Environmental plastics in the context of UV radiation, climate change, and the Montreal Protocol.

There are close links between solar UV radiation, climate change, and plastic pollution. UV-driven weathering is a key process leading to the degradation of plastics in the environment but also the formation of potentially harmful plastic fragments such as micro- and nanoplastic particles. Estimates of the environmental persistence of plastic pollution, and the formation of fragments, will need to take in account plastic dispersal around the globe, as well as projected UV radiation levels and climate change factors.

Plastics in the environment in the context of UV radiation, climate change and the Montreal Protocol: UNEP Environmental Effects Assessment Panel, Update 2023.

This Assessment Update by the Environmental Effects Assessment Panel (EEAP) of the United Nations Environment Programme (UNEP) considers the interactive effects of solar UV radiation, global warming, and other weathering factors on plastics. The Assessment illustrates the significance of solar UV radiation in decreasing the durability of plastic materials, degradation of plastic debris, formation of micro- and nanoplastic particles and accompanying leaching of potential toxic compounds. Micro- and nanoplastics have been found in all ecosystems, the atmosphere, and in humans. While the potential biological risks are not yet well-established, the widespread and increasing occurrence of plastic pollution is reason for continuing research and monitoring. Plastic debris persists after its intended life in soils, water bodies and the atmosphere as well as in living organisms. To counteract accumulation of plastics in the environment, the lifetime of novel plastics or plastic alternatives should better match the functional life of products, with eventual breakdown releasing harmless substances to the environment.

Nanotechnology in wood science: Innovations and applications.

Application of nanomaterials is gaining tremendous interest in the field of wood science and technology for value addition and enhancing performance of wood and wood-based composites. This review focuses on the use of nanomaterials in improving the properties of wood and wood-based materials and protecting them from weathering, biodegradation, and other deteriorating agents. UV-resistant, self-cleaning (superhydrophobic) surfaces with anti-microbial properties have been developed using the extraordinary features of nanomaterials. Scratch-resistant nano-coatings also improve durability and aesthetic appeal of wood. Moreover, nanomaterials have been used as wood preservatives for increasing the resistance against wood deteriorating agents such as fungi, termites and borers. Wood can be made more resistant to ignition and slower to burn by introducing nano-clays or nanoparticles of metal-oxides. The use of nanocellulose and lignin nanoparticles in wood-based products has attracted huge interest in developing novel materials with improved properties. Nanocellulose and lignin nanoparticles derived/synthesized from woody biomass can enhance the mechanical properties such as strength and stiffness and impart additional functionalities to wood-based products. Cellulose nano-fibres/crystals find application in wide areas of materials science like reinforcement for composites. Incorporation of nanomaterials in resin has been used to enhance specific properties of wood-based composites. This review paper highlights some of the advancements in the use of nanotechnology in wood science, and its potential impact on the industry.

Transparent wood composite prepared from two commercially important tropical timber species.

Transparent wood (TW) has garnered significant global attention due to its unique properties. In this study, TW composites were fabricated using two timber species of different density classes: Ailanthus triphysa (common name: Ailanthus wood) and Hevea brasiliensis (common name: Rubberwood). Sodium hydroxide (NaOH) and Hydrogen peroxide-based alkali method was used to modify the lignin in these veneer samples, producing a white cellulose template with a fully intact hierarchical cell structure. Subsequently, a cost-effective thermosetting unsaturated polyester resin (UPR) was infiltrated into the redesigned framework and polymerized to create rigid nanostructured transparent composites. High optical haze (of 94% and 89%) and favourable light transmittance of 59 and 55 percent were exhibited by the UPR-TW composites made from rubberwood and ailanthus wood, respectively. TW was characterised using Scanning electron microscopy and Fourier-transform infrared spectroscopy. The mechanical properties of TW were measured and compared with those of natural wood and pure-polymer. Furthermore, the anisotropic light diffusion behaviour displayed by TW in accordance with the fibre orientation indicates the utility of material as a potential light shaping device. Therefore, a cost-effective and commercially viable strategy to fabricate multipurpose TW composites using a combination of lesser-known timber species (LKTS) and UPR resin was successfully demonstrated.

The success of the Montreal Protocol in mitigating interactive effects of stratospheric ozone depletion and climate change on the environment.

