Complexes of the methyl tris(3,5-dimethylpyrazol-1-yl) gallate ligand, MeGa(N2C5H7)3−, and its hydroxy derivative, MeGa(N2C5H7)2(OH)−. Crystal and molecular structure of [MeGa(N2C5H7)2(OH)]Mo(CO)2(η3-C4H7)

Breakell, Kenneth R.; Rettig, Steven J.; Storr, Alan; Trotter, James

doi:10.1139/v79-023

Cited by 24 publications

(1 citation statement)

References 6 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The OC−M−CO angle was fixed at 90° for these molecular orbital studies. Crystallographic studies of d 4 dicarbonyl group VI metal η 3 -allyl complexes containing anionic, tridentate ligands reveal acute OC−W−CO bond angles in all cases. ,− ,,,− A correlation exists between the OC−W−CO bond angle and the orientation of single-faced π-donors for d 4 dicarbonyl transition metal complexes …”

Section: Resultsmentioning

confidence: 96%

Orientational and Stereochemical Preferences in [Hydridotris(3,5-dimethyl-1-pyrazolyl)borato](CO)₂W(η³-allyl) Complexes

Frohnapfel¹,

White²,

Templeton³

et al. 1997

Organometallics

View full text Add to dashboard Cite

Irradiation of Tp‘(CO)3WH in the presence of alkynes or unconjugated dienes generates η3-allyl complexes, Tp‘(CO)2W(η3-CHRCHCHR‘). A kinetic preference for anti-alkyl substitution due to η2-vinyl intermediates exists for the reactions with terminal alkyne substrates. The monoalkyl-substituted allyl complexes are configurationally stable on the NMR time scale but show a thermodynamic preference for syn-substitution upon heating in solution. Separate crystal structures of the syn and anti isomers of the 1-methylallyl complex, Tp‘(CO)2W(η3-CH2CHCHCH3), have revealed isomers which differ by approximately 90° in allyl orientation (θ). The term meso is introduced to emphasize the orthogonal relationship between the anti (θ = 30°, exo) and the syn (θ = 120°, meso) isomers. The change in orientation of the allyl is accompanied by a change in the OC−W−CO angle from acute to obtuse in order to maximize donation from the π-nonbonding orbital of the allyl into the dπ metal orbitals. EHMO (extended Hückel molecular orbital) calculations on a model complex [H3W(CO)2(η3-C3H5)]2- show electronic minima at θ = 30° and 115° corresponding to the two orientations.

show abstract

Section: Resultsmentioning

confidence: 96%

Orientational and Stereochemical Preferences in [Hydridotris(3,5-dimethyl-1-pyrazolyl)borato](CO)₂W(η³-allyl) Complexes

Frohnapfel¹,

White²,

Templeton³

et al. 1997

Organometallics

View full text Add to dashboard Cite

show abstract

The Coordination Chemistry of Pyrazole‐Derived Ligands

Trofimenko¹

1986

Progress in Inorganic Chemistry

658

View full text Add to dashboard Cite

Reactivity of Molybdenum and Rhenium Hydroxo‐Carbonyl Complexes toward Organic Electrophiles

