Metal-nitrogen Bonds Research Articles

Complexation of Transition Metals by 3-Azidopropionitrile. An Electrospray Ionization Mass Spectrometry Study

Most complexes of azides and transition metals involve the N(3)(-) azide anion as a ligand other than an organic azide. Complexes of organic azides with metals are involved in biological applications and in the deposition of nitrenes on metal surfaces, producing nitride layers for semi-conductors preparation; this makes the study of these interactions an important issue. This work describes a study of the complexation of nickel and cobalt by 3-azidopropionitrile by means of electrospray ionization mass spectrometry (ESI-MS). Complexes were obtained from solutions of NiCl(2) and CoCl(2) in methanol/water. In the case of nickel, other NiX(2) salts were investigated (where X = Br or NO(3)) and other solvents were also studied (notably ethanol/water). All complexes detected were single positively charged, with various stoichiometries, some resulted from the fragmentation of the ligand, the loss of N(2), and HCN being quite common. The most abundant cations observed were [Ni(II)AzAzX](+), where X = Cl, Br, NO(3). Some of the complexes showed solvation with methanol/ethanol/water. Metal reduction was observed in complexes where a radical was lost, resulting from the homolytic cleavage of a metal-nitrogen bond. Collision induced dissociation (CID) experiments followed by tandem mass spectrometry (MS-MS) analysis were not absolutely conclusive about the coordination site. However, terminal ions observed from the fragmentation routes were explained by a proposed gas-phase mechanism. Density functional theory calculations were carried out and provided structures for some complexes, pointing to the possibility of 3-azidopropionitrile acting as a mono- or a bidentate ligand.

Nona-coordinated MO 6N 3 centers M = Zr, Hf as a stable building block for the construction of heterometallic alkoxide precursors

The modification of zirconium or hafnium alkoxides with diethanolamine, H 2dea, leads to the formation of unique nona-coordinated M{μ-η 3-NH(C 2H 4O) 2} 3 cores. The mechanism is used to develop a self-assembly approach to the first thermodynamically stable zirconium–titanium and hafnium–titanium precursors, Zr{μ-η 3-NH(C 2H 4O) 2} 3[Ti(O i Pr) 3] 2 ( 1) and Hf{μ-η 3-NH(C 2H 4O) 2} 3[Ti(O i Pr) 3] 2 ( 2). Mass spectrometric characterization of these compounds demonstrates their volatility. In addition to the solution stability of these compounds the volatility makes them attractive single source precursors for MOCVD and ALD applications. These precursors are also interesting candidates for application in sol–gel synthesis of microporous materials as the stability of the core prevents self-assembly of ligands on the outer surface of the primary particles formed during the hydrolysis. A n-propoxide analog of 1 can be prepared from zirconium n-propoxide but does not yield any crystalline material. It is demonstrated that 1 can be prepared from [Zr(O n Pr)(O i Pr) 3( i PrOH)] 2, however, with a lower yield compared to the use of zirconium isopropoxide. The single crystals obtained from systems containing zirconium isopropoxide, titanium isopropoxide and triethanolamine H 3tea turned out to be Ti 2(O i Pr) 2({μ-η 4-NH(C 2H 4O) 3} 2) 2 ( 4). Theoretical calculations indicate that the octacoordinate M{μ-η 4-N(C 2H 4O) 3} 2 core, anticipated in reaction with H 3tea, will have metal–nitrogen bonds that are too long for its stabilization. This explains why the formation of 4 is thermodynamically favored over the formation of heterometallic species.

Lewis acidity of group 14 tetrahalides in gas phase

Donor–acceptor complexes of silicon, germanium and tin tetrahalides with nitrogen-containing donors MX 4· nL (M=Si,Ge,Sn; X=F,Cl,Br; L=NH 3, Py, 2,2′bipy, 1,10-phen) have been theoretically studied at the B3LYP/DZP level of theory. It was found that some of the complexes possess negative Gibbs free energies, i.e. their decomposition into components is thermodynamically favorable. At the same time the formation of normal covalent (by means of the bond length) donor–acceptor bond was evidenced. Scanning of the potential energy surface (PES) revealed that such complexes are metastable species with barriers to dissociation 4–60 kJ mol −1. Energies of the element-nitrogen donor–acceptor bond are strongly dependent on the coordination polyhedron type; however, for the given type of the coordination polyhedron they are independent on the nature of the donor molecule (NH 3, Py, bipy, phen). It is shown that the reorganization energy of the acceptor molecule (36–280 kJ mol −1) governs the stability of the complexes. The reorganization energies of the donor molecules (1–32 kJ mol −1) are much smaller. Dissociation enthalpies of the complexes decrease in order Sn>Ge>Si, in line with increasing reorganization energy of the acceptor. At the same time, the donor–acceptor bond energy changes nonmonotonically: Ge<Si<Sn. The values of the gas phase dissociation enthalpy should not be used to estimate the metal-nitrogen bond energy. On the basis of theoretical studies, the most promising candidates for stable gaseous complexes of group 14 halides are complexes of tin tetrahalides with bidentate donor ligands, such as SnF 4phen.