The Montreal Protocol and its Amendments have been highly effective in protecting the stratospheric ozone layer, preventing global increases in solar ultraviolet-B radiation (UV-B; 280-315 nm) at Earth's surface, and reducing global warming. While ongoing and projected changes in UV-B radiation and climate still pose a threat to human health, food security, air and water quality, terrestrial and aquatic ecosystems, and construction materials and fabrics, the Montreal Protocol continues to play a critical role in protecting Earth's inhabitants and ecosystems by addressing many of the United Nations Sustainable Development Goals.

UV stabilization of wood by nano metal oxides dispersed in propylene glycol.

Nanoparticles of some of the metal oxides are known to have high UV protective efficiency. The UV filtering efficiency of nanoparticles invariably depends on their size and stability in the dispersion. In the present work, a stable dispersion of nanoparticles of three metal oxides, zinc oxide (ZnO), cerium oxide (CeO2) and titanium dioxide (TiO2), was prepared in propylene glycol (PG) using ultrasonication. The method is easy and useful as no additional surfactant or dispersant is needed. The particle size and its distribution was confirmed by Scanning Electron Microscopy and Dynamic Light Scattering. The stability of dispersion was assessed by UV-visible absorption spectroscopy. The UV stability of wood surfaces of Wrightia tinctoria coated with nanodispersions of ZnO, CeO2 and TiO2 was evaluated under laboratory conditions in an accelerated weathering tester. Changes in the colour and FTIR spectra of exposed specimens were measured periodically. Rapid colour darkening (yellowing) was observed in uncoated and PG coated specimens. In contrast, nanodispersion coated specimens prevented photo-yellowing considerably with significant reduction in colour changes examined by CIE L*, a*, b* and ΔE*. Increase in concentration of nanoparticles in the dispersion imparted higher resistance to UV induced degradation. However, increased concentration of nanoparticles reduced the transparency of the coating. FTIR analysis indicated rapid degradation of lignin in uncoated and PG coated specimens due to UV exposure. Coating of wood surfaces with nanodispersions restricted lignin degradation. The study also demonstrates the potential of propylene glycol as a dispersant for developing stable and efficient UV protective nanodispersions for wood coating.

UV resistance and dimensional stability of wood modified with isopropenyl acetate.

Chemical modification of Rubberwood (Hevea brasiliensis Müll.Arg) with isopropenyl acetate (IPA) in the presence of anhydrous aluminum chloride as a catalyst has been carried out under solvent free conditions. The level of modification was estimated by determining the weight percent gain and modified wood was characterized by FTIR-ATR and CP/MAS (13)C NMR spectroscopy. The effect of catalyst concentration on WPG was studied. UV resistance, moisture adsorption and dimensional stability of modified wood were evaluated. UV resistance of modified wood was evaluated by exposing unmodified and modified wood to UV irradiation in a QUV accelerated weathering tester. Unmodified wood showed rapid color changes and degradation of lignin upon exposure to UV light. Chemical modification of wood polymers with IPA was effective in reducing light induced color changes (photo-yellowing) at wood surfaces. In contrast to unmodified wood, modified wood exhibited bleaching. FTIR analysis of modified wood exposed to UV light indicated stabilization of wood polymers against UV degradation. Modified wood showed good dimensional stability and hydrophobicity. Thermogravimetric analysis showed that modification with IPA improved thermal stability of wood. Improved dimensional stability and UV resistance of modified wood indicates IPA as a promising reagent since there is no acid byproduct of reaction as observed in case of other esterification reactions.

Dispersion-Corrected Relativistic Density Functional Theory (DFT) Calculations of Structure and (119)Sn Mössbauer Parameters for M≡SnR Bonding in Filippou's Stannylidyne Complexes of Molybdenum and Tungsten.

