Abstract:We have synthesized and characterized the monomeric diiminophosphinate-stabilized group 13 metal(I) complexes [ Dip LE:], Dip L = Ph 2 P(NDip) 2 , Dip = 2,6-iPr 2 C 6 H 3 ; E = Ga (1), In (2) and Tl (3). In addition, we structurally characterized the dimeric complex [( Dip LGa) 2 ], 1 2 . Similar synthetic attempts using Mes L = Ph 2 P(NMes) 2 , Mes = 2,4,6-Me 3 C 6 H 2 afforded product mixtures from which the mixed oxidation state species [( Mes L) 3 2 ], E = Al-Tl, shed light on the bonding in these compounds and show that the newly formed E-E bonding interactions can be described as weak single σ-bond with no significant π-bonding contribution for E = Al, Ga. A large contribution to the dimer binding enthalpies results from London dispersion forces.

We have prepared the new aminophosphine Ph2PNHMes 2 [Mes = mesityl (2,4,6‐Me3C6H2)], and the aminoiminophosphorane Ph2P(=NMes)NHMes 4 (MesLH), and obtained the new alkali metal complexes [(DipLLi)2] 5 [DipL = Ph2P(NDip)2, Dip = 2,6‐iPr2C6H3], [(MesLLi)2] 6, [(DipL)(DipN2L)Li2] 7 [DipN2L = Ph2P(NDip)(N3Dip)], [(DipN2L)2Li2] 8, [DipLLi(THF)] 9, [DipLLi(THF)2] 10, [(DipLNa)2] 11, [(MesLNa)n] 12, [DipLNa(THF)2] 13, [{MesLNa(THF)}2] 14 and [MesLK] 16 by deprotonation of their respective ligand precursors with standard strong alkali metal bases in various solvents. The crystal structures of 2, 4–6, 7·8, 9–14, and 16 are reported. The different coordination modes in their solid‐state structures are discussed and generally compared to the solution behavior of those species.