{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"submitter":["Alvarez MA"],"funding":["Ministerio de Ciencia e Innovaci??n"],"pagination":["11548-11561"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC8901102"],"repository":["biostudies-literature"],"omics_type":["Unknown"],"volume":["60(15)"],"pubmed_abstract":["The triphosphorus complex [Mo<sub>2</sub>Cp<sub>2</sub>(μ-η<sup>3</sup>:η<sup>3</sup>-P<sub>3</sub>)(μ-P<sup><i>t</i></sup>Bu<sub>2</sub>)] was prepared in 83% yield by reacting the methyl complex [Mo<sub>2</sub>Cp<sub>2</sub>(μ-κ<sup>1</sup>:η<sup>2</sup>-CH<sub>3</sub>)(μ-P<sup><i>t</i></sup>Bu<sub>2</sub>)(μ-CO)] with P<sub>4</sub> at 333 K, a process also giving small amounts of the methyldiphosphenyl complex [Mo<sub>2</sub>Cp<sub>2</sub>(μ-η<sup>2</sup>:η<sup>2</sup>-P<sub>2</sub>Me)(μ-P<sup><i>t</i></sup>Bu<sub>2</sub>)(CO)<sub>2</sub>]. The latter could be better prepared by first reacting the anionic complex Na[Mo<sub>2</sub>Cp<sub>2</sub>(μ-P<sup><i>t</i></sup>Bu<sub>2</sub>)(μ-CO)<sub>2</sub>] with P<sub>4</sub> to give the diphosphorus derivative Na[Mo<sub>2</sub>Cp<sub>2</sub>(μ-η<sup>2</sup>:η<sup>2</sup>-P<sub>2</sub>)(μ-P<sup><i>t</i></sup>Bu<sub>2</sub>)(CO)<sub>2</sub>] and further reaction of the latter with MeI. Density functional theory calculations on the title complex revealed that its triphosphorus group can be viewed as an allylic-like P<sub>3</sub><sup>-</sup> ligand acting as a six-electron donor via the external P atoms, while coordination of the internal P atom involves donation from the π orbital of the ligand and back-donation to its π* orbital, both interactions having a weakening effect on the Mo-Mo and P-P connections. The reactivity of the title compound is dominated by the electron-donor ability associated with the lone pairs located at the P atoms. Its reaction with CF<sub>3</sub>SO<sub>3</sub>Me gave [Mo<sub>2</sub>Cp<sub>2</sub>(μ-η<sup>3</sup>:η<sup>3</sup>-P<sub>3</sub>Me)(μ-P<sup><i>t</i></sup>Bu<sub>2</sub>)](CF<sub>3</sub>SO<sub>3</sub>) as a result of methylation at an external atom of the P<sub>3</sub> ligand, while its reaction with [Fe<sub>2</sub>(CO)<sub>9</sub>] enabled the addition of one, two, or three Fe(CO)<sub>4</sub> fragments at these P atoms, but only the diiron derivative [Mo<sub>2</sub>Fe<sub>2</sub>Cp<sub>2</sub>(μ-η<sup>3</sup>:η<sup>3</sup>:κ<sup>1</sup>:κ<sup>1</sup>-P<sub>3</sub>)(μ-P<sup><i>t</i></sup>Bu<sub>2</sub>)(CO)<sub>8</sub>] could be isolated. This complex bears a Fe(CO)<sub>4</sub> fragment at each of the external atoms of the P<sub>3</sub> ligand, and the central P atom of the latter displays the lowest <sup>31</sup>P chemical shift reported to date (δ<sub>P</sub> -721.8 ppm). The related complexes [Mo<sub>2</sub>M<sub>2</sub>Cp<sub>2</sub>(μ-η<sup>3</sup>:η<sup>3</sup>:κ<sup>1</sup>:κ<sup>1</sup>-P<sub>3</sub>)(μ-P<sup><i>t</i></sup>Bu<sub>2</sub>)(CO)<sub>10</sub>] (M = Mo, W) were prepared by reacting the title compound with the corresponding [M(CO)<sub>5</sub>(THF)] complexes in toluene, while reaction with [Mo(CO)<sub>4</sub>(THF)<sub>2</sub>] also enabled the formation of the heptanuclear derivative [Mo<sub>7</sub>Cp<sub>4</sub>(μ-η<sup>3</sup>:η<sup>3</sup>:κ<sup>1</sup>:κ<sup>1</sup>-P<sub>3</sub>)<sub>2</sub>(μ-P<sup><i>t</i></sup>Bu<sub>2</sub>)<sub>2</sub>(CO)<sub>14</sub>]. The interatomic distances in the above compounds indicate that the central Mo<sub>2</sub>P<sub>3</sub> skeleton of these molecules is little modified by the attachment of 16-electron M(CO)<sub><i>n</i></sub> fragments at the external atoms of the P<sub>3</sub> ligand."],"journal":["Inorganic chemistry"],"pubmed_title":["Electronic Structure and Donor Ability of an Unsaturated Triphosphorus-Bridged Dimolybdenum Complex."],"pmcid":["PMC8901102"],"funding_grant_id":["PGC2018-097366-B-I00"],"pubmed_authors":["Casado-Ruano