, respectively. Complex 1 presents the first example of silver (I) compound of the tripodal ligand possessing propeller-like structure.

Synthesis and X-Ray Crystal Structures of Mononuclear Complexes of 1,3-Bis(8-quinolyloxy)propane

The preparations and X-ray crystal structures of the first transition metal complexes of 1,3-bis(8-quinolyloxy)propane (2) are described. The ligand acts as a trans-chelating N,N′-bidentate ligand in the three-coordinate silver(I) nitrate complex (3) and four-coordinate copper(II) chloride complex (4), but as an N,O,O′,N′-tetradentate ligand in the octahedral nickel(II) chloride complex (5).

Bridged poly(1-imidazolyl)borate silver(I) complexes containing tertiary mono(phosphine) ligands. The first structurally authenticated bis(imidazolyl)borate metal complex †

New silver(I) derivatives containing triorganophosphines and the anionic dihydrobis(1-imidazolyl)borate [H2B(im)2]−, or the tetrakis(1-imidazolyl)borate ligand, [B(im)4]−, have been synthesized from reaction of AgNO3 with PR3 (R = phenyl, cyclohexyl, o-, m- or p-tolyl) or (PPh2R′) (R′ = methyl or ethyl) and K{H2B(im)2}·DMAC [DMAC = dimethylacetamide) or K[B(im)4]. Binuclear [Ag(PR3)2{(im)BX2(im)}]2 or polymeric [Ag(PR3){(im)BX2(im)}]n (X = H or imidazolate) complexes have been obtained and fully characterized by elemental analyses and FT-IR in the solid state and by NMR (1H and 31P) spectroscopy and conductivity measurements in solution. Solution data are consistent with partial dissociation of complexes, occurring through breaking of both Ag–N and Ag–P bonds. The structures of [Ag{P(C6H4Me-p)3}2{(im)BH2(im)}]2·2CHCl3, [Ag{P(cy)3}{(im)BH2(im)}]n and [{P(cy)3}Ag{(im)B(im)2(im)}]2·MeCN have been determined by single crystal X-ray studies. The [Ag{P(cy)3}{(im)BH2(im)}]n adduct is a single-stranded polymer containing three-coordinate silver atoms (PAgN2 core), while in the two other adducts, the silver atoms are four-coordinate (P2AgN2 cores). In all structures the two silver atoms are bridged by independent imidazolate donors from a pair of (im)BX2(im) moieties.

Synthesis and crystal structure of a luminescent infinite 2D brick-wall network with two- and three-coordinate silver(I) atoms and ligand-unsupported silver–silver interactions

Assembly of a novel flexible tetradentate ligand 1,7-bis(4′-pyridyl)-2,6-diazaheptane (py-hep) with silver perchlorate hydrate provides an interesting two-dimensional (2D) brick-wall network: [Ag3(py-hep)2](ClO4)3·0.5CH3CN. The X-ray crystal structural analysis indicates that the framework consists of trigonal and linearly coordinated silver(I) atoms and ligand-unsupported metal–metal interactions. The complex shows photoluminescence in both the solid state and in acetonitrile solution.

Crystal structures and vibrational and solid-state (CPMAS) NMR spectroscopy of some bis(triphenylphosphine)silver(I) sulfate, selenate and phosphate systems

The crystal structures of [Ag2(PPh3)4(EO4)]·2H2O (E = S 1 or Se 2) showed that these contain [Ag2(PPh3)4(EO4)] units with three-coordinate silver and EO42− bridging the two silver atoms via two oxygen atoms. The complexes [Ag(PPh3)2(HEO4)]·H2O (E = S 3 or Se 4) contain [Ag(PPh3)2(HEO4)] molecules in which HEO4− is terminally bound to the silver atoms by a single oxygen atom. The complex [Ag(PPh3)2(H2PO4)]·2EtOH 5 contains [Ag(PPh3)2(H2PO4)] molecules in which H2PO4− is terminally bound to the silver atom, which is essentially three-coordinate. Heteronuclear 1J(107/109Ag,31P) and homonuclear 2J(31P,31P) spin–spin coupling constants for these compounds were determined by analysis of their high- (9.40 T) and very high-field (17.62 T) 31P CPMAS NMR spectra, with the aid of the 2-D 31P CPCOSY technique, and a strong inverse correlation was found between 1J(107/109Ag,31P) and the Ag–P bond length. IR and Raman studies show that the effect of a bound proton on the vibrational frequencies of EO42− is much greater than that of an attached metal atom.

Synthesis and crystal structure of three-coordinated silver(I) and copper(I) complexes with N2P binding set containing a novel tripodal ligand: 1,3,5-tris(benzimidazol-2-ylmethyl)benzene

Assembly of a novel tripodal ligand, 1,3,5-tris(benzimidazol-2-ylmethyl)benzene (tbib), and triphenylphosphine with silver(I) and copper(I) salts gave the corresponding mononuclear complexes, which were characterized by electrospray mass spectrometry and 31P NMR spectroscopy. The structure of the silver(I) complex, [Ag(tbib)(PPh3)]NO3 ·CH3OH·H2O, determined by X-ray crystallography, indicates that the silver(I) atom is coordinated by two nitrogen atoms of one tbib ligand and one phosphorus atom of triphenylphosphine. Another nitrogen atom of the tbib ligand is uncoordinated. The complex provides another example of a structurally characterized silver(I) complex with N2P binding set.