(119)Sn Mössbauer isomer shift (IS) and quadrupole splitting (ΔEQ) for M≡SnR bonding in metal-stannylidyne complexes trans-[Cl(PMe3)4Mo≡Sn-R] (1), trans-[Cl(PMe3)4W≡Sn-R] (2), trans-[Cl(dppe)2Mo≡Sn-R] (3), trans-[Cl(dppe)2W≡Sn-R] (4), [(dppe)2Mo≡Sn-R](+) (5), [(dppe)2W≡Sn-R](+) (6) (R = C6H3-2,6-Mes2) have been investigated for the first time. Calculations of optimized structures and (119)Sn Mössbauer parameters were carried out at the DFT/TPSS-D3(BJ)/TZVPP/ZORA level of theory. The calculated geometry parameters of stannylidyne complexes of molybdenum and tungsten (1-6) are in good agreement with experimental values of W-Sn and Sn-C bond distances. The calculated values of the isomer shift for the complexes (1-6) are almost same to the experimental values (within ±0.1 mm/s). Experimental values (ISexptl, 2.38-2.50 mm/s) and calculated values (IScalcd, 2.37-2.49 mm/s) of isomer shifts indicate that the oxidation state of tin in the studied complexes with M≡Sn-R bonding is Sn(II). The variations of ISexptl, as a function of Sn s electrons (Ns(Sn)), also exhibit a linear trend. (IS = 0.477Ns(Sn) - 1.888, R(2) = 0.9973). Calculated values of isomer shift (IScalcd) using the linear regression with the Ns(Sn) electron density are in excellent concord with the ISexptl.The calculated values of nuclear quadrupole splitting parameters (ΔEQ(calcd)) of (119)Sn using the relation ΔEQ(calcd) = (0.540 + 0.28) V are in agreement with the experimental values.

New bonding modes of carbon and heavier group 14 atoms Si-Pb.

Recent theoretical studies are reviewed which show that the naked group 14 atoms E = C-Pb in the singlet (1)D state behave as bidentate Lewis acids that strongly bind two σ donor ligands L in the donor-acceptor complexes L→E←L. Tetrylones EL2 are divalent E(0) compounds which possess two lone pairs at E. The unique electronic structure of tetrylones (carbones, silylones, germylones, stannylones, plumbylones) clearly distinguishes them from tetrylenes ER2 (carbenes, silylenes, germylenes, stannylenes, plumbylenes) which have electron-sharing bonds R-E-R and only one lone pair at atom E. The different electronic structures of tetrylones and tetrylenes are revealed by charge- and energy decomposition analyses and they become obvious experimentally by a distinctively different chemical reactivity. The unusual structures and chemical behaviour of tetrylones EL2 can be understood in terms of the donor-acceptor interactions L→E←L. Tetrylones are potential donor ligands in main group compounds and transition metal complexes which are experimentally not yet known. The review also introduces theoretical studies of transition metal complexes [TM]-E which carry naked tetrele atoms E = C-Sn as ligands. The bonding analyses suggest that the group-14 atoms bind in the (3)P reference state to the transition metal in a combination of σ and π∥ electron-sharing bonds TM-E and π⊥ backdonation TM→E. The unique bonding situation of the tetrele complexes [TM]-E makes them suitable ligands in adducts with Lewis acids. Theoretical studies of [TM]-E→W(CO)5 predict that such species may becomes synthesized.

Assessment of density functionals and paucity of non-covalent interactions in aminoylyne complexes of molybdenum and tungsten [(η(5)-C5H5)(CO)2M≡EN(SiMe3)(R)] (E = Si, Ge, Sn, Pb): a dispersion-corrected DFT study.

Electronic, molecular structure and bonding energy analyses of the metal-aminosilylyne, -aminogermylyne, -aminostannylyne and -aminoplumbylyne complexes [(η(5)-C5H5)(CO)2M[triple bond, length as m-dash]EN(SiMe3)(Ph)] (M = Mo, W) and [(η(5)-C5H5)(CO)2Mo[triple bond, length as m-dash]GeN(SiMe3)(Mes)] have been investigated at DFT, DFT-D3 and DFT-D3(BJ) levels using BP86, PBE, PW91, RPBE, TPSS and M06-L functionals. The performance of metaGGA functionals for the geometries of aminoylyne complexes is better than GGA functionals. Significant dispersion interactions between OH, EC(O) and EH pairs appeared in the dispersion-corrected geometries. The non-covalent distances of these interactions follow the order DFT > DFT-D3(BJ) > DFT-D3. The values of Nalewajski-Mrozek bond order (1.22-1.52) and Pauling bond order (2.23-2.59) of the optimized structures at BP86/TZ2P indicate the presence of multiple bonds between metal and E atoms. The overall electronic charges transfer from transition-metal fragments to ligands. The topological analysis based on QTAIM has been performed to determine the analogy of non-covalent interactions. The strength of M[triple bond, length as m-dash]EN(SiMe3)(R) bonds has been evaluated by energy decomposition analysis. The electrostatic interactions are almost equal to orbital interactions. The M ← E σ-donation is smaller than the M → E π-back donation. Upon going from E = Si to E = Pb, the M-E bond orders decrease as Si > Ge > Sn > Pb, consistent with the observed geometry trends. The M-E uncorrected bond dissociation energies vary with the density functionals as RPBE < BP86 < PBE < TPSS < PW91. The largest DFT-D3 dispersion corrections to the BDEs correspond to the BP86 functional, ranging between 5.6-8.1 kcal mol(-1), which are smaller than the DFT-D3(BJ) dispersion corrections (10.1-12.0 kcal mol(-1)). The aryl substituents on nitrogen have an insignificant effect on M-E-N bending. The bending of the M-E-N bond angle has been discussed in terms of Jahn-Teller distortion. The larger noncovalent interaction and smaller absolute values of ΔE(HOMO-LUMO) with the M06-L functional are responsible for lowering the M-E-N bond angle.

