Structurally Characterized Organometallic Hydroxo Complexes of the f- and d-Block Metals

Gilje, John W.; Roesky, H. W.

doi:10.1021/cr00028a003

Cited by 80 publications

(41 citation statements)

References 21 publications

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“…[6] In truth, many hydroxo compounds have been adventitiously obtained when traces of water have been present in the reaction media. [7] On the other hand, hydroxo compounds show a strong tendency to form bi-or polynuclear species [7] in which the nucleophilicity of the OH group is decreased because it is bound to several metal atoms. This aggregation takes place when a lone electron pair of an OH group is donated into an empty coordination site of a second molecule.…”

Section: Introductionmentioning

confidence: 99%

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

Cuesta

Gerbino

Hevia

et al. 2004

Chemistry A European J

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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.

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Section: Introductionmentioning

confidence: 99%

“…Indeed, most structurally characterized hydroxo complexes are polynuclear species. [7] However, binuclear complexes with a single OH ligand as the only bridge are quite rare. An example is the cationic complex [{Mo(m 3 -methallyl)(CO) 2 (phen)} 2 (m-OH)]…”

mentioning

confidence: 99%

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

Cuesta

Gerbino

Hevia

et al. 2004

Chemistry A European J

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“…[61] The energy in solution comprises the electronic energy of the polarised solute, the electrostatic solute-solvent interaction energy ϽΨ f |H+½V f |Ψ f Ͼ and the nonelectrostatic terms corresponding to cavitation, dispersion and short range repulsion. A relative permittivity of 8.93 was assumed in the calculations to simulate dichloromethane which was the solvent used experimentally in related reactions between [Re(OH)(CO) 3 (Me 2 -bipy)] and several organic electrophiles. [15][16][17] The computational scheme chosen in this work is similar to that used in a theoretical study on the reactivity of [Re(OH)(CO) 3 -(N 2 C 2 H 4 )] towards phenyl acetate, [45] wherein the validity of the B3LYP mechanistic predictions compared with X-ray experimental data and more sophisticated quantum-chemical computations was confirmed.…”

Section: Methodsmentioning

confidence: 99%

“…In recent years, several groups have started to investigate the chemistry of hydroxo complexes of the central (Groups 6 and 7) transition metals. [4,[13][14][15][16][17][18][19][20][21][22][23] In particular, it has been reported that the hydroxo complex [Re(OH)(CO) 3 (Me 2 -bipy)] (Me 2 -bipy = 4,4Ј-dimethyl-2,2Ј-bipyridine) reacts with a variety of organic electrophiles such as carbon disulfide, esters, aryl isocyanates, alkyl/aryl isothiocyanates, dimethyl acetylenedicarboxylate, ketenes, maleic anhydride and rac-lactide. [15][16][17] Some of these processes evolve through the cleavage of a single C-O bond [15,16] to form metal-carboxylate products which are subsequently demetalated by reaction with triflic acid to afford the corresponding free carboxylic acids.…”

Section: Introductionmentioning

confidence: 99%

A Theoretical Study on the Reactivity of a Rhenium Hydroxo‐Carbonyl Complex Towards β‐Lactams

2008

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The mechanism of the reaction between the complex [Re(OH)(CO) 3 (N 2 C 2 H 4 )] and azetidin-2-one or 3-formylamino-N-sulfonatoazetidin-2-one was investigated by using the B3LYP density functional theory methodology in conjunction with the PCM-UAHF model to take into account solvent effects. According to our calculations, the rate-determining energy barrier for the azetidin-2-one case of 38.8 kcal mol Ϫ1 , becomes 25.7 kcal mol Ϫ1 in the case of the 3-formylamino-Nsulfonatoazetidin-2-one species. The presence of the sul-

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“…It should be noted that terminal hydroxo complexes of Ti(IV) are rather rare. Examples of structurally characterized Ti(IV) terminal hydroxo complexes include those supported by cyclopentadienyl [10][11][12] and a tripodal aminotriphenoxide ligand [13]. The geometry around Ti is pseudo octahedral.…”

Section: X-ray Crystallographymentioning

confidence: 99%

Titanium(IV) terminal hydroxo complexes containing chelating bis(phosphine oxide) ligands

Yi¹,

Williams²,

Leung³

2006

Journal of Organometallic Chemistry

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Structurally Characterized Organometallic Hydroxo Complexes of the f- and d-Block Metals

Cited by 80 publications

References 21 publications

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

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

A Theoretical Study on the Reactivity of a Rhenium Hydroxo‐Carbonyl Complex Towards β‐Lactams

Titanium(IV) terminal hydroxo complexes containing chelating bis(phosphine oxide) ligands

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