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.     

Metal-metal interactions in heterobimetallic d8-d10 complexes. Structures and spectroscopic investigation of [M'M' '(mu-dcpm)2(CN)2]+ (M' = Pt,Pd; M' ' = Cu,Ag, Au) and related complexes by UV-vis absorption and resonance Raman spectroscopy and ab initio calculations

X-ray structural and spectroscopic properties of a series of heterodinuclear d(8)-d(10) metal complexes [M'M' '(mu-dcpm)(2)(CN)(2)](+) containing d(8) Pt(II), Pd(II), or Ni(II) and d(10) Au(I), Ag(I), or Cu(I) ions with a dcpm bridging ligand have been studied (dcpm = bis(dicyclohexylphosphino)methane; M' = Pt, M' ' = Au 4, Ag 5, Cu, 6; M' ' = Au, M' = Pd 7, Ni 8). X-ray crystal analyses showed that the metal...metal distances in these heteronuclear metal complexes are shorter than the sum of van der Waals radii of the M' and M' ' atoms. The UV-vis absorption spectra of 4-6 display red-shifted intense absorption bands from the absorption spectra of the mononuclear trans-[Pt(phosphine)(2)(CN)(2)] and [M' '(phosphine)(2)](+) counterparts, attributable to metal-metal interactions. The resonance Raman spectra confirmed assignments of (1)[nd(sigma)-->(n + 1)p(sigma)] electronic transitions to the absorption bands at 317 and 331 nm in 4 and 6, respectively. The results of theoretical calculations at the MP2 level reveal an attractive interaction energy curve for the skewed [trans-Pt(PH(3))(2)(CN)(2)-Au(PH(3))(2)(+)] dimer. The interaction energy of Pt(II)-Au(I) was calculated to be ca. 0.45 ev.     

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.     

The structure and chemistry of tris(pentafluorophenyl)borane protected mononuclear nitridotitanium complexes

Treatment of TiCl(NMe(2))(3) with H(3)N·B(C(6)F(5))(3) results in N-H activation and ligand exchange to yield the structurally characterised salt [TiCl(NMe(2))(2)(NMe(2)H)(2)](+)[Ti[triple bond]NB(C(6)F(5))(3)(Cl)(2)(NMe(2)H)(2)](-). Cation exchange with [Me(4)N]Cl, [Ph(4)P]Cl and [(PhCH(2))Ph(3)P]Cl yields the respective ammonium and phosphonium salts of the [Ti[triple bond]NB(C(6)F(5))(3)(Cl)(2)(NMe(2)H)(2)](-) anion. X-ray crystallography reveals that the essential trigonal bipyramidal geometry and composition of the anion is retained in each of these salts despite some minor variations in the Ti-N-B angle and the nature of the interionic interactions. Electronic investigation by DFT calculations confirmed the Ti-N triple bond character implied by the experimentally determined bond length, with the HOMO and HOMO-1 having Ti-N π-bonding character. The dimethylamine ligands of the anion resist substitution by moderate bases but can be displaced by pyridine to give a pentacoordinate anion. In contrast, addition of 2,2'-bipyridyl gives a neutral octahedral complex. Treatment of the pyridine complex with TlCp results in the formation of a four coordinate anionic cyclopentadienyl complex.     

Low-valent group-13 chemistry. Theoretical investigation of the structures and relative stabilities of donor-acceptor complexes R(3)E[bond]E'R' and their isomers R(2)E[bond]E'RR'