Structure and Bonding analysis of the cationic electrophilic phosphinidene complexes of iron, ruthenium, and osmium [(η(5)-C5Me5)(CO)2M{PN(i)Pr2}]+, [(η(5)-C5H5)(CO)2M{PNR2}]+ (R = Me, (i)Pr), and [(η(5)-C5H5)(PMe3)2M{PNMe2}]+ (M = Fe, Ru, Os).

Quantum-chemical DFT calculations for the electronic, molecular structure and M-PNR(2) bonding analyses of the experimentally known cationic electrophilic phosphinidene complexes [(η(5)-C(5)Me(5))(CO)(2)M{PN(i)Pr(2)}](+) and of the model complexes [(η(5)-C(5)H(5))(CO)(2)M{PNR(2)}](+) (R = (i)Pr, Me) and [(η(5)-C(5)H(5))(PMe(3))(2)M{PNMe(2)}](+) were carried out using BP86/TZ2P/ZORA level of theory. The calculated geometrical parameters of the studied complexes are in good agreement with the reported experimental values. The short M-P bond distances and calculated Pauling bond orders (range of 1.23-1.68), suggest the presence of M-P multiple bond characters. The Hirshfeld charge analysis shows that the overall charge flows from phosphinidene ligand to metal fragment. The M-P σ-bonding orbitals are well-occupied (>1.80e). The energy decomposition analysis revealed that the contribution of the electrostatic interaction ΔE(elstat) is, in all studied complexes, significantly larger (55.2-62.6%) than the orbital interactions ΔE(orb). The orbital interactions between metal and PNR(2) in [(η(5)-C(5)H(5))(L)(2)M{PNR(2)}](+) arise mainly from M ← PNR(2) σ-donation. The π-bonding contribution (19-36%) is much smaller than the σ-bonding. The interaction energies, as well as bond dissociation energies, depend on the auxiliary ligand framework around the metal and decrease in the order (η(5)-C(5)H(5)) > (η(5)-C(5)Me(5)) and CO > PMe(3). Upon substitution of R = (i)Pr with smaller group R = Me, the M-PNR(2) bond strength slightly decreases.

Photodegradation of thermally modified wood.

Natural wood, being biological material, undergoes rapid degradation by ultraviolet (UV) radiations and other environmental factors under outdoor exposure. In order to protect wood from such degradation, the chemical structure of wood is altered by chemical modification or heat treatment. In the present study, heat treated specimens of rubberwood (Hevea brasiliensis) were exposed to xenon light source in a weather-o-meter for different periods up to 300 h. Photostability of modified and unmodified wood was evaluated in terms of colour and chemical changes. Light coloured untreated wood became dark upon UV irradiation whereas, dark colour of heat treated wood lightened on UV exposure. CIE lightness parameter (L(*)) decreased for untreated wood whereas its value increased for heat treated wood upon irradiation. Other colour coordinates a(*) and b(*) increased with exposure duration for both untreated and heat treated wood. The overall colour change (ΔE(*)) increased for both untreated and heat treated wood. The Fourier Transform Infrared (FTIR) spectroscopic studies revealed severe lignin degradation of heat treated wood due to UV light exposure. Colour changes and FTIR measurements indicate that thermal modification of wood was ineffective in restricting light induced colour changes and photodegradation of wood polymers.

What is the best bonding model of the (σ-H-BR) species bound to a transition metal? Bonding analysis in complexes [(H)2Cl(PMe3)2M(σ-H-BR)] (M = Fe, Ru, Os).