Theoretical, spectroscopic, and mechanistic studies on transition‐metal dinitrogen complexes: Implications to reactivity and relevance to the nitrogenase problem

Dinitrogen complexes of transition metals exhibit different binding geometries of N2 (end-on terminal, end-on bridging, side-on bridging, side-on end-on bridging), which are investigated by spectroscopy and DFT calculations, analyzing their electronic structure and reactivity. For comparison, a bis(mu-nitrido) complex, where the N--N bond has been split, has been studied as well. Most of these systems are highly covalent, and have strong metal-nitrogen bonds. In the present review, particular emphasis is put on a consideration of the activation of the coordinated dinitrogen ligand, making it susceptible to protonation, reactions with electrophiles or cleavage. In this context, theoretical, structural, and spectroscopic data giving informations on the amount of charge on the N2 unit are presented. The orbital interactions leading to a charge transfer from the metals to the dinitrogen ligand and the charge distribution within the coordinated N2 group are analyzed. Correlations between the binding mode and the observed reactivity of N2 are discussed.

Synthesis of Metal Nanoparticles Stabilized by Metal−Carbon Bonds

A new method for the preparation of metal nanoparticles in organic media is proposed. This is based on the formation of metal-carbon bonds after reduction of the corresponding diazonium derivative of the capping ligand. The particles are very stable due to the strong metal-ligand covalent bond, and the proposed method appears to be an alternative for the preparation of monolayer-protected metal nanoparticles when the formation of metal-sulfur or metal-nitrogen bonds needs to be avoided.

Actinide(III) and lanthanide(III) complexes with nitrogen ligands: Counterions and ligand substituent effects on the metal–ligand bond

Relativistic density functional theory calculations are reported for actinide(III) (An=U, Am, Cm) and lanthanide(III) (Ln=La, Nd) complexes with tridentate aromatic nitrogen ligands. Calculations have been performed on 2,2′:6′,2″-terpyridine (Terpy) complexes with various species in the first coordination sphere of the metal ion besides one Terpy ligand (H 2O, Cl − and NO 3 − ) and on bis(1,2-4-triazin-3-yl)pyridine (Btp) complexes with various susbtituents attached to the triazine rings (CH 3, OCH 3 and CN). Metal–ligand bonds in trivalent lanthanum, neodynium, americium and curium complexes are predominantly ionic, and significant variations are found in metal–nitrogen bond lengths when the total charge of the complexes is changed by the number of counterions or when the charges on the coordinating nitrogen atoms are altered by substituents. Uranium–ligand bonds are more covalent and smaller variations are found in uranium–nitrogen bond distances. The most remarkable effect on uranium–ligand bonds is obtained by attaching CN groups to the Btp, uranium(5f)-to-Btp(π*) back-bonding is enhanced and uranium–nitrogen bonds are shortened.

Carbon dioxide and related heterocumulenes at zinc and lithium cations: bioinspired reactions and principles

This Perspective starts with the discussion of the properties of an interesting metalloenzyme (carbonic anhydrase, CA) that performs extremely successfully the activation of carbon dioxide. Conclusions from that are important for many synthetic procedures and include experimental and theoretical investigation (DFT calculations) of such metal mediated processes in the condensed and in the gas phase in which the zinc cation plays a dominant role. This is extended to the bio-analogue activation of further heterocumulenes such as COS, an important atmospheric trace gas, and CS(2). Novel metal complexes which serve as useful catalysts for the reactions (copolymerisations and cyclisation) of CO(2) and oxiranes are discussed subject to the inclusion of recently published DFT calculations. We continue with the discussion of the very general aspect of the insertion of CO(2) into metal-nitrogen bonds (formation of carbamates). This again is closely related to many biological or bio-analogue processes. We describe the synthesis and mechanistic aspects of characteristic metal carbamates of a wide variety of metals and include a discussion of the mechanistic aspects, especially for the formation of Mg(2+) and Li(+) carbamates and the formation of related cyclic products after addition of the heterocumulenes CO(2), Ph-NCO or CS(2) to novel ligands, the 4H-pyridin-1-ides which finally result in the formation of e.g. 1,3-thiazole-5(2H)-thiones.