The results of quantum chemical calculations at the gradient-corrected density functional theory (DFT) level with the B3LYP functional of the donor-acceptor complexes R(3)E[bond]E'R' and their isomers R(2)E[bond]E'RR', where E, E' = B[bond]Tl and R, R' = H, Cl, or CH(3), are reported. The theoretically predicted energy differences between the donor-acceptor form R(3)E[bond]E'R' and the classical isomer R(2)E[bond]E'RR' and the bond dissociation energies of the E[bond]E' bonds are given. The results are discussed in order to show which factors stabilize the isomers R(3)E[bond]E'R'. There is no simple correlation of the nature of the group-13 elements E, E' and the substituents R, R' with the stability of the complexes. The isomers R(3)E[bond]'R' come stabilized by pi donor groups R', while the substituents R may either be sigma- or pi-bonded groups. Calculations of Cl(3)B[bond]BR' [R' = Cl, cyclopentadienyl (Cp), or Cp*] indicate that the Cp* group has a particularly strong effect on the complex form. The calculations show that the experimentally known complex Cl(3)B[bond]BCp* is the strongest bonded donor-acceptor complex of main-group elements that has been synthesized until now. The theoretically predicted B[bond]B bond energy is D(o) = 50.6 kcal/mol. However, the calculations indicate that it should also be possible to isolate donor-acceptor complexes R(3)E[bond]E'R' where R' is a sigma-bonded bulky substituent. Possible candidates that are suggested for synthetic work are the borane complexes (C(6)F(5))(3)B[bond]E'R' and (t)Bu(3)B[bond]E'R' (E' = Al[bond]Tl) and the alane complexes Cl(3)Al[bond]E'R' (E' = Ga[bond]Tl).     

Syntheses, structures, and surface aromaticity of the new carbaalane [(AlH)(6)(AlNMe(3))(2)(CCH(2)R)(6)] (R = Ph, CH(2)SiMe(3)) and a stepwise functionalization of the inner and outer sphere of the cluster

The reaction of the acetylene RC triple bond CH (R = Ph, CH(2)SiMe(3)) with an excess of AlH(3).NMe(3) in boiling toluene leads to the carbaalane [(AlH)(6)(AlNMe(3))(2)(CCH(2)R)(6)] (R = Ph 1, CH(2)SiMe(3) 2) in good yield. Treatment of 2 with BCl(3) under varying conditions gives the chlorinated products [(AlCl)(6)(AlNMe(3))(2)(CCH(2)CH(2)SiMe(3))(6)] 3 and [(AlCl)(6)(AlNMe(3))(2)(CCH(2)CH(2)SiMe(2)Cl)(6)] 4, respectively. The latter clearly demonstrates that the cluster can be stepwise functionalized within the inner and outer sphere. The X-ray single-crystal structures of 1, 2, and 4 have been determined. All compounds have in common that the central core consists of a cluster having eight aluminum and six carbon atoms. The bonding properties in this cluster are described as a new manifestation of three-dimensional surface aromaticity. Each Al(4)C fragment of the cube is formed by four bonds with three electron pairs, thus leading to a strong delocalization of the electrons. A phenomenological modeling using a three-dimensional Hückel scheme with fitted parameters to reproduce the energies from ab initio calculations revealed that the orbital scheme localized at one Al(4)C fragment possesses an orbital sextet with a large HOMO-LUMO gap. This is in line with the criteria of aromaticity. The idea of aromaticity was sustained also by qualitative valence bond reasons enumerating the different resonance structures by means of graph theoretical methods.     

Binuclear homoleptic manganese carbonyls: Mn2(CO)x (x = 10, 9, 8, 7)