M","Garcia ME","Ruiz MA","Guerra AM","Alvarez MA","Garcia-Vivo D"],"additional_accession":[]},"is_claimable":false,"name":"Electronic Structure and Donor Ability of an Unsaturated Triphosphorus-Bridged Dimolybdenum Complex.","description":"The triphosphorus complex [Mo<sub>2</sub>Cp<sub>2</sub>(μ-η<sup>3</sup>:η<sup>3</sup>-P<sub>3</sub>)(μ-P<sup><i>t</i></sup>Bu<sub>2</sub>)] was prepared in 83% yield by reacting the methyl complex [Mo<sub>2</sub>Cp<sub>2</sub>(μ-κ<sup>1</sup>:η<sup>2</sup>-CH<sub>3</sub>)(μ-P<sup><i>t</i></sup>Bu<sub>2</sub>)(μ-CO)] with P<sub>4</sub> at 333 K, a process also giving small amounts of the methyldiphosphenyl complex [Mo<sub>2</sub>Cp<sub>2</sub>(μ-η<sup>2</sup>:η<sup>2</sup>-P<sub>2</sub>Me)(μ-P<sup><i>t</i></sup>Bu<sub>2</sub>)(CO)<sub>2</sub>]. The latter could be better prepared by first reacting the anionic complex Na[Mo<sub>2</sub>Cp<sub>2</sub>(μ-P<sup><i>t</i></sup>Bu<sub>2</sub>)(μ-CO)<sub>2</sub>] with P<sub>4</sub> to give the diphosphorus derivative Na[Mo<sub>2</sub>Cp<sub>2</sub>(μ-η<sup>2</sup>:η<sup>2</sup>-P<sub>2</sub>)(μ-P<sup><i>t</i></sup>Bu<sub>2</sub>)(CO)<sub>2</sub>] and further reaction of the latter with MeI. Density functional theory calculations on the title complex revealed that its triphosphorus group can be viewed as an allylic-like P<sub>3</sub><sup>-</sup> ligand acting as a six-electron donor via the external P atoms, while coordination of the internal P atom involves donation from the π orbital of the ligand and back-donation to its π* orbital, both interactions having a weakening effect on the Mo-Mo and P-P connections. The reactivity of the title compound is dominated by the electron-donor ability associated with the lone pairs located at the P atoms. Its reaction with CF<sub>3</sub>SO<sub>3</sub>Me gave [Mo<sub>2</sub>Cp<sub>2</sub>(μ-η<sup>3</sup>:η<sup>3</sup>-P<sub>3</sub>Me)(μ-P<sup><i>t</i></sup>Bu<sub>2</sub>)](CF<sub>3</sub>SO<sub>3</sub>) as a result of methylation at an external atom of the P<sub>3</sub> ligand, while its reaction with [Fe<sub>2</sub>(CO)<sub>9</sub>] enabled the addition of one, two, or three Fe(CO)<sub>4</sub> fragments at these P atoms, but only the diiron derivative [Mo<sub>2</sub>Fe<sub>2</sub>Cp<sub>2</sub>(μ-η<sup>3</sup>:η<sup>3</sup>:κ<sup>1</sup>:κ<sup>1</sup>-P<sub>3</sub>)(μ-P<sup><i>t</i></sup>Bu<sub>2</sub>)(CO)<sub>8</sub>] could be isolated. This complex bears a Fe(CO)<sub>4</sub> fragment at each of the external atoms of the P<sub>3</sub> ligand, and the central P atom of the latter displays the lowest <sup>31</sup>P chemical shift reported to date (δ<sub>P</sub> -721.8 ppm). The related complexes [Mo<sub>2</sub>M<sub>2</sub>Cp<sub>2</sub>(μ-η<sup>3</sup>:η<sup>3</sup>:κ<sup>1</sup>:κ<sup>1</sup>-P<sub>3</sub>)(μ-P<sup><i>t</i></sup>Bu<sub>2</sub>)(CO)<sub>10</sub>] (M = Mo, W) were prepared by reacting the title compound with the corresponding [M(CO)<sub>5</sub>(THF)] complexes in toluene, while reaction with [Mo(CO)<sub>4</sub>(THF)<sub>2</sub>] also enabled the formation of the heptanuclear derivative [Mo<sub>7</sub>Cp<sub>4</sub>(μ-η<sup>3</sup>:η<sup>3</sup>:κ<sup>1</sup>:κ<sup>1</sup>-P<sub>3</sub>)<sub>2</sub>(μ-P<sup><i>t</i></sup>Bu<sub>2</sub>)<sub>2</sub>(CO)<sub>14</sub>]. The interatomic distances in the above compounds indicate that the central Mo<sub>2</sub>P<sub>3</sub> skeleton of these molecules is little modified by the attachment of 16-electron M(CO)<sub><i>n</i></sub> fragments at the external atoms of the P<sub>3</sub> ligand.","dates":{"release":"2021-01-01T00:00:00Z","publication":"2021 Aug","modification":"2025-04-22T10:01:45.848Z","creation":"2025-04-05T23:22:34.313Z"},"accession":"S-EPMC8901102","cross_references":{"pubmed":["34279915"],"doi":["10.1021/acs.inorgchem.1c01552"]}}