Four-Membered Group 13 Metal(I) N-Heterocyclic Carbene Analogues:  Synthesis, Characterization, and Theoretical Studies

Abstract

The synthesis, spectroscopic and structural characterization of the monomeric, four-membered group 13 metal(I) heterocycles ([:M{eta2-N,N'-(Ar)NC(NCy2)N(Ar)}], M = Ga or In, Ar = C6H3Pri2-2,6) and an isomeric thallium complex are reported. Theoretical studies on these complexes, which are analogues of four-membered N-heterocyclic carbenes, suggest they should act as good sigma-donor ligands.

Synthesis of the Sterically Related Nickel Gallanediyl Complexes [Ni(CO)3(GaAr′)] (Ar′ = C6H3-2,6-(C6H3-2,6-iPr2)2) and [Ni(CO)3(GaL)] (L = HC[C(CH3)N(C6H3-2,6-iPr2)]2): Thermal Decomposition of [Ni(CO)3(GaAr′)] to give the Cluster [Ni4(CO)7(GaAr′)3]

“…The early compounds were stabilized by g 5 -C 5 Me 5 and C(SiMe 3 ) 3 substituents. Later, the range of available examples was further expanded with use of terphenyl [4][5][6] and b-diketiminate and related ligands [7][8][9][10][11]. The ability of these low-valent metal (I) compounds to act as strong terminal or bridging r-donor ligands has been well demonstrated by the experimental studies of Fischer, Jutzi and Uhl and by the theoretical work of Frenking [12][13][14][15][16][17][18][19][20].…”

Platin‐Komplexe mit terminal gebundenen Ga+‐ und In+‐Ionen

“…[1, [3][4][5][6][7] Die s-Donorund p-Acceptoreigenschaften dieser Liganden wurden ausführlich diskutiert (Abbildung 1) und lösten in manchen Fällen nicht wenige Kontroversen aus. [8][9][10] Solche Eigenschaften hängen stark von der Art des Diylsubstituenten R ab; so ist Cp*Ga ein sehr guter sDonor-Ligand, fungiert aber wegen der stark konkurrierenden p-Donoreigenschaften des Cp*-Fragments als schwacher p-Acceptor gegenüber Über-gangsmetallzentren.…”

Recent Developments of Boryl Anions: Boron Analogues of Carbanion

“…) and 13 (Al, 33 Ga, [34][35][36][37][38] In, [38][39][40] and Tl 40,41 ), being isoelectronic to boryl anion with a four-, five-, or six-membered N-heterocyclic skeleton ( Figure 1) inspired us to introduce five-membered ring diamino substituents to stabilize the boryl anion, containing low-valent boron(I) atom, with strong support from theoretical calculation. 42,43 Why is It Difficult to Prepare Boryl Anion?…”