Monovalent Group 13 Organometallic Compounds: Weak Association to Monomeric, Versatile Two-Electron Donors

Abstract

A weakly associated hexamer is formed for [GaCp*] (Cp*=C Me ) in the solid state (see picture). The recent X-ray crystal structure analyses of [GaCp*] as well as the monomeric In and Tl compounds [M(2,4,6-Trip C H )] (Trip=2,4,6-iPr C H ) throw new light on the association and aggregation of monovalent Group 13 elements in the solid state. The synthesis of [Ni {In[C(SiMe ) ]} ], a complex with terminally bonded In R ligands, offers alternative σ-donor/π-acceptor ligands to organometallic chemists. The newest results in this area are likely to open up new and intriguing possibilities in the preparation of main group-transition metal clusters.

The [Ga2(C5Me5)]+ Ion: Bipyramidal Double‐Cone Structure and Weakly Coordinated, Monovalent Ga+

“…In this context, Al I and Ga I compounds and metalloid clusters of Group 13 investigated by Schnöckel and co‐workers are considered as milestones 1. 2 The good accessibility of low‐coordinate Ga I organyls such as [GaCp*],3, 4 [Ga(ddp)] (Cp*=C 5 Me 5 ; ddp=2‐{(2,6‐diisopropylphenyl)amino}‐4‐{(2,6‐diisopropylphenyl)imino}‐2‐pentene)5 and GaR (R=C(SiMe 3 ) 3 ,6 Si(SiMe 3 )7) allows inter alia their use as exceptionally electron‐rich carbenoid ligands in organometallic chemistry,8, 9 a field which we have been focusing on for quite some time 10. Aiming at complex cations of the type [M(ECp*) n ] m + , we recently investigated the reaction of [GaCp*] with [M(NCCH 3 ) 6 ][BAr F ] 2 (M=V, Cr, Fe, Co, Ni; BAr F =[B{C 6 H 3 (CF 3 ) 2 } 4 ] 11.…”

[Pd3(InCp*)4(μ2‐InCp*)4]: Three Linearly Arranged Palladium Atoms Wrapped into a Fluxional Shell of Eight InCp* Ligands

“…In 1999 Murugavel and Chandrasekhar stated in a Highlight article in this journal on monovalent Group 13 organometallic compounds that ™the use of these compounds º in transition metal chemistry is likely to have a huge impact on the way new metal±metal bonds are made in the future º and there is no doubt that we will be witnessing the synthesis of a whole range of new cluster types in the future.∫ [1] The monovalent homoleptic complexes [M{EC(SiMe 3 Uhl et al in 1998 [2] and [Ni(GaCp*) 4 ] (Cp* ¼ pentamethylcyclopentadienide) synthesized by [3] confirmed this statement. Hitherto, most of the studies concerning complexes of these new ligands ER (E ¼ Al, Ga, In, R ¼ Alkyl, Aryl), which are isolobal to CO, were focused on the coordination to transition metal carbonyl fragments [(CO) n M a ], [4,5] a chemistry that has also been stimulated by our work on [(CO) 4 Fe(AlCp*)].…”

“…are exceedingly rich sources of bioactive macrolides. [1] Though structurally quite diverse, all ™amphidi-nolides∫ known to date exhibit pronounced cytotoxicity against various cancer cell lines, with some members reaching potencies which rank them amongst the most cytotoxic compounds that are presently known. [2] In contrast to macrolide antibiotics derived from terrestrial microorganisms, the majority of amphidinolides feature an odd-numbered macrolide ring, which raises questions concerning the biosynthesis of these structurally unique secondary metabolites.…”

Das [Ga2(C5Me5)]+‐Ion: bipyramidale Doppelkegelstruktur und schwach koordiniertes, monovalentes Ga+

“…In diesem Sinne gelten insbesondere die von Schnöckel und Mitarbeitern untersuchten Al I ‐ und Ga I ‐Verbindungen und metalloiden Cluster der Gruppe 13 als richtungweisend 1. 2 Die einfache Synthese von Ga I ‐Organylen wie [GaCp*],3, 4 [Ga(ddp)] (Cp*=C 5 Me 5 ; ddp=2‐{(2,6‐Diisopropylphenyl)amino}‐4‐{(2,6‐diisopropylphenyl)imino}‐2‐penten)5 und GaR (R=C(SiMe 3 ) 3 ,6 Si(SiMe 3 )7) ermöglicht ihren Einsatz als elektronenreiche carbenoide Liganden in der Organometallchemie8, 9 – ein Thema, dem wir uns schon seit geraumer Zeit widmen 10. Auf der Suche nach Komplexkationen des Typs [M(ECp*) n ] m + untersuchten wir kürzlich Reaktionen von [GaCp*] mit [M(NCCH 3 ) 6 ][BAr F ] 2 (M=V, Cr, Fe, Co, Ni; BAr F =[B{C 6 H 3 (CF 3 ) 2 } 4 ]) 11.…”