The unsaturated homoleptic manganese carbonyls Mn(2)(CO)(n)() (n = 7, 8, 9) are characterized by their equilibrium geometries, thermochemistry, and vibrational frequencies using methods from density functional theory (DFT). The computed metal-metal distances for global minima range from 3.01 A for the unbridged Mn(2)(CO)(10) with a Mn-Mn single bond to 2.14 A for a monobridged Mn(2)(CO)(7) formulated with a metal-metal quadruple bond. The global minimum for Mn(2)(CO)(9) has a four-electron bridging mu-eta(2)-CO group and a 2.96 A Mn-Mn distance suggestive of the single bond required for 18-electron configurations for both metal atoms. This structure is closely related to an experimentally realized structure for the isolated and structurally characterized stable phosphine complex [R(2)PCH(2)PR(2)](2)Mn(2)(CO)(4)(mu-eta(2)-CO). An unbridged (OC)(4)Mn-Mn(CO)(5) structure for Mn(2)(CO)(9) has only slightly (<6 kcal/mol) higher energy with a somewhat shorter metal-metal distance of 2.77 A. For Mn(2)(CO)(8) the lowest energy structure is a D(2)(d)() unbridged structure with a 2.36 A metal-metal distance suggesting the triple bond required for the favored 18-electron configuration for both metal atoms. However, the unbridged unsymmetrical (CO)(3)Mn-Mn(CO)(5) structure with a metal-metal bond distance of 2.40 A lies only 1 to 3 kcal/mol above this global minimum. The lowest energy structure of Mn(2)(CO)(7) is an unbridged C(s)() structure with a short metal-metal distance of 2.26 A. This is followed energetically by another C(s)() unbridged Mn(2)(CO)(7) structure with a somewhat longer metal-metal distance of 2.38 A.     

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.     

Chemistry of the oxophosphinidene ligand. 2. Reactivity of the anionic complexes [MCp{P(O)R*}(CO)(2)](-) (M = Mo, W; R* = 2,4,6-C(6)H(2)(t)Bu(3)) toward electrophiles based on elements different from carbon

The anionic oxophosphinidene complexes (H-DBU)[MCp{P(O)R*}(CO)(2)] (M = Mo, W; R* = 2,4,6-C(6)H(2)(t)Bu(3); Cp = η(5)-C(5)H(5), DBU = 1,8-diazabicyclo [5.4.0] undec-7-ene) displayed multisite reactivity when faced with different electrophilic reagents. The reactions with the group 14 organochloride compounds ER(4-x)Cl(x) (E = Si, Ge, Sn, Pb) led to either phosphide-like, oxophosphinidene-bridged derivatives [MCp{P(OE')R*}(CO)(2)] (E' = SiMe(3), SiPh(3), GePh(3), GeMe(2)Cl) or to terminal oxophosphinidene complexes [MCp{P(O)R*}(CO)(2)(E')] (E' = SnPh(3), SnPh(2)Cl, PbPh(3); Mo-Pb = 2.8845(4) ? for the MoPb compound). A particular situation was found in the reaction with SnMe(3)Cl, this giving a product existing in both tautomeric forms, with the phosphide-like complex [MCp{P(OSnMe(3))R*}(CO)(2)] prevailing at room temperature and the tautomer [MCp{P(O)R*}(CO)(2)(SnMe(3))] being the unique species present below 203 K in dichloromethane solution. The title anions also showed a multisite behavior when reacting with transition-metal based electrophiles. Thus, the reactions with the complexes [M'Cp(2)Cl(2)] (M' = Ti, Zr) gave phosphide-like derivatives [MCp{P(OM')R*}(CO)(2)] (M = Mo, M' = TiCp(2)Cl, ZrCp(2)Cl; M = W, M' = ZrCp(2)Cl), displaying a bridging κ(1),κ(1)-P,O- oxophosphinidene ligand connecting MCp(CO)(2) and M'Cp(2)Cl metal fragments (W-P = 2.233(1) ?, O-Zr = 2.016(4) ? for the WZr compound]. In contrast, the reactions with the complex [AuCl{P(p-tol)(3)}] gave the metal-metal bonded derivatives trans-[MCp{P(O)R*}(CO)(2){AuP(p-tol)(3)}] (M = Mo, W; Mo-Au = 2.7071(7) ?). From all the above results it was concluded that the terminal oxophosphinidene complexes are preferentially formed under conditions of orbital control, while charge-controlled reactions tend to give derivatives with the electrophilic fragment bound to the oxygen atom of the oxophosphinidene ligand (phosphide-like, oxophosphinidene-bridged derivatives).     

