Alkenyl Derivatives of the Unsaturated Dimolybdenum Hydride Complex [Mo₂(η⁵-C₅H₅)₂(μ-H)(μ-PCy₂)(CO)₂]

Abstract

The 30-electron hydride complex [Mo 2 Cp 2 (µ-H)(µ-PCy 2 )(CO) 2 ] reacts at room temperature with p-tolylacetylene to give the unsaturated σ:π-bonded alkenyl derivatives trans-[Mo 2 Cp 2 (µ-η 1 :η 2 -CRCH 2 )-(µ-PCy 2 )(CO) 2 ] and trans-[Mo 2 Cp 2 (µ-η 1 :η 2 -CHCHR)(µ-PCy 2 )(CO) 2 ] (R ) ptol; Cp ) η 5 -C 5 H 5 ), with the R-substituted alkenyl complex being transformed completely into its -substituted isomer slowly at room temperature. In solution, both compounds exhibit an isomeric equilibrium (rapid on the NMR time scale) involving the alternate π-binding of the alkenyl ligand to each of the metal centers. In addition, the presence of CO allows the partial conversion of the R-substituted complex into its cis-dicarbonyl isomer cis-[Mo 2 Cp 2 (µ-η 1 :η 2 -CRCH 2 )(µ-PCy 2 )(CO) 2 ], so as to reach a roughly equimolar equilibrium ratio. In contrast, the -substituted alkenyl complex experiences full carbonylation under the same conditions to give the tricarbonyl complex [Mo 2 Cp 2 {µ-η 1 :η 2 -CHCHR}(µ-PCy 2 )(CO) 3 ], but similarly displaying a cisoid arrangement of the Cp ligands. The title hydride complex also reacts at room temperature with methyl propiolate, to afford the R-alkenyl complexes cis-and trans-[Mo 2 Cp 2 {µ-η 1 :η 2 -C(CO 2 Me)CH 2 }-(µ-PCy 2 )(CO) 2 ], which are in a solvent-dependent equilibrium and are also involved in further dynamic processes derived from the flipping of the alkenyl ligand, but do not undergo R-alkenyl isomerization. This reaction also gives smaller amounts of the 30-electron alkenylphosphine complex [Mo 2 Cp 2 {µ-κ 1 : η 2 -Cy 2 PCHCH(CO 2 Me)}(CO) 2 ] (Mo-Mo ) 2.526(2) Å), formed through a reductive elimination between the alkenyl and dicyclohexylphosphide ligands. The title hydride complex also reacts at room temperature with an internal alkyne such as dimethylacetylenedicarboxylate to give alkenyl derivatives, but now the unsaturation of the metal center induces the coordination of one of the oxygen atoms of the carboxylate group in the -position to give three different C,C,O-bonded isomers of the electron-precise [Mo 2 Cp 2 -{µ-η 1 ,κ: 2 -C(CO 2 Me)CH(CO 2 Me)}(µ-PCy 2 )(CO) 2 ], all of them characterized through single-crystal X-ray diffraction studies. Two of these isomers, which are in a slow equilibrium in solution, display a similar transoid arrangement of the CO and Cp ligands, but have different relative arrangements of the alkenyl and phosphide bridges, implying transoid or cisoid positions of the metal-bound P and O atoms, respectively. The third isomer displays a cisoid arrangement of the Cp and CO ligands, but a transoid position of the metal-bound P and O atoms. All three isomers exhibit relatively large intermetallic separations (ca. 2.88-2.96 Å), as expected for molecules having single Mo-Mo bonds.

Reactivity of the 30-electron dimolybdenum anion [Mo2(η5-C5H5)2(μ-PCy2)(μ-CO)2]− towards β,γ-unsaturated organic halides: Alkenyl, allenyl and alkoxycarbyne derivatives

“…These values are analogous to those found for the related alkenyl compounds mentioned above [4] and are also consistent with the formulation of a metal-metal double bond for these compounds. The 1 H and 13 C NMR spectra are also in good agreement with the presence in each case of a single species in solution having no symmetry elements.…”

“…Thus, compounds 2a-d all exhibit separate resonances for the inequivalent Cp ( 1 H, 13 C), CO ( 13 C) and Cy groups (twelve different signals in the 13 C NMR spectra). The chemical shifts and coupling constants of these resonances (Table 1 and experimental section) are comparable to those measured for the above mentioned alkenyl complexes trans-[Mo 2 Cp 2 (lg 1 :g 2 -CRCHR')(l-PCy 2 )(CO) 2 ] (R, R 0 = H, ptol, CO 2 Me) [4], and therefore deserve no further comments. Table 1 Selected IR a and NMR b spectroscopic data for new compounds.…”

“…1 h at room temperature. We note that the carbonylation reaction of the related complex trans-[Mo 2 Cp 2 {l-g 1 :g 2 -CHCH(ptol)}(l-PCy 2 )(CO) 2 ] to give an analogous tricarbonyl derivative requires 24 h for completion [4], a difference possibly reflecting the higher protection of the unsaturated center provided by the ptol substituent.…”

“…The spectroscopic data for compounds 2a-d are comparable to those of the alkenyl complexes trans-[Mo 2 Cp 2 (l-g 1 :g 2 -CRCHR')(l-PCy 2 )(CO) 2 ] (R, R' = H, ptol, CO 2 Me), recently prepared by us through the reaction of the unsaturated hydride [Mo 2 Cp 2 (l-H)(l-PCy 2 )(CO) 2 ] with the pertinent 1-alkynes [4]. The solution structure of the latter compounds has been discussed at length already, and therefore only the relevant details for compounds 2a-d will be discussed here.…”

Alkyne to carbyne coupling reactions of the unsaturated methoxycarbyne-bridged complex [Mo2(η5-C5H5)2(μ-COMe)(μ-PCy2)(CO)2]

“…Such a circumstance is readily apparent in the corresponding IR spectrum, now displaying two CÀO stretching bands of strong and weak relative intensities (in order of decreasing frequency), as expected for a Mo 2 (CO) 2 oscillator with carbonyl ligands almost parallel to each other, and crystallographically verified for the related C,C,O-bonded alkenyl complex cis-[Mo 2 Cp 2 {l-g 1 ,j:g 2 -C(CO 2-Me)CH(CO 2 Me)}(l-PCy 2 )(CO) 2 ] [15]. In this sort of structure, the Cp ligands are placed close to the intermetallic axis, and the carbonyl ligands are almost perpendicular to that axis.…”