Density Functional Theory calculations have been performed for the σ-hydroboryl complexes of iron, ruthenium and osmium [(H)(2)Cl(PMe(3))(2)M(σ-H-BR)] (M = Fe, Ru, Os; R = OMe, NMe(2), Ph) at the BP86/TZ2P/ZORA level of theory in order to understand the interactions between metal and HBR ligands. The calculated geometries of the complexes [(H)(2)Cl(PMe(3))(2)Ru(HBNMe(2))], [(H)(2)Cl(PMe(3))(2)Os(HBR)] (R = OMe, NMe(2)) are in excellent agreement with structurally characterized complexes [(H)(2)Cl(P(i)Pr(3))(2)Os(σ-H-BNMe(2))], [(H)(2)Cl(P(i)Pr(3))(2)Os{σ-H-BOCH(2)CH(2)OB(O(2)CH(2)CH(2))}] and [(H)(2)Cl(P(i)Pr(3))(2)Os(σ-H-BNMe(2))]. The longer calculated M-B bond distance in complex [(H)(2)Cl(PMe(3))(2)M(σ-H-BNMe(2))] are due to greater B-N π bonding and as a result, a weaker M-B π-back-bonding. The B-H2 bond distances reveal that (i) iron complexes contain bis(σ-borane) ligand, (ii) ruthenium complexes contain (σ-H-BR) ligands with a stretched B-H2 bond, and (iii) osmium complexes contain hydride (H2) and (σ-H-BR) ligands. The H-BR ligands in osmium complexes are a better trans-directing ligand than the Cl ligand. Values of interaction energy, electrostatic interaction, orbital interaction, and bond dissociation energy for interactions between ionic fragments are very large and may not be consistent with M-(σ-H-BR) bonding. The EDA as well as NBO and AIM analysis suggest that the best bonding model for the M-σ-H-BR interactions in the complexes [(H)(2)Cl(PMe(3))(2)M(σ-H-BR)] is the interaction between neutral fragments [(H)(2)Cl(PMe(3))(2)M] and [σ-H-BR]. This becomes evident from the calculated values for the orbital interactions. The electron configuration of the fragments which is shown for C in Fig. 1 experiences the smallest change upon the M-σ-H-BR bond formation. Since model C also requires the least amount of electronic excitation and geometry changes of all models given by the ΔE(prep) values, it is clearly the most appropriate choice of interacting fragments. The π-bonding contribution is 14-22% of the total orbital contribution.

Structure and bonding analysis of dimethylgallyl complexes of iron, ruthenium, and osmium [(η5-C5H5)(CO)2M(GaMe2)] and [(η5-C5H5)(Me3P)2M(GaMe2)].

Density functional theory calculations have been performed for the dimethylgallyl complexes of iron, ruthenium, and osmium [(η(5)-C(5)H(5))(L)(2)M(GaMe(2)] (M = Fe, Ru, Os; L = CO, PMe(3)) at the DFT/BP86/TZ2P/ZORA level of theory. The calculated geometry of the iron complex [(η(5)-C(5)H(5))(CO)(2)Fe(GaMe(2))] is in excellent agreement with structurally characterized complex [(η(5)-C(5)H(5))(CO)(2)Fe(Ga(t)Bu(2))]. The Pauling bond order of the optimized structures shows that the M-Ga bonds in these complexes are nearly M-Ga single bond. Upon going from M = Fe to M = Os, the calculated M-Ga bond distance increases, while on substitution of the CO ligand by PMe(3), the calculated M-Ga bond distances decrease. The π-bonding component of the total orbital contribution is significantly smaller than that of σ-bonding. Thus, in these complexes the GaX(2) ligand behaves predominantly as a σ-donor. The contributions of the electrostatic interaction terms ΔE(elstat) are significantly smaller in all gallyl complexes than the covalent bonding ΔE(orb) term. The absolute values of the ΔE(Pauli), ΔE(int), and ΔE(elstat) contributions to the M-Ga bonds increases in both sets of complexes via the order Fe < Ru < Os. The Ga-C(CO) and Ga-P bond distances are smaller than the sum of van der Waal radii and, thus, suggest the presence of weak intermolecular Ga-C(CO) and Ga-P interactions.

Structure and bonding energy analysis of cationic metal-ylyne complexes of molybdenum and tungsten, [(MeCN)(PMe3)4M≡EMes]+ (M = Mo, W; E = Si, Ge, Sn, Pb): a theoretical study.