Recoordination of a metal ion in the cavity of a crown compound: a theoretical study 2.* Effect of the metal ion— solvent interaction on the conformations of calcium complexes of arylazacrown ethers

The effect of the local interaction of a metal ion with the solvent on the conformations of calcium complexes of arylazacrown ethers and an azacrown-containing dye was studied using the density functional method with the PBE and B3LYP functionals. The structures were studied and the interaction energies were determined for the calcium complexes with n = 1–12 water or acetonitrile molecules. It was found that the inner coordination sphere of the free Ca2+ cation contains six H2O or seven MeCN molecules. The cation—acetonitrile interaction energy is higher than the cation—water interaction energy up to the moment the second solvation shell of the cation is almost complete (n = 11). The inner coordination sphere of Ca2+ in the macrocycle cavity contains at most three water molecules, while the fourth one is displaced to the second coordination sphere. Taking into account the local interaction with the solvent (H2O or MeCN), the conformers of the calcium complexes of arylazacrown ethers and the azacrown-containing dye were studied. It was shown that the presence of two to four water molecules in the coordination sphere of the cation reduces the relative energies of the conformers with broken metal—nitrogen bond, thus favoring ground-state metal recoordination.

A Gallium-Nitrogen Heteronorbornane With Bulky Tbutyl Substituents

Selective formation of 3,3,6,6-tetra-tbutyl-1,4-dimethyl-3,6-digallium-1,4-diaza-norborane is achieved by the reaction of bis(lithiomethyl-methylamino)methane with ditbutylgallium chloride by simultaneous formation of two dative metal-carbon and two metal-nitrogen bonds accompanied by two ring closures. Despite the high steric demand of the tbutyl groups, the norbornane-like structure is favoured over potential isomers containing three-membered rings and over polymeric aggregation. The compound was identified by elemental analysis, NMR spectroscopy (1H, 13C) and by determination of its crystal structure in which it is present as a monomer

Structural Properties and Dissociative Fluxional Motion of 2,9-Dimethyl-1,10-Phenanthroline in Platinum(II) Complexes

A dynamic 1H NMR study has been carried out on the fluxional motion of the symmetric chelating ligand 2,9-dimethyl-1,10-phenanthroline (Me2-phen) between nonequivalent exchanging sites in a variety of square-planar complexes of the type [Pt(Me)(Me2-phen)(PR3)]BArf, 1-14, (BArf = B[3,5-(CF3)2C6H3]4). In these compounds, the P-donor ligands PR3 encompass a wide range of steric and electronic characteristics [PR3 = P(4-XC6H4)3, X = H 1, F, 2, Cl 3, CF3 4, MeO 5, Me 6; PR3 = PMe(C6H5)2 7, PMe2(C6H5) 8, PMe3 9, PEt3 10, P(i-Pr)3 11, PCy(C6H5)2 12, PCy2(C6H5) 13, PCy3 14]. All complexes have been synthesized and fully characterized through elemental analysis, 1H and 31P{1H} NMR. X-ray crystal structures are reported for the compounds 8, 11, 14, and for [Pt(Me)(phen)(P(C6H5)3)]PF6 (15), all but the last showing loss of planarity and a significant rotation of the Me2-phen moiety around the N1-N2 vector. Steric congestion brought about by the P-donor ligands is responsible for tetrahedral distortion of the coordination plane and significant lengthening of the Pt-N2 (cis to phosphane) bond distances. Application of standard quantitative analysis of ligand effects (QALE) methodology enabled a quantitative separation of steric and electronic contributions of P-donor ligands to the values of the platinum-phosphorus 1J(PtP) coupling constants and of the free activation energies DeltaG++ of the fluxional motion of Me2-phen in 1-14. The steric profiles for both 1J(PtP) and DeltaG++ show the onset of steric thresholds (at cone angle values of 150 degrees and 148 degrees , respectively), that are associated with an overload of steric congestion already evidenced by the crystal structures of 11 and 14. The sharp increase of the fluxional rate of Me2-phen can be assumed as a perceptive kinetic tool for revealing ground-state destabilization produced by the P-donor ligands. The mechanism involves initial breaking of a metal-nitrogen bond, fast interconversion between two 14-electron three-coordinate T-shaped intermediates containing eta1-coordinated Me2-phen, and final ring closure. By use of the results from QALE regression analysis, a free-energy surface has been constructed that represents the way in which any single P-donor ligand can affect the energy of the transition state in the absence of aryl or pi-acidity effects.