Reversal of stability on metalation of pentagonal-bipyramidal (1-MB6H7(2-) 1-M-2-CB5H7(1-) and 1-M-2,4-C2B4H7) and Icosahedral (1-MB11H12(2-) 1-M-2-CB10H12(1-) and 1-M-2,4-C2B9H12) boranes (M = Al, Ga, In, and Tl): energetics of condensation and relationship to binuclear metallocenes

The usual assumption of the extra stability of icosahedral boranes (2) over pentagonal-bipyramidal boranes (1) is reversed by substitution of a vertex by a group 13 metal. This preference is a result of the geometrical requirements for optimum overlap between the five-membered face of the ligand and the metal fragment. Isodesmic equations calculated at the B3LYP/LANL2DZ level indicate that the extra stability of 1-M-2,4-C(2)B(4)H(7) varies from 14.44 kcal/mol (M = Al) to 15.30 kcal/mol (M = Tl). Similarly, M(2,4-C(2)B(4)H(6))(2)(1-) is more stable than M(2,4-C(2)B(9)H(11))(2)(1-) by 9.26 kcal/mol (M = Al) and by 6.75 kcal/mol (M = Tl). The preference for (MC(2)B(4)H(6))(2) over (MC(2)B(9)H(11))(2) at the same level is 30.54 kcal/mol (M = Al), 33.16 kcal/ mol (M = Ga) and 37.77 kcal/mol (M = In). The metal-metal bonding here is comparable to those in CpZn-ZnCp and H(2)M-MH(2) (M= Al, Ga, and In).     

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.     

Electronic structure and metal-metal interactions in trinuclear face-shared [M3X12]3- (M = Mo, W; X = F, Cl, Br, I) systems

The molecular and electronic structures of trinuclear face-shared [M3X12]3-species of Mo (X = F, Cl, Br, I) and W (X = Cl), containing linear chains of metal atoms, have been investigated using density functional theory. The possibility of variations in structure and bonding has been explored by considering both symmetric (D3d) and unsymmetric (C3v) forms, the latter having one long and one short metal-metal distance. Analysis of the bonding in the structurally characterized [Mo3I12]3- trimer reveals that the metal-metal interaction qualitatively corresponds to a two-electron three-center sigma bond between the Mo atoms and, consequently, a formal Mo-Mo bond order of 0.5. However, the calculated spin densities suggest that the electrons in the metal-metal sigma bond are not fully decoupled and therefore participate in the antiferromagnetic interactions of the metal cluster. Although the same observation applies to [Mo3X12]3- (X = Br, Cl, F) and [W3Cl12]3-, both the spin densities and shorter distances between the metal atoms indicate that the metal-metal interaction is stronger in these systems. The broken-symmetry approach combined with spin projection has been used to determine the energy of the low-lying spin multiplets arising from the magnetic coupling between the metal centers. Either the symmetric and unsymmetric S = 3/2 state is predicted to be the ground state for all five systems. For [Mo3X12]3- (X = Cl, Br, I), the symmetric form is more stable but the unsymmetric structure, where two metal centers are involved in a metal-metal triple bond while the third center is decoupled, lies close in energy and is thermally accessible. Consequently, at room temperature, interconversion between the two energetically equivalent configurations of the unsymmetric form should result in an averaged structure that is symmetric. This prediction is consistent with the reported structure of [Mo3I12]3-, which, although symmetric, indicates significant movement of the central Mo atom toward the terminal Mo atoms on either side. In contrast, unsymmetric structures with a triple bond between two metal centers are predicted for [Mo3F2]3- and [W3C12]3-, as the symmetric structure lies too high in energy to be thermally accessible.     

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.     

