Theoretical investigation of M≡E bonds in transition metal–ylidyne complexes trans-[H(PMe3)4M≡ER] (M = Mo, W; E = Si, Ge, Sn, Pb; R = Mes, Xylyl)

Pandey, Krishna K.; Patidar, Pankaj

doi:10.1016/j.jorganchem.2011.12.026

Cited by 15 publications

(8 citation statements)

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“…The electronic structures of 16 trans -[H(PMe 3 ) 4 M  ER ] (M = Mo, W; E = Si, Ge, Sn, Pb; R = Mes, Xylyl) complexes have been investigated using DFT at the BP86/TZ2P/ZORA level and reported by Pandey and Patidar . Discussed here are just the 4 SiR systems (R = Mes, xylyl; two isomers for each) that describe hypothetical molecules.…”

Section: Bonding and Calculationssupporting

confidence: 74%

“…The WBIs for M–E are 2.00 (Mo) and 2.07 (W). Thus, the overall electronic charge is transferred in the direction of metal to silicon, [H(PMe 3 ) 4 M] − →[Si(Mes)] with the π-bonding orbitals highly polarized toward the metal atom …”

Section: Bonding and Calculationsmentioning

confidence: 88%

“…In this grouping, 1 paper includes calculations for Si–M, where M represents all three of the metals, Cr, Mo, and W, and 2 that describe hypothetical Mo–Si and W–Si complexes. , …”

Section: Bonding and Calculationsmentioning

confidence: 99%

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Reactions of Hydrosilanes with Transition Metal Complexes

2016

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This third review in a series involving reactions of hydrosilanes and transition metal complexes and characterization of the products covers the period 2009 thru 2013. After a brief discussion of other synthetic methods used for the formation of Si-TM complexes, Section 3 provides an extended discussion of the types of ligands and metal complexes used as reactants with hydrosilanes. The increase in use of pincer ligands in forming stable, isolable complexes is featured. Three tables list the complexes reported for primary, secondary, and tertiary silanes. Many reactions leading to SiTM complexes are initiated by loss of a ligand prior to oxidative addition of the hydrosilane or by a metathesis reaction. Structural data are tabulated for the isolated complexes and provide the Si-TM bond ranges for the elements in the "d" block. A major section on nonclassical (σ or agostic) complexes includes two general groupings with Si-H···TM and M-H···Si interactions. A section on solution processes identified by NMR spectroscopy is dominated by hydride exchange examples. A section on bonding outlines a unifying bonding description that has been proposed as well as calculations reported for Si-TM complexes, both real and hypothetical examples.

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Section: Bonding and Calculationssupporting

confidence: 74%

Section: Bonding and Calculationsmentioning

confidence: 88%

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Reactions of Hydrosilanes with Transition Metal Complexes

2016

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“…Both the W–W and W–O distances conform to the present r 3 ; see Table . Pandey and Patidar calculate WGe and WPb distances of 232 and 258 pm, compared to the r 3 prediction of 229 and 252 pm, respectively.…”

Section: Comparisons With Later Experimental Datamentioning

confidence: 99%

Additive Covalent Radii for Single-, Double-, and Triple-Bonded Molecules and Tetrahedrally Bonded Crystals: A Summary

2014

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The recent fits of additive covalent radii R(AB) = r(A) + r(B) for the title systems are reviewed and compared with alternative systems of radii by other authors or with further experimental data. The agreement of the predicted R with experiment is good, provided that the A-B bond is not too ionic, or the coordination numbers of the two atoms too different from the original input data, used in the fit. Bonds between transition metals and halides are not included in the single-bond set, because of their partial multiple-bond character.

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“…The electronic structure and the bonding situation of transition metal-ylyne (M-ER) complexes of chromium, molybdenum, tungsten and iron have been investigated in theoretical studies [25][26][27][28][29][30][31] including the differences between the chemical bonding situation of metal-ylynes and metalloylenes. 25,28 In a recent publication, the nature of M-Ge bonds in aminogermylene complexes of chromium, molybdenum and tungsten complexes has also been reported.…”

Section: Introductionmentioning

confidence: 99%

Assessment of density functionals and paucity of non-covalent interactions in aminoylyne complexes of molybdenum and tungsten [(η⁵-C₅H₅)(CO)₂MEN(SiMe₃)(R)] (E = Si, Ge, Sn, Pb): a dispersion-corrected DFT study

et al. 2014

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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.

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Theoretical investigation of M≡E bonds in transition metal–ylidyne complexes trans-[H(PMe3)4M≡ER] (M = Mo, W; E = Si, Ge, Sn, Pb; R = Mes, Xylyl)

Cited by 15 publications

References 60 publications

Reactions of Hydrosilanes with Transition Metal Complexes

Reactions of Hydrosilanes with Transition Metal Complexes

Additive Covalent Radii for Single-, Double-, and Triple-Bonded Molecules and Tetrahedrally Bonded Crystals: A Summary

Assessment of density functionals and paucity of non-covalent interactions in aminoylyne complexes of molybdenum and tungsten [(η⁵-C₅H₅)(CO)₂MEN(SiMe₃)(R)] (E = Si, Ge, Sn, Pb): a dispersion-corrected DFT study

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Theoretical investigation of M≡E bonds in transition metal–ylidyne complexes trans-[H(PMe3)4M≡ER] (M = Mo, W; E = Si, Ge, Sn, Pb; R = Mes, Xylyl)

Cited by 15 publications

References 60 publications

Reactions of Hydrosilanes with Transition Metal Complexes

Reactions of Hydrosilanes with Transition Metal Complexes

Additive Covalent Radii for Single-, Double-, and Triple-Bonded Molecules and Tetrahedrally Bonded Crystals: A Summary

Assessment of density functionals and paucity of non-covalent interactions in aminoylyne complexes of molybdenum and tungsten [(η5-C5H5)(CO)2MEN(SiMe3)(R)] (E = Si, Ge, Sn, Pb): a dispersion-corrected DFT study

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Assessment of density functionals and paucity of non-covalent interactions in aminoylyne complexes of molybdenum and tungsten [(η⁵-C₅H₅)(CO)₂MEN(SiMe₃)(R)] (E = Si, Ge, Sn, Pb): a dispersion-corrected DFT study