Rahman, A. K. Fazlur; Bennett, Martin A. published the artcile< Protonation of Group 9 Metal (Co, Rh, Ir) Coordinated Bicyclo-[2.2.1]-hepta-2,5-diene and Bicyclo[2.2.2]octa-2,5-diene complexes: Facile Activation of Carbon-Carbon Bond in Bicyclo-[2.2.1]hepta-2,5-diene via M-H or M-H-C interactions>, Related Products of 67421-02-7, the main research area is protonation norbornadiene bicyclooctadiene Group 9 half sandwich bond activation; carbon carbon bond activation protonation cyclopentadienyl cobalt rhodium iridium; crystal mol structure norbornadiene bicyclooctadiene cyclopentadienyl complex.
The activation of C-C bond in coordinated M (η4-bicyclo[2.2.1]heptadiene) (NBD) via protonation for 3d, 4d and 5d transition metals have been examined Monoprotonation of the diolefin complexes [M(η5-C5R5)(η4-NBD)] (R = H, Me; M = Co, Rh), with CF3COOH or CF3SO3H forms transient agostic metal hydrides (M-H-C) at -80°. Similar reaction with HPF6 (60% aqueous), the Ir analogs give terminal hydrides [IrH(η5-C5Me4R)(η4-NBD)][PF6] (R = Me, or Et) as isolable solids at room temperature All these hydride complexes coordinated to NBD subsequently undergo ligand migration to give stable η2-vinyl η3-cyclopentenyl cations [M(η5-C5R5)(C7H9)]+ (M = Co, Rh, Ir). Protonation of the cobalt and rhodium coordinated bicyclo[2.2.2]octa-2,5-diene (BCOD) gives unstable M-H-C ground state structures at -80°, which decompose upon warming to room temperature Protonation reactions of the BCOD complexes of Ir also give terminal hydrides [IrH(η5-C5Me5)(η4-BCOD)][PF6] as solids. Thermolysis of [IrH(η5-C5Me5)(η4-BCOD)][PF6] did not give the expected, isomerized or C-C bond activated product, probably because BCOD is less strained than NBD. Coupling constant [JCH] and stretching frequency [ν M-H] data indicate the electron d. donation from the Me groups in the Cp ring favors agostic structures. The C-C bond activation in the coordinated norbornadiene, via hydride migration is slower for the terminal hydride, M-H (M = Ir) compared to agostic hydrides for (M = Co, Rh) compounds The vinyl cyclopentenyl cations of Rh, Ir undergo further isomerization in CF3COOH to give corresponding η6-toluene cations [M(η5-C5R5)(η6-C6H5CH3)]+. At 50° in vacuo the salt [(η5-C5Me5)Ir(H)(η4-NBD)][PF6] forms a neutral tetramethylfulvenyliridium complex [(η5-C5Me4:CH2)Ir(η4-NBD)] by C-H activation of a Me group in the C5Me5 ring.
Journal of Organometallic Chemistry published new progress about Agostic bond. 67421-02-7 belongs to class chlorides-buliding-blocks, and the molecular formula is C24H36Cl4Ru2, Related Products of 67421-02-7.
Referemce:
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics