Crystal and molecular structure of bis(methylcyclopentadienyl)oxomolybdenum [(MeCp)2MoO (MeCp = .eta.5-CH3C5H4)]

Silavwe, Ned D.; Chiang, Michael Y.; Tyler, David R.

doi:10.1021/ic00218a049

Cited by 28 publications

(6 citation statements)

References 3 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Furthermore, the Mayer bond orders (MBO) for the TM–O bond in Tables , S2, and S3 are larger than or close to two, meaning strong covalent interaction between TM and O atoms in (Cp) 2 TMO (Cp = C 5 H 5 , C 5 MeH 4 , C 5 Me 5 ; TM = Cr, Mo, W). This result is in accordance with the above frontier molecular orbital analysis and the previous reports in theory. ,, …”

Section: Resultssupporting

confidence: 93%

Stabilities, Electronic Structures, and Bonding Properties of 20-Electron Transition Metal Complexes (Cp)₂TMO and their One-Dimensional Sandwich Molecular Wires (Cp = C₅H₅, C₅(CH₃)H₄, C₅(CH₃)₅; TM = Cr, Mo, W)

Pei

et al. 2021

J. Phys. Chem. A

View full text Add to dashboard Cite

First-principles calculations have been carried out for the 20-electron transition metal complexes (Cp)2TMO and their molecular wires (Cp = C5H5, C5(CH3)H4, C5(CH3)5; TM = Cr, Mo, W). The calculation results at the BP86/def2-TZVPP level reveal that the ground state is singlet and the optimized geometries are in good agreement with the experimental values. The analysis of frontier molecular orbitals shows that two electrons in the highest occupied molecular orbital HOMO-1 are mainly localized on cyclopentadienyl and oxygen ligands. Furthermore, the nature of the TM–O bond was investigated with the energy decomposition analysis-natural orbitals for chemical valence (EDA-NOCV). The attraction term in the intrinsic interaction energies ΔE int is mainly composed of two important parts, including electrostatic interaction (about 52% of the total attractive interactions ΔE elstat + ΔE orb) and orbital interaction, which might be the major determinant of the stability of these (Cp)2TMO complexes. All of the TM–O bonds should be described as electron-sharing σ single bonds [(Cp)2TM]+–[O]− with the contribution of 53–57% of ΔE orb and two π backdonations from the occupied p orbitals of oxygen ligands into vacant π* MOs of the [(Cp)2TM]+ fragments, which are 35–40% of ΔE orb. The results of bond order and interaction energy from EDA-NOCV calculations suggest the influence of the radius of TM and methyl in the interactions between TM and O in (Cp)2TMO. Additionally, the relativistic effects slightly amplify the strength of bonding with increasing ΔE orb for the EDA-NOCV calculations on three metal complexes (C5H5)2TMO. Finally, the geometries, electronic structures, and magnetics of infinitely extended systems, [(C5H5)TMO]∞, have also been explored. The results of the density of states (DOS) and band structure revealed that [(C5H5)CrO]∞ and [(C5H5)WO]∞ are semiconductors with the narrow bands, whereas [(C5H5)MoO]∞ behaves as metal.

show abstract

Section: Resultssupporting

confidence: 93%

Stabilities, Electronic Structures, and Bonding Properties of 20-Electron Transition Metal Complexes (Cp)₂TMO and their One-Dimensional Sandwich Molecular Wires (Cp = C₅H₅, C₅(CH₃)H₄, C₅(CH₃)₅; TM = Cr, Mo, W)