Catalytic ammonia decomposition: miniaturized production of CO x-free hydrogen for fuel cells

Hydrogen, free from trace compounds that poison PEM fuel cell electrodes, is produced by catalytic decomposition of ammonia at low temperature in micro-fabricated reactors; this constitutes a possible option for easy and compact supply of fuel to miniaturized devices. A versatile method for depositing support materials in micro-fabricated reactors that also allows convenient introduction of active components by conventional impregnation methods is reported. This allows for easy screening of various metal catalyst since conventional catalyst preparation techniques can be applied in miniaturized form. For the catalytic decomposition of ammonia with transition metal catalysts, a volcano-type relation is found to exist analogously to that for the synthesis reaction but apparently shifted towards metals with lower metal–nitrogen bond energies. By use of supported ruthenium catalysts promoted with barium, highly efficient hydrogen production for miniaturized, and possibly mobile, units is demonstrated. If appropriate sequestration strategies are implemented at the central ammonia production facilities this provides a CO 2-free energy currency.

Synthesis, structure and biomimetic properties of Cu(II)–Cu(II) and Cu(II)–Zn(II) binuclear complexes: possible models for the chemistry of Cu–Zn superoxide dismutase

Four imidazolate-bridged binuclear copper(II)–copper(II) and copper(II)–zinc(II) complexes viz., [(Bipy) 2Cu–Im–Cu(Bipy) 2](ClO 4) 3 · CH 3OH, [(Phen) 2Cu–Im–Cu(Phen) 2](BF 4) 3 · 2CH 3OH, [(Bipy) 2Cu–Im–Zn(Bipy) 2](BF 4) 3, and [(Phen) 2Cu–Im–Zn(Phen) 2](BF 4) 3, (Bipy = 2,2′-Bipyridyl, Phen = 1-10-Phenanthroline and Im = imidazolate ion) were synthesized as a possible models for superoxide dismutase (SOD). Complex [(Bipy) 2Cu–Im–Cu(Bipy) 2](ClO 4) 3 · CH 3OH has been structurally characterized. This complex crystallizes in the triclinic space group P 1 ¯ , with the unit parameters a = 8.88(5) Å, b = 13.79(17) Å, c = 20.18(18) Å, α = 76.424(8)°, β = 85.888(6)°, γ = 82.213(7). The metal–nitrogen bond length from 1.972–2.273 Å and the distance Cu–Cu is 5.92 Å. The five-coordinate geometry about the copper(II) ion is square pyramidal. Magnetic moment and electron paramagnetic resonance (e.p.r.) spectral measurements of the homobinuclear complexes have shown an antiferromagnetic exchange interaction. From the e.p.r. and UV–Vis spectral measurement studies, these complexes have been found to be stable (pH 8.5–10.5 for 1, 10.5 for 2,3 and 8.5 for 4). These complexes catalyse the dismutation of superoxide radical ( O 2 - ) at biological pH. All the observations indicate that these complexes act as good possible models for superoxide dismutase.

Trioxorhenium(VII) Complexes with Imidazolin-2-iminato Ligands

Abstract The Staudinger reaction of the N-heterocyclic carbenes 1,3-di-tert-butylimidazolin-2-ylidene (1a), 1,3-dimesitylimidazolin-2-ylidene (1b) and 1,3-diisopropyl-4,5-dimethylimidazolin-2- ylidene (1c) with trimethylsilyl azide in boiling toluene furnishes the corresponding 2- (trimethylsilylimino)imidazolines 2a - c. Treatment of Re2O7 with a twofold excess of these N-silylated imines results in the formation of the imidazolin-2-iminato trioxorhenium(VII) complexes 3a - c and hexamethyldisiloxane, Me3SiOSiMe3. The molecular structures of 2a, 3a and 3b are reported. In addition, the X-ray crystal structure determination of complex 3c · H2O is presented, which has formed by hydrolysis and cleavage of the metal-nitrogen bond in 3c. 3c · H2O consists of 2-aminoimidazolium cations and tetraoxorhenate(VII) anions, which are linked by N-H-O hydrogen bonds.

