Fluxionality in (BH4)Mn(CO)4 and (BH4)Cu(PH3)2

Theoretical study on interaction of different coordination modes of BH4 ligand with transition metal in [TM(BH4)(CO)4]− (TM = Cr, Mo)

“…From computed structures, we find a positive value for R in all calculations (Table 12). These positive values support an I d mechanism rather than I a , which reported earlier [30,33]. This result is consistent with general rule in substitution reactions of organometallic compounds that favors mainly disociative mechanisms [34,35].…”

Theoretical study on interaction of different coordination modes of BH4 ligand with transition metal in [TM(BH4)(CO)4]− (TM = Cr, Mo)

“…From computed structures, we find a positive value for R in all calculations (Table 12). These positive values support an I d mechanism rather than I a , which reported earlier [30,33]. This result is consistent with general rule in substitution reactions of organometallic compounds that favors mainly disociative mechanisms [34,35].…”

Hydride Exchange Processes in the Coordination Sphere of Transition Metal Complexes: The OsH 3 (BH 4 )(PR 3 ) 2 System

“…Both our result and the qualitative reasoning just presented support strongly the feasibility of the dissociative pathway for the exchange mechanism between bridging and terminal hydrogen atoms of the BH 4 ligand in the OsH 3 (BH 4 )(PR 3 ) 2 system. Contradiction between this result and those proposing an associative pathway for the (BH 4 )Mn(CO) 4 and (BH 4 )Cu(PH 3 ) 2 systems is only an illusion, since we feel that the differences can be traced back to the diverse electron counting of the complexes. Apart from the change in the coordination mode of tetrahydroborate, the structure of 3 is quite similar to that of 1 .…”

Chelating Phosphane–Boranes as Hemilabile Ligands – Synthesis of[Mn(CO)3(η2‐H3B·dppm)][BArF4] and [Mn(CO)4(η1‐H3B·dppm)][BArF4]

“…[29] Related complexes with monodentate phosphanes such as [Mn(CO) 4 [20] are also unstable in solution. The stability of 2 is doubtlessly associated with the chelate ring, as we have commented on previously.…”

Theoretical study on interaction of different coordination modes of BH4 ligand with transition metal in [TM(BH4)(CO)4]− (TM = Cr, Mo)

“…From computed structures, we find a positive value for R in all calculations (Table 12). These positive values support an I d mechanism rather than I a , which reported earlier [30,33]. This result is consistent with general rule in substitution reactions of organometallic compounds that favors mainly disociative mechanisms [34,35].…”

Hydride Exchange Processes in the Coordination Sphere of Transition Metal Complexes: The OsH 3 (BH 4 )(PR 3 ) 2 System

“…Both our result and the qualitative reasoning just presented support strongly the feasibility of the dissociative pathway for the exchange mechanism between bridging and terminal hydrogen atoms of the BH 4 ligand in the OsH 3 (BH 4 )(PR 3 ) 2 system. Contradiction between this result and those proposing an associative pathway for the (BH 4 )Mn(CO) 4 and (BH 4 )Cu(PH 3 ) 2 systems is only an illusion, since we feel that the differences can be traced back to the diverse electron counting of the complexes. Apart from the change in the coordination mode of tetrahydroborate, the structure of 3 is quite similar to that of 1 .…”

Chelating Phosphane–Boranes as Hemilabile Ligands – Synthesis of[Mn(CO)3(η2‐H3B·dppm)][BArF4] and [Mn(CO)4(η1‐H3B·dppm)][BArF4]

“…[29] Related complexes with monodentate phosphanes such as [Mn(CO) 4 [20] are also unstable in solution. The stability of 2 is doubtlessly associated with the chelate ring, as we have commented on previously.…”

Theoretical study on interaction of different coordination modes of BH4 ligand with transition metal in [TM(BH4)(CO)4]− (TM = Cr, Mo)

“…From computed structures, we find a positive value for R in all calculations (Table 12). These positive values support an I d mechanism rather than I a , which reported earlier [30,33]. This result is consistent with general rule in substitution reactions of organometallic compounds that favors mainly disociative mechanisms [34,35].…”

Hydride Exchange Processes in the Coordination Sphere of Transition Metal Complexes: The OsH 3 (BH 4 )(PR 3 ) 2 System

“…Both our result and the qualitative reasoning just presented support strongly the feasibility of the dissociative pathway for the exchange mechanism between bridging and terminal hydrogen atoms of the BH 4 ligand in the OsH 3 (BH 4 )(PR 3 ) 2 system. Contradiction between this result and those proposing an associative pathway for the (BH 4 )Mn(CO) 4 and (BH 4 )Cu(PH 3 ) 2 systems is only an illusion, since we feel that the differences can be traced back to the diverse electron counting of the complexes. Apart from the change in the coordination mode of tetrahydroborate, the structure of 3 is quite similar to that of 1 .…”

Chelating Phosphane–Boranes as Hemilabile Ligands – Synthesis of[Mn(CO)3(η2‐H3B·dppm)][BArF4] and [Mn(CO)4(η1‐H3B·dppm)][BArF4]

“…[29] Related complexes with monodentate phosphanes such as [Mn(CO) 4 [20] are also unstable in solution. The stability of 2 is doubtlessly associated with the chelate ring, as we have commented on previously.…”