The molecular and electronic structures and bonding analysis of terminal cationic metal-ylyne complexes (MeCN)(PMe(3))(4)M≡EMes](+) (M = Mo, W; E = Si, Ge, Sn, Pb) were investigated using DFT/BP86/TZ2P/ZORA level of theory. The calculated geometrical parameters for the model complexes are in good agreement with the reported experimental values. The M-E σ-bonding orbitals are slightly polarized toward E except in the complex [(MeCN)(PMe(3))(4)W(SnMes)](+), where the M-E σ-bonding orbital is slightly polarized toward the W atom. The M-E π-bonding orbitals are highly polarized toward the metal atom. In all complexes, the π-bonding contribution to the total M≡EMes bond is greater than that of the σ-bonding contribution and increases upon going from M = Mo to W. The values of orbital interaction ΔE(orb) are significantly larger in all studied complexes I-VIII than the electrostatic interaction ΔE(elstat). The absolute values of the interaction energy, as well as the bond dissociation energy, decrease in the order Si > Ge > Sn > Pb, and the tungsten complexes have stronger bonding than the molybdenum complexes.

Nature of M-Ga Bonds in cationic metal-gallylene complexes of iron, ruthenium, and osmium, [(η5-C5H5)(L)2M(GaX)]+: a theoretical study.

Density Functional Theory calculations have been performed for the cationic half-sandwich gallylene complexes of iron, ruthenium, and osmium [(η(5)-C(5)H(5))(L)(2)M(GaX)](+) (M = Fe, L = CO, PMe(3); X = Cl, Br, I, NMe(2), Mes; M = Ru, Os: L = CO, PMe(3); X = I, NMe(2), Mes) at the BP86/TZ2P/ZORA level of theory. Calculated geometric parameters for the model iron iodogallylene system [(η(5)-C(5)H(5))(Me(3)P)(2)Fe(GaI)](+) are in excellent agreement with the recently reported experimental values for [(η(5)-C(5)Me(5))(dppe)Fe(GaI)](+). The M-Ga bonds in these systems are shorter than expected for single bonds, an observation attributed not to significant M-Ga π orbital contributions, but due instead primarily to high gallium s-orbital contributions to the M-Ga bonding orbitals. Such a finding is in line with the tenets of Bent's Rule insofar as correspondingly greater gallium p-orbital character is found in the bonds to the (more electronegative) gallylene substituent X. Consistent with this, ΔE(σ) is found to be overwhelmingly the dominant contribution to the orbital interaction between [(η(5)-C(5)H(5))(L)(2)M](+) and [GaX] fragments (with ΔE(π) equating to only 8.0-18.6% of the total orbital contributions); GaX ligands thus behave as predominantly σ-donor ligands. Electrostatic contributions to the overall interaction energy ΔE(int) are also very important, being comparable in magnitude (or in some cases even larger than) the corresponding orbital interactions.

Nature of bonding in terminal borylene, alylene, and gallylene complexes of vanadium and niobium [(η(5)-C5H5)(CO)3M(ENR2)] (M = V, Nb; E = B, Al, Ga; R = CH3, SiH3, CMe3, SiMe3): a DFT study.

Density functional theory calculations have been performed for the terminal borylene, alylene, and gallylene complexes [(η(5)-C(5)H(5))(CO)(3)M(ENR(2))] (M = V, Nb; E = B, Al, Ga; R = CH(3), SiH(3), CMe(3), SiMe(3)) using the exchange correlation functional BP86. The calculated geometry parameters of vanadium borylene complex [(η(5)-C(5)H(5))(CO)(3)V{BN(SiMe(3))(2)}] are in excellent agreement with their available experimental values. The M-B bonds in the borylene complexes have partial M-B double-bond character, and the B-N bonds are nearly B═N double bonds. On the other hand, the M-E bonds in the studied metal alylene and gallylene complexes represent M-E single bonds with a very small M-E π-orbital contribution, and the Al-N and Ga-N bonds in the complexes have partial double-bond character. The orbital interactions between metal and ENR(2) in [(η(5)-C(5)H(5))(CO)(3)M(ENR(2))] arise mainly from M ← ENR(2) σ donation. The π-bonding contribution is, in all complexes, much smaller. The contributions of the electrostatic interactions ΔE(elstat) are significantly larger in all borylene, alylene, and gallylene complexes than the covalent bonding ΔE(orb); that is, the M-ENR(2) bonding in the complexes has a greater degree of ionic character.