Quantum-chemical calculations of the effect of cycloaliphatic groups in α-diimine and bis(imino)pyridine ethylene polymerization precatalysts on their stabilities with respect to deactivation reactions

For the first time, it is attempted to interpret an experimentally found enhancing effect of cycloaliphatic substituents in aromatic rings of Ni II- and Pd II-α-diimine and Fe II-bis(imino)pyridine ethylene polymerization precatalysts on their catalytic activities at elevated temperatures (60–80 °C), using quantum chemical density functional theory calculations of relative stabilities of the complexes with respect to different deactivation processes, including thermal decomposition and one-electron reduction. It was shown that the effect correlates with the calculated higher thermal stabilities of cycloalkyl-substituted Fe II-, Ni II- and Pd II-complexes as compared to the corresponding alkyl-substituted ones. Ni II- and Pd II-α-diimine complexes with cycloalkyl substituents are shown to be more stable than their alkyl-substituted analogues with respect to both thermal decomposition and one-electron reduction. The averaged difference of the thermal decomposition energies between the complexes with cycloaliphatic substituents on one side and aliphatic ones on the other side is ∼2.3 kcal/mol, corresponding to ∼30 times lower equilibrium constant of the thermal decomposition reaction for the cycloalkyl-containing complexes. For the Fe II- and Pd II-complexes, the thermal stability correlates with the calculated overlap population of the metal–nitrogen bonds. It was shown that the structure of o-substituents (cycloalkyls vs. alkyls) in the phenyl rings of the ligands does not affect the reaction energies for the transformation reactions of the precatalysts into their corresponding active catalytic cationic forms.

Composition and formation mechanism of zirconium oxynitride films produced by reactive direct current magnetron sputtering

Direct current magnetron sputtered zirconium oxynitride films show an improvement in both deposition rate and physical properties compared to zirconium oxide. Here we seek to understand these beneficial effects and report on the film composition and crystallographic structure. Based on a thermochemical description together with a modeling of formation kinetics we propose a film formation mechanism, which explains many of the observations. Rutherford backscattering spectroscopy (RBS) shows early nitrogen incorporation at 64% N2 flow in disagreement with the predictions of thermochemistry. The stoichiometry is only successfully simulated with the use of an expanded Berg–Larsson model with a low replacement coefficient of about 0.1 of nitrogen by oxygen after metal-nitrogen bond formation. The deviation from complete replacement as predicted by thermodynamics illustrates the importance of kinetics in film formation. The model further successfully predicts the variation of the mass deposition rate. The X-ray diffraction analyses suggest that, within the crystalline phase, nitrogen atoms occupy oxygen sites, resulting in an unchanged zirconium oxide structure. (© 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

Synthesis and Structure of an Aluminium-Nitrogen Heteronorbornane with Bulky tButyl Substituents and the Crystal Structure of Tri(tbutyl)aluminium

The reaction of bis(lithiomethyl-methylamino)methane with ditbutylaluminium chloride leads to the formation of 3,3,6,6-tetra-tbutyl-1,4-dimethyl-3,6-dialumina-1,4-diaza-norbornane by simultaneous formation of two metal-carbon and two metal nitrogen bonds accompanied by two ring closure reactions. The compound was identified by an NMR analysis (1H, 13C, 27Al) and by determination of its crystal structure. Despite the high steric demand of the tbutyl groups, the norbornane-basket structure is favoured over potential isomers containing three-membered rings and over polymeric aggregation. The crystal structure of tri(tbutyl)aluminium has been determined. tBu3Al crystallizes as a monomer, with the molecules interconnected by weak secondary Al···C contacts (2.95 Å) leading to a slight deviation of the AlC3 units from a planar coordination geometry at the Al atoms

Recoordination of a metal ion in the cavity of an arylazacrown ether: Model study of the conformations and microsolvation of calcium complexes of arylazacrown ethers

AbstractPhotoinduced recoordination of Ca2+ complexes of photochromic azacrown ethers is studied by the density functional method using model arylazacrown ethers and a real azacrown‐containing styryl dye. Two types of previously found conformations of the crown ether–calcium complexes, axial and equatorial, are studied, taking into account water molecules in the first coordination sphere of the cation. It is found that the first coordination sphere of the cation contains no more than three water molecules, the fourth one belonging to the second coordination sphere. The presence of three or four water molecules in the coordination sphere of the cation decreases relative energies of the conformations with broken metal–nitrogen bond, thus favoring metal recoordination. In the azacrown‐containing styryl dye, this leads to the ground‐state equilibrium (i.e., tautomerism) between the axial and equatorial forms of the complex. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2004