Isolable Tetragold(0) Clusters with Polarity-Tunable exo-Au−Au Bond via Intramolecular σ-Aromatization

Intramolecular π-aromatization is a trait of many organic compounds that enhances the stability of their structures and polarizes related C−C π bonds. In contrast, rare study is focused on this phenomenon in metal clusters. Many existing homometallic clusters exhibit aromaticity, often characterized by nonpolar metal-metal bonds and a high degree of symmetry. However, synthesizing low-symmetric homometallic clusters with high-polar metal-metal bonds is challenging due to their limited thermodynamic stability. Herein, we report a facile strategy for the synthesis of [Au(μ₂-ER₂)]₃−AuPMe₃ (E=Ge, Sn; R₂=1,1,4,4-tetrakis(trimethylsilyl)butane-1,4-diyl) clusters and reveal a novel stabilization mode, intramolecular σ-aromatization. Our electronic structure analyses show that these low-symmetric clusters possess a ten-electron σ-aromatic system, which is achieved via intramolecular σ-aromatization. Moreover, the strength of σ-aromaticity gives rise to a polarity-tunable exo-Au−Au bond.     

Third-order nonlinear optical properties of complexes with MM triple and quadruple bonds (M = Mo, W) at 1064 nm by degenerate four-wave mixing

Measurements of the third-order nonlinear optical responses of solutions of the metal-metal multiply bonded complexes Mo(2)(OPr(i))(6), W(2)(OBu(t))(6), M(2)(NMe(2))(6), M(2)(O(2)CBu(t))(4), and M(2)Cl(4)(PMe(3))(4) (M = Mo, W), using picosecond degenerate four-wave mixing at 1064 nm, are reported. These complexes display only very small instantaneous electronic polarizations when excited with cross-polarized beams. When the excitation beams are similarly polarized, a significant third-order optical response is detected, which is attributable to the formation of bulk thermal excitation gratings. Time-dependent measurements support this view.     

Synthesis,characterization, and theoretical studies of group 4 amido hydrotris(pyrazolyl)borate complexes

Titanium and zirconium amido complexes containing a hydrotris(pyrazolyl)borate (Tp) or hydrotris(3,5-dimethylpyrazolyl)borate (Tp*) ligand TpM(NMe(2))(3) (M = Ti, 1; M = Zr, 2) and Tp*M(NMe(2))(3) (M = Ti, 3; M = Zr, 4) were prepared by the reactions of M(NMe(2))(3)Cl (M = Ti, Zr) with sodium hydridotris(pyrazol-1-yl)borate and potassium hydridotris(3,5-dimethylpyrazol-1-yl)borate, respectively. The structures of 1, 2, and 4.CH(2)Cl(2) were determined by X-ray diffraction and show octahedral coordination geometry around the metal centers. Density functional theory calculations at the B3PW91 level were performed to understand the orientations and the rotational behavior of amido ligands in these metal complexes.     

Electronic structure of [(CpCr)[(CO)3M]]mu-Cot (M = Cr, Fe): a theoretical study

The electronic structure of two cyclooctatetraene-bridged dinuclear first-row transition metal complexes of the type [(CpM)[(CO)3M']]mu-Cot (M = Cr; M' = Fe (1), Cr (2)) was investigated by complete active space self-consistent field (CASSCF) calculations. In this context the differences in the binding capabilities of the complex fragments CpM and (CO)3M are discussed on the basis of extended Huckel molecular orbital (MO) calculations. The geometries used for the CASSCF calculations for complex 1 were obtained from the crystal structure. For 2 a model structure was established by geometry optimization using density functional methods. The CASSCF results agree well with the experimental findings and provide insight into the binding situation of the two compounds. Complex 1 can be regarded as being composed of a chromocene-like subunit CpCr(eta5-C5H5) and the fragment (CO)3Fe(eta3-C3H3). A direct metal-metal bond is found, involving one initially singly occupied orbital of each fragment, leading to a doublet ground state for 1 with the remaining unpaired electron localized at the chromium center. For 2 no such direct metal-metal bond can be recognized. A very weak direct metal-metal interaction is induced by electron donation from the Cot2- ligand into a formally unoccupied metal-metal binding orbital combination. In the quartet ground state all three unpaired electrons are localized at the chromium center of the formally doubly positive charged CpCr unit, on which complex fragment [(CO)3Cr(eta5-Cot)]2- acts like a cyclopentadienyl ligand. The coordination sphere of the chromium center of the CpCr unit resembles that of a metallocene metal center and its metal 3d occupation scheme corresponds to that of vanadocene.     