Cuesta

Gerbino

Hevia

et al. 2004

Chemistry A European J

View full text Add to dashboard Cite

The hydroxo compounds [Re(OH)(CO)(3)(N-N)] (N-N=bipy, 2 a; Me(2)-bipy, 2 b) were prepared in a biphasic H(2)O/CH(2)Cl(2) medium by reaction of [Re(OTf)(CO)(3)(N-N)] with KOH. In contrast, when anhydrous CH(2)Cl(2) was used, the binuclear hydroxo-bridged compound [[Re(CO)(3)(bipy)](2)(mu-OH)]OTf (3-OTf) was obtained. Compound [Re(OH)(CO)(3)(Me(2)-bipy)] (2 b) reacted with phenyl acetate or vinyl acetate to afford [Re(OAc)(CO)(3)(Me(2)-bipy)] (4) and phenol or acetaldehyde, respectively. The reactions of [Mo(OH)(eta(3)-C(3)H(4)-Me-2)(CO)(2)(phen)] (1), 2 a, and 2 b toward several unsaturated organic electrophiles were studied. The reaction of 1 with (p-tolyl)isocyanate afforded an adduct of N,N'-di(p-tolyl)urea and the carbonato-bridged compound [[Mo(eta(3)-C(3)H(4)-Me-2)(CO)(2)(phen)](2)(mu-eta(1)(O),eta(1)(O)-CO(3))] (5). In contrast, the reaction of 2 a with phenylisocyanate afforded [Re(OC(O)NHPh)(CO)(3)(bipy)] (6); this results from formal PhNCO insertion into the O-H bond. On the other hand, compounds [Mo[SC(O)NH(p-tolyl)](eta(3)-C(3)H(4)-Me-2)(CO)(2)(phen)] (7), [Re[SC(O)NH(p-tolyl)](CO)(3)(Me(2)-bipy)] (8 a), and [Re[SC(O)NHEt](CO)(3)(Me(2)-bipy)] (8 b) were obtained by reaction of 1 or 2 b with the corresponding alkyl or aryl isothiocyanates. In those cases, RNCS was inserted into the M-O bond. The reactions of 1, 2 a, and 2 b with dimethylacetylenedicarboxylate (DMAD) gave the complexes [Mo[C(OH)-C(CO(2)Me)C(CO(2)Me)-O](eta(3)-C(3)H(4)-Me-2)(CO)(phen)] (9) and [Re[C(OH)C(CO(2)Me)C(CO(2)Me)O](CO)(2)(N-N)] (N-N=bipy, 10 a; Me(2)-bipy, 10 b). The molecules of these compounds contain five-membered metallacycles that are the result of coupling between the hydroxo ligand, DMAD, and one of the CO ligands. The new compounds were characterized by a combination of IR and NMR spectroscopy, and for [[Re(CO)(3)(bipy)(2)(mu-OH)]BF(4) (3-BF(4)), 4, 5, 6, 7, 8 b, 9, and 10 b, also by means of single-crystal X-ray diffraction.

show abstract

Complexes of the methyl tris(3,5-dimethylpyrazol-1-yl) gallate ligand, MeGa(N₂C₅H₇)₃⁻, and its hydroxy derivative, MeGa(N₂C₅H₇)₂(OH)⁻. Crystal and molecular structure of [MeGa(N₂C₅H₇)₂(OH)]Mo(CO)₂(η³-C₄H₇)

Cited by 24 publications

References 6 publications

Orientational and Stereochemical Preferences in [Hydridotris(3,5-dimethyl-1-pyrazolyl)borato](CO)₂W(η³-allyl) Complexes

Orientational and Stereochemical Preferences in [Hydridotris(3,5-dimethyl-1-pyrazolyl)borato](CO)₂W(η³-allyl) Complexes

The Coordination Chemistry of Pyrazole‐Derived Ligands

Reactivity of Molybdenum and Rhenium Hydroxo‐Carbonyl Complexes toward Organic Electrophiles

Contact Info

Product

Resources

About

Complexes of the methyl tris(3,5-dimethylpyrazol-1-yl) gallate ligand, MeGa(N2C5H7)3−, and its hydroxy derivative, MeGa(N2C5H7)2(OH)−. Crystal and molecular structure of [MeGa(N2C5H7)2(OH)]Mo(CO)2(η3-C4H7)

Cited by 24 publications

References 6 publications

Orientational and Stereochemical Preferences in [Hydridotris(3,5-dimethyl-1-pyrazolyl)borato](CO)2W(η3-allyl) Complexes

Orientational and Stereochemical Preferences in [Hydridotris(3,5-dimethyl-1-pyrazolyl)borato](CO)2W(η3-allyl) Complexes

The Coordination Chemistry of Pyrazole‐Derived Ligands

Reactivity of Molybdenum and Rhenium Hydroxo‐Carbonyl Complexes toward Organic Electrophiles

Contact Info

Product

Resources

About

Complexes of the methyl tris(3,5-dimethylpyrazol-1-yl) gallate ligand, MeGa(N₂C₅H₇)₃⁻, and its hydroxy derivative, MeGa(N₂C₅H₇)₂(OH)⁻. Crystal and molecular structure of [MeGa(N₂C₅H₇)₂(OH)]Mo(CO)₂(η³-C₄H₇)

Orientational and Stereochemical Preferences in [Hydridotris(3,5-dimethyl-1-pyrazolyl)borato](CO)₂W(η³-allyl) Complexes

Orientational and Stereochemical Preferences in [Hydridotris(3,5-dimethyl-1-pyrazolyl)borato](CO)₂W(η³-allyl) Complexes