Endohedral nitride cluster fullerenes: Formation and spectroscopic analysis of L 3− xM xN@C 2 n (0≤ x≤3; N=39,40)

The class of endohedral fullerenes is demonstrated in its large variety by the new type of nitride cluster fullerenes. These endohedral fullerenes were obtained as the most abundant fullerenes in the soot extract. This is reached by the concept of reactive gas atmosphere in arc burning fullerene production. The chemical reactions in the gas atmosphere during the production are described. Different nitride cluster fullerenes were produced with selectivity up to 90% by using reactive gas addition to the cooling gas of the arc burning process. Fullerenes prepared by this method are Sc 3N@C 80, Sc 3− x Er x N@C 80 ( x=1,2,3), Sc 3N@C 78, Y 3N@C 80, Ho 3N@C 80 and Tb 3N@C 80. By studying Vis/NIR spectra, it is demonstrated that nitride cluster fullerenes are generally large band-gap endohedrals. Therefore, the M 3N@C 80 structures are very stable and suitable for applications. This stability is caused by a charge transfer from the cluster to the carbon cage and the formation of a M 3N–carbon cage bond as well as covalent metal–nitrogen bonds. Infrared spectroscopy of M 3N@C 80 was used to study the metal and cage size influence on the structure of the nitride cluster.

Recoordination of a metal ion in the cavity of a crown compound: a theoretical study. 1. Conformers of arylazacrown ethers and their complexes with Ca2+cation

Photoinduced recoordination of Ca2+ complexes of the photochromic azacrown ethers is studied by the density functional method. The study included model arylazacrown ethers containing various acceptor groups in the aromatic ring in the para position to the azacrown ether moiety and a real azacrown-containing styryl dye. It is found that both free azacrown ethers and their complexes can adopt two types of conformations: (1) axial conformations, in which the aromatic ring axis passing through the crown ether nitrogen Ncr and the opposite atom of the aromatic ring is perpendicular to the root-mean-square (RMS) plane of the crown ether (least-squares fitted plane for all the crown ether atoms), and (2) equatorial conformations, in which the aromatic ring axis only slightly deflects from the RMS plane of the crown ether. In the equatorial conformers, the metal cation is coordinated only to the O atoms of the azacrown ether cycle, the metal—nitrogen bond is broken, and Ncr is conjugated with the aromatic ring. In the axial conformers, the metal cation is additionally coordinated to Ncr. It is found that the presence of an acceptor group bearing a formal positive charge decreases the relative energy of the equatorial conformer and favors metal—nitrogen bond dissociation, which results in the recoordination of the metal cation. However, a long distance between the charged group and Ncr has the reverse effect. The photoinduced recoordination observed in the alkaline-earth metal complexes of the photochromic azacrown ethers is explained by the transitions between the axial and equatorial conformers facilitated by the charge transfer in the excited state of the complex.

Reactivity of vapor-deposited metal atoms with nitrogen-containing polymers and organic surfaces studied by in situ XPS

The reactivity of vapor-deposited Fe, Ni, Cu and Au atoms with nylon 6 ([NH(CH 2) 5CO] n ), a nitrogen ion beam-modified polyethylene substrate (N-PE) and a nitrile-terminated self-assembled monolayer (CN-SAM) have been investigated using in situ X-ray photoelectron spectroscopy (XPS). On nylon 6, Fe deposition produced FeO and FeN bonded species as well as an amorphous carbonaceous film at the metal/polymer interface. Metal–nitrogen bond formation was also observed during Ni and Cu deposition on nylon 6, although the CO functionality remained intact, and no evidence was found for the production of either CuO or NiO species. Deposition of Fe and Ni on N-PE and the CN-SAM also resulted in the production of metal–nitrogen bonds. In contrast, Cu exhibited little or no reactivity with N-PE and failed to activate CN bond cleavage in the CN-SAM, while the deposition of Au produced a purely metallic overlayer on all three substrates. The relative reactivity of different polymer functional groups in the present study was found to be largely determined by their respective bond strengths, while the overall metal reactivity trend (Fe>Ni>Cu>Au) can be correlated with the strength of metal–oxygen and metal–nitrogen bonds that can potentially form during metallization.