Pei

et al. 2021

J. Phys. Chem. A

View full text Add to dashboard Cite

show abstract

“…The molybdenum oxo complex (Cp Bu t ) 2 MoO, may be synthesized by the reaction of (Cp Bu t ) 2 MoCl 2 with excess LiOH (Scheme 2). The molecular structure of (Cp Bu t) 2 MoO has been determined by X-ray diffraction (Fig.8); the Mo᎐ ᎐ O bond length in (Cp Bu t ) 2 MoO [1.706(4) Å] is similar to that in the (Cp Me ) 2 MoO counterpart [1.721(2) Å] 39. The [Mo᎐ ᎐ O] moiety in (Cp Bu t ) 2 MoO is also characterized by an IR absorption at 838 cm Ϫ1 , a value that is comparable to those in, Cp 2 MoO (800 cm Ϫ1 ) and (CpMe…”

mentioning

confidence: 99%

The syntheses, structures and reactivity of bis(tert-butylcyclopentadienyl)molybdenum derivatives: nitrogen alkylation of an η2-acetonitrile ligand and influence of the chalcogen on the barrier to inversion of chalcogenoether adducts

Shin

Savage

Murphy

et al. 2001

J. Chem. Soc., Dalton Trans.

View full text Add to dashboard Cite

An investigation of the chemistry of the tert-butyl-substituted molybdenocene system, {(Cp Bu t) 2 Mo} (Cp Bu t = C 5 H 4 Bu t ), has demonstrated that the η 2 -acetonitrile ligand in (Cp Bu t ) 2 Mo(η 2 -MeCN) may be alkylated by RI (R = Me, Et) at nitrogen to give iminoacyl derivatives, [(Cp Bu t ) 2 Mo(η 2 -MeC᎐ ᎐ NR)] ϩ , which is a new type of reactivity for mononuclear acetonitrile complexes. A series of chalcogenolate-hydride complexes (Cp Bu t ) 2 Mo(EPh)H (E = S, Se, Te) have been obtained by reaction of (Cp Bu t ) 2 MoH 2 with Ph 2 E 2 , and may be alkylated by MeI to give the chalcogenoether adducts [(Cp Bu t ) 2 Mo(PhEMe)H]I. Dynamic NMR studies on [(Cp Bu t ) 2 Mo(PhEMe)H]ϩ indicate that the barrier to inversion at the chalcogen increases in the sequence S < Se < Te. The oxo complex (Cp Bu t ) 2 MoO reacts with 2 equivalents of Me 3 SiX (X = Cl, Br, I, O 2 CMe, O 3 SMe) to yield (Cp Bu t) 2 MoX 2 ; for X = CN and NCS, (Cp Bu t ) 2 -Mo(OSiMe 3 )X, the product of reaction with 1 equivalent may be isolated. (Cp Bu t) 2 Mo(OSiMe 3 )X (X = CN, NCS) reacts with Me 3 SiNCS to give the thiocyanate complex (Cp Bu t ) 2 Mo(SCN)X, rather than the isocyanate isomer, (Cp Bu t) 2 Mo(NCS)X, thereby indicating that the reactions do not involve a simple metathesis of the Si-NCS bond. Other complexes that are reported include:

show abstract

“…The hydrogen atoms of the bridging methylene group were not directly located by the X-ray analysis, but their presence is unambiguously shown by the 35 1.668(7) Å for [CpMoOCl]2(-O), 36 or 1.676(5) Å for [Cp*MoOCl]2(-O), 37 than with analogous distances in cyclopentadienyl complexes of Mo(IV), such as 1.721(2) Å for (C5H4Me)2Mo(O). 38 As mentioned above, the structure of this decomposition product is indirect evidence that the borane reagent has attacked the methyl group rather than the diene ligand in the dimethylmolybdenum(III) precursor, because one methyl group is found to bind the boron atom in the anion, while the putative residual [CpMo( 4 -C4H6)(CH3)] + becomes incorporated, after deprotonation, into the cationic unit, the methyl ligand becoming the bridging methylene group. The present study has confirmed the great resistance of the Mo(III)-CH3 bond toward heterolytic cleavage, previously shown by the fact that the bond can only be cleaved by acids stronger than H3O + .…”

Section: Resultsmentioning

confidence: 90%

Interaction of half-sandwich alkylmolybdenum(III) complexes with B(C6F5)3. The X-ray structure of [CpMo(η4-C4H6)(μ-Cl)(μ-CH2)(O)MoCp][CH3B(C6F5)3]

Grognec

Poli

Richard

et al. 2001

Journal of Organometallic Chemistry

View full text Add to dashboard Cite

HAL is a multi-disciplinary open access archive for the deposit and dissemination of scientific research documents, whether they are published or not. The documents may come from teaching and research institutions in France or abroad, or from public or private research centers. L'archive ouverte pluridisciplinaire HAL, est destinée au dépôt et à la diffusion de documents scientifiques de niveau recherche, publiés ou non, émanant des établissements d'enseignement et de recherche français ou étrangers, des laboratoires publics ou privés. Interaction of half-sandwich alkylmolybdenum(III) complexes with B(C6F5)3. The X-ray structure of [CpMo(η4-C4H6)(µ-Cl)(µ-CH2)(O)MoCp][CH3B(C6F5)3]

show abstract

Crystal and molecular structure of bis(methylcyclopentadienyl)oxomolybdenum [(MeCp)2MoO (MeCp = .eta.5-CH3C5H4)]

Cited by 28 publications

References 3 publications

Stabilities, Electronic Structures, and Bonding Properties of 20-Electron Transition Metal Complexes (Cp)₂TMO and their One-Dimensional Sandwich Molecular Wires (Cp = C₅H₅, C₅(CH₃)H₄, C₅(CH₃)₅; TM = Cr, Mo, W)

Stabilities, Electronic Structures, and Bonding Properties of 20-Electron Transition Metal Complexes (Cp)₂TMO and their One-Dimensional Sandwich Molecular Wires (Cp = C₅H₅, C₅(CH₃)H₄, C₅(CH₃)₅; TM = Cr, Mo, W)

The syntheses, structures and reactivity of bis(tert-butylcyclopentadienyl)molybdenum derivatives: nitrogen alkylation of an η2-acetonitrile ligand and influence of the chalcogen on the barrier to inversion of chalcogenoether adducts

Interaction of half-sandwich alkylmolybdenum(III) complexes with B(C6F5)3. The X-ray structure of [CpMo(η4-C4H6)(μ-Cl)(μ-CH2)(O)MoCp][CH3B(C6F5)3]

Contact Info

Product

Resources

About

Crystal and molecular structure of bis(methylcyclopentadienyl)oxomolybdenum [(MeCp)2MoO (MeCp = .eta.5-CH3C5H4)]

Cited by 28 publications

References 3 publications

Stabilities, Electronic Structures, and Bonding Properties of 20-Electron Transition Metal Complexes (Cp)2TMO and their One-Dimensional Sandwich Molecular Wires (Cp = C5H5, C5(CH3)H4, C5(CH3)5; TM = Cr, Mo, W)

Stabilities, Electronic Structures, and Bonding Properties of 20-Electron Transition Metal Complexes (Cp)2TMO and their One-Dimensional Sandwich Molecular Wires (Cp = C5H5, C5(CH3)H4, C5(CH3)5; TM = Cr, Mo, W)

The syntheses, structures and reactivity of bis(tert-butylcyclopentadienyl)molybdenum derivatives: nitrogen alkylation of an η2-acetonitrile ligand and influence of the chalcogen on the barrier to inversion of chalcogenoether adducts

Interaction of half-sandwich alkylmolybdenum(III) complexes with B(C6F5)3. The X-ray structure of [CpMo(η4-C4H6)(μ-Cl)(μ-CH2)(O)MoCp][CH3B(C6F5)3]

Contact Info

Product

Resources

About

Stabilities, Electronic Structures, and Bonding Properties of 20-Electron Transition Metal Complexes (Cp)₂TMO and their One-Dimensional Sandwich Molecular Wires (Cp = C₅H₅, C₅(CH₃)H₄, C₅(CH₃)₅; TM = Cr, Mo, W)

Stabilities, Electronic Structures, and Bonding Properties of 20-Electron Transition Metal Complexes (Cp)₂TMO and their One-Dimensional Sandwich Molecular Wires (Cp = C₅H₅, C₅(CH₃)H₄, C₅(CH₃)₅; TM = Cr, Mo, W)