Silyl,hydrido-silylene,or other bonding modes: some unusual structures of [(dhpe)Pt(SiHR2)]+ (dhpe = H2P-CH2-CH2-PH2; R = H,Me, SiH3, Cl,OMe, NMe2) and [(dhpe)Pt(SiR3)](+) (R = Me,Cl) from DFT calculations

DFT (B3LYP) calculations have been carried out in order to quantitatively evaluate the energies and stereochemistry of the accessible structures of [(dhpe)Pt(SiHR(2))](+) (dhpe = H(2)P-CH(2)-CH(2)-PH(2); R = H, CH(3), SiH(3), Cl, OMe, SMe, NMe(2)) and of [(dhpe)Pt(SiR(3))](+) (R = CH(3), Cl). A number of different isomers have been located. The expected terminal silyl or hydrido-silylene complexes are often not the most stable complexes. An isomer in which an H or an R group bridges a Pt=SiHR or Pt=SiR(2) bond is found to compete with the terminal silyl or hydrido-silylene isomers. In some cases, isomers derived from cleavage of a C-H bond and formation of a silene or disilene ligand are obtained. The structures of the platinum silyls differ from that of the equivalent alkyl complex, calculated for [(dhpe)Pt(CH(3))](+).     

Effect of geminal substitution at silicon on 1-sila- and 1,3-disilacyclobutanes' strain energies, their 2+2 cycloreversion enthalpies, and Si=C pi-bond energies in silenes.

To evaluate the effect of geminal substitution at silicon on 1-sila- and 1,3-disilacyclobutanes' strain energies, their 2+2 cycloreversion enthalpies, and Si=C pi-bond energies in silenes, an ab initio MO study of silenes, R2Si=CH2 (1), 1-silacyclobutanes, cyclo-R2Si(CH2)3 (2), and 1,3-disilacyclobutanes, cyclo-(R2SiCH2)2 (3), was performed using the level of theory denoted MP4/TZ(d)//MP2/6-31G(d) (TZ means the 6-311G(d) basis set for elements of the second period and hydrogen, and the McLean-Chandler (12s,9p)/[6s,5p](d) basis set for the third period elements). In the series R = H, CH3, SiH3, CH3O, NH2, Cl, F, the growth of the reaction enthalpies and strain energies is proportional to the substituents' electronegativities. 2+2 cycloreversion of 2 is endothermic by 40.6-63.1 kcal/mol, whereas that of 3 is endothermic by 72.7-114.2 kcal/mol. On going from a silicon to a fluorine substituent at the sp2-hybridized silicon atom, the pi-bond energy in 1 weakens by 11.3 kcal/mol, and the Si=C bond length shortens by 0.053 A. The effect of substituents' electronegativities at the double-bonded silicon atom in silenes is formulated as follows: the higher electronegativity, the shorter and the weaker the Si=C pi-bond. The latter is rationalized in terms of more strained geometry resulting from the energetic cost for planarizing the R2SiC moiety. The enthalpies of the ring-opening reaction are 68.0-80.1 kcal/mol (a cleavage of the Si-C bond in 3), 65.0-76.4 kcal/mol (a cleavage of the Si-C bond in 2), and 58.0-64.9 kcal/mol (a cleavage of the C-C bond in 2). The pronounced difference in the enthalpies of 2+2 cycloreversion of 1-sila- and 1,3-disilacyclobutanes is mainly due to the difference in the enthalpies of diradicals' decomposition. The decomposition of diradicals resulting from a cleavage of C-C and Si-C bonds in 2 is exothermic by 24.3-3.3 kcal/mol (apart from the difluoro derivative which is endothermic by 5.1 kcal/mol) and 27.0-13.3 kcal/mol, respectively. The decomposition of a 1,4-diradical resulting from ring opening of 3, apart from the disilyl derivative, is the endothermic process for which the enthalpy varies from 10.6 to 40.4 kcal/mol.