Nature of M-Ga bonds in dihalogallyl complexes (η5-C5H5)(Me3P)2M(GaX2) (M = Fe, Ru, Os) and (η5-C5H5)(OC)2Fe(GaX2) (X = Cl, Br, I): a DFT study.

Density functional theory (DFT) calculations have been performed on the terminal dihalogallyl complexes of iron, ruthenium, and osmium (η(5)-C(5)H(5))(Me(3)P)(2)M(GaX(2)) (M = Fe, Ru, Os; X = Cl, Br, I) and (η(5)-C(5)H(5))(OC)(2)Fe(GaX(2)) (X = Cl, Br, I) at the BP86/TZ2P/ZORA level of theory. On the basis of analyses suggested by Pauling, the M-Ga bonds in all of the dihalogallyl complexes are shorter than M-Ga single bonds; moreover, on going from X = Cl to X = I, the optimized M-Ga bond distances are found to increase. From the perspective of covalent bonding, however, π-symmetry contributions are, in all complexes, significantly smaller than the corresponding σ-bonding contribution, representing only 4-10% of the total orbital interaction. Thus, in these GaX(2) complexes, the gallyl ligand behaves predominantly as a σ donor, and the short M-Ga bond lengths can be attributed to high gallium s-orbital character in the M-Ga σ-bonding orbitals. The natural population analysis (NPA) charge distributions indicate that the group 8 metal atom carries a negative charge (from -1.38 to -1.62) and the gallium atom carries a significant positive charge in all cases (from +0.76 to +1.18). Moreover, the contributions of the electrostatic interaction terms (ΔE(elstat)) are significantly larger in all gallyl complexes than the covalent bonding term (ΔE(orb)); thus, the M-Ga bonds have predominantly ionic character (60-72%). The magnitude of the charge separation is greatest for dichlorogallyl complexes (compared to the corresponding GaBr(2) and GaI(2) systems), leading to a larger attractive ΔE(elstat) term and to M-Ga bonds that are stronger and marginally shorter than in the dibromo and diiodo analogues.

Structure and bonding energy analysis of M-Ga bonds in dihalogallyl complexes trans-[X(PMe3)2M(GaX2)] (M = Ni, Pd, Pt; X = Cl, Br, I).

Geometry, electronic structure, and bonding analysis of the terminal neutral dihalogallyl complexes of nickel, palladium, and platinum trans-[X(PMe(3))(2)M(GaX(2))] (M = Ni, Pd, Pt; X = Cl, Br, I) were investigated at the BP86 level of theory. The calculated geometries of platinum gallyl complexes trans-[X(PMe(3))(2)Pt(GaX(2))] (X = Br, I) are in excellent agreement with structurally characterized platinum complexes trans-[X(PCy(3))(2)M(GaX(2))]. In the gallyl complexes of nickel and palladium, the M-Ga sigma bonding orbital is slightly polarized toward the gallium atom, while in the platinum gallyl complexes, the M-Ga sigma bonding orbital is slightly polarized toward the platinum atom. It is significant to note that gallium atoms along the M-Ga sigma bonds have large p character, which is always >51% of the total AO contributions, while along the Ga-X sigma bonds, the p character varies from 72% to 73%. The short M-Ga bond distances, in spite of the significantly small M-Ga pi bonding, are due to the large s character of gallium (approximately 45-48%) along the M-Ga bonds. The calculated NPA charge distributions indicate that the metal atom carries negative charge and the Ga atom carries significantly large positive charge. The contributions of the electrostatic interaction terms, DeltaE(elstat), are significantly larger in all gallyl complexes than the covalent bonding DeltaE(orb) term. Thus, the [M]-GaX(2) bond in the studied gallyl complexes of Ni, Pd, and Pt has a greater degree of ionic character (65.7-72.5%). The pi-bonding contribution is, in all complexes, significantly smaller than the sigma bonding contribution. In the GaX(2) ligands, gallium dominantly behaves as a sigma donor. The interaction energy increases in all three sets of complexes via order of Ni < Pd < Pt, and the absolute value of DeltaE(Pauli), DeltaE(int), and DeltaE(elstat) contributions to the M-Ga bonds decreases via X = Cl < Br < I in all three sets of complexes.