CH Activated Isomers of [M(AlCp*)₅] (M=Fe, Ru)

Abstract

Quantum mechanical calculations on the model compounds [Fe(ECH 3 ) 5 ] (E = Al, Ga, In) suggest the existence of the homoleptic, trigonal-bipyramidal d 8 metal complexes of the exotic ligands E

The Mackay‐Type Cluster [Cu43Al12](Cp*)12: Open‐Shell 67‐Electron Superatom with Emerging Metal‐Like Electronic Structure

“…TheA la toms are thus embedded into an almost ideal pentagonal bipyramidal environment between the h 5 -Cp* and the h 5 -Cu 5 face with d CuC-Al of 2.622(3) to 2.655(4) .T hese values are similar to the typical d Cu-Al of the intermetallic solid-state reference compounds CuAl 2 (2.587(4) ) [21] and Cu 9 Al 4 (2.468(2)-2.737 (3)). [22,23] TheAl-Cp* centroid distance of 1.923 is within the expected range, [24][25][26] and only slightly elongated with regards to the smaller cluster [Cu 6 (AlCp*) 6 -(N = CHPh)H 3 ], [27] probably ar esult of the higher steric crowding in case of 1.T he Cu B -Al-Cp* centroid angle of 179.48 8 is almost linear.…”

“…[20] While the lower surface energy of Al with regard to Cu was held responsible for these Cu/Al species,i nt he case of 1,t he symmetric arrangement of the aluminum atoms is certainly strongly influenced by the steric demand of the Al-bound Cp* ligand. [22,23] TheAl-Cp* centroid distance of 1.923 is within the expected range, [24][25][26] and only slightly elongated with regards to the smaller cluster [Cu 6 (AlCp*) 6 -(N = CHPh)H 3 ], [27] probably ar esult of the higher steric crowding in case of 1.T he Cu B -Al-Cp* centroid angle of 179.48 8 is almost linear. [22,23] TheAl-Cp* centroid distance of 1.923 is within the expected range, [24][25][26] and only slightly elongated with regards to the smaller cluster [Cu 6 (AlCp*) 6 -(N = CHPh)H 3 ], [27] probably ar esult of the higher steric crowding in case of 1.T he Cu B -Al-Cp* centroid angle of 179.48 8 is almost linear.…”

Synthesis and Characterization of the Novel AlI Compound Al(C5Me4Ph): Comparison of the Coordination Chemistry of Al(C5Me5) and Al(C5Me4Ph) at d10 Metal Centers1)

“…In contrast to the related Ga and In chemistry, the coordination of AlCp* to a transition metal centers causes the Al centre to become very electrophilic and prone to subsequent reactions. Thus, the reaction of [Ni(cod) 2 ] with AlCp* in benzene does neither lead to homoleptic monomeric [Ni(AlCp*) 4 ] nor cluster structures [Ni a (AlCp*) b ], but instead yields a new complex of the formula [Ni(AlCp*) 3 {AlCp*(Ph)}(H)] by C-H activation of the solvent [9]. The product was shown to be formed via the reactive intermediate [Ni(AlCp*) 3 ].…”

Der Mackay‐Cluster [Cu43Al12](Cp*)12: Ein offenschaliges 67‐Elektronen‐Superatom mit metallähnlicher elektronischer Struktur

“…[20] Während die niedrigere Oberflächenenergie von Al im Vergleich zu Cu fürl etzteres verantwortlich gemacht wurde,w ird im Fall von 1 die symmetrische Anordnung der Aluminiumatome sicherlich stark durch den sterischen Anspruch des Al-gebundenen Cp*-Liganden beeinflusst. -Abstand von 1.923 liegt im erwarteten Bereich [24][25][26] und ist nur wenig länger als im kleineren Cluster [Cu 6 (AlCp*) 6 (N= CHPh)H 3 ]. Diese Werte sind den typischen d Cu-Al -Abständen in den intermetallischen Festkçrper-Referenzverbindungen CuAl 2 (2.587(4) ) [21] und Cu 9 Al 4 (2.468(2)-2.737(3)) ähnlich.…”

“…[22,23] Der Al-Cp* centr. -Abstand von 1.923 liegt im erwarteten Bereich [24][25][26] und ist nur wenig länger als im kleineren Cluster [Cu 6 (AlCp*) 6 (N= CHPh)H 3 ]. [27] Dies liegt vermutlich am insgesmt grçßeren sterischen Anspruch in Verbindung 1.D er Winkel Cu B -Al-Cp* centr.…”